Anionic synthesis of well‐defined,poly[(styrene)‐block‐(propylene oxide)] block copolymers

Well‐defined, narrow molecular weight distribution (M_w/M_n ≤ 1.1) poly[(styrene)‐block‐(propylene oxide)] block copolymers with relatively high molecular weight poly(propylene oxide) blocks [e. g. M_n (PPO) = 10 000–12 000 g/mol] have been prepared by anionic polymerization. The polystyrene block (M_n = 5 000; M_w/M_n = 1.1) was prepared by alkyllithium‐initiated polymerization of styrene followed by chain‐end functionalization with ethylene oxide and protonation with acidic methanol. The resulting ω‐hydroxyl‐functionalized polystyrene was converted to the corresponding alkali metal salts with alkali metals (Na/K alloy, Rb, Cs) and then used to initiate block polymerization of propylene oxide in tetrahydrofuran. The effects of crown ethers (18‐crown‐6 and dicyclohexano‐24‐crown‐8) and added dimethylsulfoxide were investigated. Chain transfer to the monomer resulted in significant amounts of poly(propylene oxide) formation (50%); however, the diblock molecular weight distributions were narrow. The highest molecular weight poly(propylene oxide) blocks (12 200 g/mol) were obtained in tetrahydrofuran with cesium as counterion without additives.     

The Aggregation Behavior of Poly(ethylene oxide)‐Poly(methyl methacrylate) Diblock Copolymers in Organic Solvents

Poly(ethylene oxide)‐poly(methyl methacrylate) and poly(ethylene oxide)‐poly(deuteromethyl methacrylate) block copolymers have been prepared by group transfer polymerization of methyl methacrylate (MMA) and deuteromethyl methacrylate (MMA‐d₈), respectively, using macroinitiators containing poly(ethylene oxide) (PEO). Static and dynamic light scattering and surface tension measurements were used to study the aggregation behavior of PEO‐PMMA diblock copolymers in the solvents tetrahydrofuran (THF), acetone, chloroform, N,N‐dimethylformamide (DMF), 1,4‐dioxane and 2,2,2‐trifluoroethanol. The polymer chains are monomolecularly dissolved in 1,4‐dioxane, but in the other solvents, they form large aggregates. Solutions of partially deuterated and undeuterated PEO‐PMMA block copolymers in THF have been studied by small‐angle neutron scattering (SANS). Generally, large structures were found, which cannot be considered as micelles, but rather fluctuating structures. However, ¹H NMR measurements have shown that the block copolymers form polymolecular micelles in THF solution, but only when large amounts of water are present. The micelles consist of a PMMA core and a PEO shell.     

Synthesis and Characterization of Amphiphilic Poly(ethylene oxide)‐block‐poly(hexyl methacrylate) Copolymers

We describe the preparation of amphiphilic diblock copolymers made of poly(ethylene oxide) (PEO) and poly(hexyl methacrylate) (PHMA) synthesized by anionic polymerization of ethylene oxide and subsequent atom transfer radical polymerization (ATRP) of hexyl methacrylate (HMA). The first block, PEO, is prepared by anionic polymerization of ethylene oxide in tetrahydrofuran. End capping is achieved by treatment of living PEO chain ends with 2‐bromoisobutyryl bromide to yield a macroinitiator for ATRP. The second block is added by polymerization of HMA, using the PEO macroinitiator in the presence of dibromobis(triphenylphosphine) nickel(II), NiBr₂(PPh₃)₂, as the catalyst. Kinetics studies reveal absence of termination consistent with controlled polymerization of HMA. GPC data show low polydispersities of the corresponding diblock copolymers. The microdomain structure of selected PEO‐block‐PHMA block copolymers is investigated by small angle X‐ray scattering experiments, revealing behavior expected from known diblock copolymer phase diagrams.

SAXS diffractograms of PEO‐block‐PHMA diblock copolymers with 16, 44, 68 wt.‐% PEO showing spherical (A), cylindrical (B), and lamellae (C) morphologies, respectively.     

Radical telomerization of vinyl acetate with chloroform. Application to the synthesis of poly(vinyl acetate)‐block‐polystyrene copolymers by consecutive telomerization and atom transfer radical polymerization

This paper demonstrates that radical telomerization and atom transfer radical polymerization (ATRP) can be combined in a two‐step procedure to prepare poly‐(vinyl acetate)‐block‐polystyrene (PVOAc‐b‐PSt) diblock copolymers. The first step consists in telomerizing VOAc with chloroform, leading to trichloromethyl‐terminated VOAc telomers CCl₃(VOAc)_nH. A detailed ¹H NMR analysis shows that nearly pure telomer structures are obtained over a broad range of DP_n values (up to at least 60 units). When ATRP of styrene is initiated with a model telomer adduct (CCl₃CH₂CH₂OAc), molecular weights increase linearly with monomer conversion and match theoretical values. Moreover, polydispersities are consistently low (1.22 < M_w/M_n < 1.38) throughout polymerization. Similarly, VOAc telomers (DP_n = 9 and 62) are good ATRP macroinitiators. The high purity of the resulting diblock copolymers is confirmed by GPC using RI/UV dual detection.     

SET‐LRP Synthesis of Well‐Defined Light‐Responsible Block Copolymer Micelles

Herein, the synthesis of well‐defined light‐sensitive amphiphilic diblock copolymers consisting of UV‐responsive poly(2‐nitrobenzyl acrylate) (PNBA) and hydrophilic poly(ethylene oxide) (PEO) blocks is reported. This is achieved by a single electron transfer living radical polymerization (SET‐LRP) of 2‐nitrobenzyl acrylate monomer initiated by PEO‐containing macroinitiator. Despite several reports on PEO‐b‐PNBA copolymers, this is the first time the PNBA block is synthesized by a controlled radical polymerization leading to the copolymers with low dispersity (Ð = 1.10). In water, the copolymers self‐assemble into well‐defined micelles with a hydrodynamic diameter of 25 nm. Upon irradiation with UV‐light, the PNBA units degrade to hydrophilic poly(acrylate) resulting in disassembly of the micelles. Considering the robustness of the reported synthetic protocol, the prepared polymers represent an interesting platform for the construction of new stimuli‐responsive drug delivery systems.     

Calcium Alcoholates of Hydroxytelechelic Poly(ethylene oxide)s as Initiators for the Ring‐Opening Polymerization of 3‐(S)‐Isopropylmorpholine‐2,5‐dione

Block copolymers with poly[3‐isopropylmorpholine‐2,5‐dione] (PIPMD) and poly(ethylene oxide) (M̄_n = 6 000, PEO) blocks, PIPMD‐b‐PEO‐b‐PIPMD, were synthesized via the ring‐opening polymerization of 3‐(S)‐isopropylmorpholine‐2,5‐dione (IPMD) in the presence of the calcium alcoholate of hydroxytelechelic poly(ethylene oxide) as an initiator at 140°C within 24 or 96 h. The number‐average molecular weight (M̄_n) of the resulting copolymers increases with increasing IPMD content in the feed and with reaction time. According to ¹H NMR spectroscopic analysis, about 40% of IPMD is racemized during polymerization within 96 h at 140°C, while about 12% is racemized within 24 h. The melting temperature of the PEO block upon first heating is lower than that of pure PEO homopolymer, and the melting endotherm decreases with increasing length of the PIPMD block upon second heating.     

Tunable Arrangement of Gold Nanoparticles in Epoxidated Poly(styrene‐block‐butadiene) Diblock Copolymer Matrices

A new approach to synthesize block‐copolymer‐mediated/gold nanoparticle (Au NP) composites is developed. Stable and narrowly distributed Au NPs modified with a 2‐phenylethanethiol ligand are prepared by a two‐phase liquid–liquid method. A new epoxidation of a poly(styrene‐block‐butadiene) diblock copolymer, to form poly(styrene‐block‐vinyl oxirane) (PS‐b‐PBO), is achieved through chemical modification. It is found that the Au NPs disperse well in the PS block segment by partially crosslinking the PBO block segment with poly(ethylene oxide bisamine) (D230), a curing agent. The aggregation of Au NPs leads to a red‐shift of the plasmon absorption with the increase in the D230 content. However, without crosslinking the PBO block segment with D230, Au NPs distributes in both the PS and PBO segments.     

Association Behavior between End‐Functionalized Block Copolymers PEO‐PPO‐PEO and Poly(acrylic acid)

Summary: The end groups of ABA‐triblock copolymers HO–PEO–PPO–PEO–OH, (PEO – poly(ethylene oxide), PPO – poly(propylene oxide)), have been modified with ammonia, ethylene diamine and linear polyethylenimine (LPEI) by substitution of the α,ω‐ditosyl ester of the triblock copolymer (TsO–PEO–PPO–PEO–OTs) with amines, or by the hydrolysis of the corresponding poly(2‐methyl‐2‐oxazoline) (PMeOx) containing ABCBA block copolymers. The latter block copolymer structures have been obtained by the polymerization of MeOx using TsO–PEO–PPO–PEO–OTs as a macro‐initiator. Adding poly(acrylic acid) (PAA) to these (poly)amine terminated block copolymers leads to the formation of networks through a combination of PAA–PEO hydrogen bonding and PAA–(poly)amine acid‐base reaction. Depending on the number of amino groups at both chain ends of the block copolymer, the corresponding complexes behave as liquids, gels or precipitates. Introduction of as little as 1–5 wt.‐% block copolymers H₂N–PEO–PPO–PEO–NH₂ or H₂NCH₂CH₂NH–PEO–PPO–PEO–NHCH₂CH₂NH₂ to the system of HO–PEO–PPO–PEO–OH/PAA leads to viscous liquids with strong shear‐thickening behavior.

Reversible gel formation via the ternary PAA/HO–PEO–PPO–PEO–OH/H₂N–PEO–PPO–PEO–NH₂ system under shear conditions.     

Synthesis of amphiphilic star-shaped and graft copolymers based on polystyrene and poly(ethylene oxide)

Amphiphilic block macromonomers possessing a central unsaturation were synthesized by condensation of polystyrene half-ester of maleic acid {α-[2-(3-carboxyacryloyloxy)ethyl]-ω-sec-butylpoly[1-phenylethylene]} with poly(ethylene glycol) monoether or polystyrene-block-poly(ethylene oxide). In the radical monomer cis-trans-isomerization homopolymerization of the diblock macromonomers, four-to eight-armed amphiphilic star-shaped copolymers were obtained. Radical copolymerization of the diblock macromonomers with styrene led to graft copolymers with low degree of grafting. The triblock macromonomers proved to be unable to polymerize.     

Synthesis and Characterization of Poly(trimethylene oxide)‐block‐Polystyrene and Poly(trimethylene oxide)‐block‐Polystyrene‐block‐Poly(methyl methacrylate) by Combination of Atom Transfer Radical Polymerization (ATRP) and Cationic Ring‐Opening Polymerization (CROP)

Summary: Diblock copolymers, poly(trimethylene oxide)‐block‐poly(styrene)s abbreviated as poly(TMO)‐block‐poly(St), and triblock copolymers, poly(TMO)‐block‐poly(St)‐block‐poly(MMA)s (MMA = methyl methacrylate), with controlled molecular weight and narrow polydispersity have been successively synthesized by a combination of atom transfer radical polymerization (ATRP) and cationic ring‐opening polymerization using the bifunctional initiator, 2‐hydroxylethyl α‐bromoisobutyrate, without intermediate function transformation. The gel permeation chromatography (GPC) and NMR analyses confirmed the structures of di‐ and triblock copolymers obtained.

GPC curves of (a) poly(St); (b) diblock copolymer, poly(St)‐block‐poly(MMA) before precipitation; (c) poly(St)‐block‐poly(MMA) after precipitation in cyclohexane/ethanol (2:1); (d) triblock copolymer, poly(TMO)‐block‐poly(St)‐block‐poly(MMA).     

β‐Cyclodextrin‐Based Star Amphiphilic Copolymers: Synthesis,Characterization, and Evaluation as Artificial Channels

14‐arm amphiphilic star copolymers are synthesized according to different strategies. First, the anionic ring polymerization of 1,2‐butylene oxide (BO) initiated by per(2‐O‐methyl‐3,6‐di‐O‐(3‐hydroxypropyl))‐β‐CD (β‐CD’OH₁₄) and catalyzed by t‐BuP₄ in DMF is investigated. Analyses by NMR and SEC show the well‐defined structure of the star β‐CD’‐PBO₁₄. To obtain a 14‐arm poly(butylene oxide‐b‐ethylene oxide) star, a Huisgen cycloaddition between an α‐methoxy‐ω‐azidopoly(ethylene oxide) and the β‐CD’‐PBO₁₄,whose end‐chains are beforehand alkyne‐functionalized, is performed. In parallel, 14‐arm star copolymers composed of butylene oxide‐b‐glycidol arms are successfully synthesized by the anionic polymerization of ethoxyethylglycidyl ether (EEGE) initiated by β‐CD’‐PBO₁₄ with t‐BuP₄. The deprotection of EEGE units is then performed to provide the polyglycidol blocks. These amphiphilic star polymers are evaluated as artificial channels in lipid bilayers. The effect of changing a PEO block by a polyglycidol block on the insertion properties of these artificial channels is discussed.     

Protection and Polymerization of Functional Monomers, 31. Living Anionic Polymerization of Styrene Derivatives m,m′‐Disubstituted with Acetal‐Protected Monosaccharide Residues

Two new styrene derivatives m,m′‐disubstituted with acetal‐protected monosaccharide residues, 3,5‐bis(1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose‐3‐oxymethyl)styrene ( 1 ) and 3,5‐bis(1,2:3,4‐di‐O‐isopropylidene‐α‐D ‐galactopyranose‐6‐oxymethyl)styrene ( 2 ) were synthesized viahigh yielding eight reaction steps starting from isophthalic acid. Their anionic polymerizations were carried out with sec‐BuLi in THF at –78°C for 30 min. Both monomers, 1 and 2 , were found to undergo living anionic polymerization to afford quantitatively the polymers of predictable molecular weights and narrow molecular weight distributions (M̄_w/M̄_n < 1.08). Novel AB and BA diblock copolymers of 1 and styrene were also successfully synthesized. Complete deprotection of the acetal protective groups by treatment with trifluoroacetic acid was achieved to quantitatively regenerate D ‐glucose and D ‐galactose. The resulting polymers were highly water‐soluble polymers as expected.     

Novel Polyesteramide‐Based Diblock Copolymers: Synthesis by Ring‐Opening Copolymerization and Characterization

Block copolymers based on a polyesteramide sequence and a polyether block were synthesized in bulk at 250 °C by ring‐opening copolymerization (ROP) of ε‐caprolactone (CLo) and ε‐caprolactam (CLa) as initiated by Jeffamine® M1000, i.e., ω‐NH₂ copoly[(ethylene oxide)‐co‐(propylene oxide)] copolymer [P(EO‐co‐PO)‐NH₂]. For an initial molar ratio of [CLa]₀/[CLo]₀ = 1, the copolymerization allowed for the formation of a diblock copolymer with a statistical polyesteramide sequence, as evidenced by ¹³C NMR. Investigation of the ROP mechanism highlighted that CLo was first polymerized, leading to the formation of a diblock copolymer P(EO‐co‐PO)‐b‐PCLo‐OH, followed by CLa hydrolysis to aminocaproic acid that inserted into the ester bonds of PCLo via aminolysis and subsequent condensation reactions. The outcome is the selective formation of P(EO‐co‐PO)‐b‐P(CLa‐co‐CLo)‐OH diblock copolymers where the composition and length of the polyesteramide sequence can be fine‐tuned by the [CLa]₀/[CLo]₀ and ([CLa]₀ + [CLo]₀)/[P(EO‐co‐PO)‐NH₂]₀ initial molar ratios.     

Micro‐ and Macrophase Separation in Phenolic Resol Resin/PEO‐PPO‐PEO Block Copolymer Blends: Effect of Hydrogen‐Bonded PEO Length

We demonstrate microphase‐separated thermosets based on blends of phenolic resol resin and poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐PPO‐PEO), i. e., so‐called Pluronics. Three triblock copolymers are used (PE 9200, PE 10300 and PE 9400) where the molecular weights of the PPO blocks are nearly equal and the weight fractions of the PEO blocks f_PEO are 0.20, 0.30 and, 0.40, respectively. The blends are prepared in a particularly straightforward way using aqueous solutions and thermal crosslinking. Structure formation is characterized using transmission electron microscopy and small‐angle X‐ray scattering. PPO turns out to be sufficiently repulsive to allow microphase separation in the bulk crosslinked phase and the tendency for macrophase separation upon curing is reduced due to the hydrogen bonding between the PEO and resol. The weight fraction of PEO‐PPO‐PEO in the present blends has been limited to a relatively small value, i. e., 20 wt.‐%, and spherical microphase‐separated structure is observed for f_PEO = 0.40 with a long period of the order 120 Å. Macrophase separation manifests upon curing if the weight fraction of the PEO blocks is smaller, i. e., f_PEO = 0.30 or f_PEO = 0.20. In addition, in order to prevent macrophase separation, the molecular weights of PEO blocks and resol resin before curing are of the same order. In that respect, the system behaves qualitatively similar to the corresponding thermoplastic homopolymer/block copolymer blends.     

Living coordination polymerization of end‐allenyloxy poly(ethylene glycol) macromonomer by a π‐allylnickel catalyst

The living coordination polymerization of end‐allenyloxy poly(ethylene oxide)s ( 2A – 2C ) was carried out by [(η³‐allyl)NiOCOCF₃]₂ ( 1 ) in the presence of PPh₃ to produce narrowly dispersed polyallenes bearing poly(ethylene oxide) side chains. For instance, the polymerization of 2B (M_n = 590, [ 2 ]/[ 1 ] = 100) proceeded smoothly to give a polymer (M_n = 39 800, M_w/M_n = 1.13) in high yield. The molecular weight of poly( 2 ) could be controlled by the ratio of 2 to 1 and by the molecular weight of 2 . The block copolymers of 2B with various alkoxyallenes ( 3A – 3C ) or with 1‐phenylethyl isonitrile ( 3D ) were also obtained by the two‐stage copolymerization process (i. e., the polymerization of 2 , followed by that of 3A – 3D ). The resulting block copolymers were found to serve as polymeric surfactants in the polymer blend systems of PSt and PMMA.     

Copolymerization of ethylene and styrene with a MgCl2‐supported CpTiCl3 catalyst

Copolymerization of ethylene and styrene was carried out with CpTiCl₃/MgCl₂‐PMAO as a catalyst at various temperatures and comonomer concentrations. The present catalyst system produces a pseudorandom copolymer of ethylene and styrene beside syndiotactic poly(styrene) (sPS) and poly(ethylene) (PE). The copolymers were obtained at temperature ⪈60°C, indicating the active species promoting the copolymerization being formed at elevated temperatures. On the other hand, styrene incorporation in the copolymer increases progressively with the increase of styrene concentration.     

Study of the compatibility of poly[(styrene)‐co‐ (4‐vinylbenzoic acid)] with poly[(ethyl methacrylate)‐co‐(4‐vinylpyridine)] blends

Binary systems of poly[(ethyl methacrylate)‐co‐(4‐vinylpyridine)] (12.5 mol‐%), PEMAVP‐13, with poly[(styrene)‐co‐4‐(vinylbenzoic acid)] (3.5, 6.5 and 7.4 mol‐%), PSVBA, are investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The calorimetric results show that PEMAVP‐13 is miscible with the three PSVBA copolymers in the studied proportions of 2 : 1, 1 : 1 and 1 : 2 by weight. The thermogram of each mixture shows a single composition‐dependent glass transition temperature, T_g. The experimental value of T_g for each blend is higher than the calculated weight average T_g of its components. Such a positive deviation implies the presence of strong specific interactions within these blends. A comparison of the determined Kwei q‐value reveals an increase of the specific interactions with acidic units in PSVBA composition. Fourier transform infrared measurements in the carbonyl stretching vibration region show the occurrence of hydrogen bonding involving the carboxylic acid groups of PSVBA with the carbonyl groups of PEMAVP‐13.     

Star‐Like Poly(N‐isopropylacrylamide) and Poly(ethylene glycol) Copolymers Self‐Arranged in Newfound Single Crystals and Associated Novel Class of Polymer Brush Regimes with V‐Type Tethers

Linear poly(ethylene glycol) (PEG)‐block‐poly(N‐isopropylacrylamide) (PNIPAM) and star‐like three‐arm PEG‐star‐(PNIPAM)₂ copolymers having one PEG and two PNIPAM blocks are synthesized by atom transfer radical polymerization (ATRP). Single crystals of these block copolymers are grown from amyl acetate and toluene dilute solutions. To recognize PNIPAM and PEG thicknesses, small angle X‐ray scattering (SAXS) is applied. V‐type brushes behave differently from linear brushes because doubly grafted PNIPAM blocks from a common point onto PEG substrate exert a higher osmotic pressure, leading to a thinner crystal. In addition to three ordinary regimes, a fourth or extremely stretched regime is detected for V‐type PNIPAM brushes. Although in PEG₅₀₀₀‐star‐(PNIPAM)₂ single crystals with overall PNIPAM molecular weight of 37 000 g/mol, each PNIPAM arm is shorter than PNIPAM grafts in linear PEG₅₀₀₀‐block‐PNIPAM₂₆₀₀₀ single crystals, their switching point from second to third regime is significantly lower (22 vs 33 °C). The V‐type configuration of PNIPAM brushes cause them to be entered into the extremely stretched or fourth regime, which has not been previously detected for coily brushes. The boundary between third and fourth regimes for PEG₅₀₀₀‐star‐(PNIPAM)₂ single crystals is verified at 31.5 and 23.5 °C in amyl acetate and toluene, respectively.     

Allyl End‐Functionalized Poly(ethylene oxide)‐block‐poly(methylidene malonate 2.1.2) Block Copolymers: Synthesis,Characterization, and Chemical Modification

Summary: Poly(ethylene oxide)‐block‐poly(methylidene malonate 2.1.2) block copolymer (PEO‐b‐PMM 2.1.2) bearing an allyl moiety at the poly(ethylene oxide) chain end was synthesized by sequential anionic polymerization of ethylene oxide (EO) and methylidene malonate 2.1.2 (MM 2.1.2). This allyl functional group was subsequently modified by reaction with thiol‐bearing functional groups to generate carboxyl and amino functionalized biodegradable block copolymers. These end‐group reactions, performed in good yields both in organic media and in aqueous micellar solutions, lead to functionalized PEO‐b‐PMM 2.1.2 copolymers which are of interest for cell targeting purposes.

Synthetic route to α‐allyl functionalized PEO‐b‐PMM 2.1.2 copolymers.     

Miscibility of C60‐end‐capped poly(ethylene oxide) with poly(p‐vinylphenol)

A fullerene (C₆₀)‐end‐capped poly(ethylene oxide) (FPEO) has been prepared by the cycloaddition reaction of monoazido‐terminated poly(ethylene oxide) with C₆₀. The majority of the FPEO sample is the monoadduct as shown by thermogravimetry and X‐ray photoelectron spectroscopy. Most electronic characteristics of C₆₀ are retained in the polymer as shown by its UV‐visible absorption spectrum. The incorporation of C₆₀ reduces the extent of crystallinity of PEO by 17%. The miscibility behavior of FPEO with poly(p‐vinylphenol) (PVPh) was studied. Similar to PEO, FPEO is miscible with PVPh over the entire composition range. The hydrogen‐bonding interaction between FPEO and PVPh is as strong as that between PEO and PVPh as shown by Fourier‐transform infrared spectroscopy.