Synthesis of multiblock copolymers of poly(2‐vinylpyridine) and polyoxyethylene

Telechelic dihydroxy poly(2‐vinylpyridine) (THPVP) samples with different molecular weights were synthesized by using lithium α‐methylnaphthalene as an anionic initiator in mixed solvents of benzene and tetrahydrofuran (THF). Then multiblock copolymers of poly(2‐vinylpyridine) (P2VP) and polyoxyethylene (PEO) were obtained by condensing THPVP and PEO with dichloromethane in the presence of potassium hydroxide. The effects of reaction time, molecular weight of PEO and THPVP, and raw meal ratio PEO/THPVP (w/w) were investigated. The best conditions were found. The copolymers can be purified by water and toluene. The purified copolymers were characterized by infrared (IR) and ¹H nuclear magnetic resonance (¹H‐NMR). The PEO segment content was calculated from the integral curve of ¹H‐NMR spectra. The results showed that these multiblock copolymers were connected through oxymethylene. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1632–1636, 2003     

Thermal and structural analysis of heparin–PEO–PDMS–PEO–heparin pentablock copolymers

ABCBA-type amphiphilic block copolymers comprising polydimethylsiloxane (PDMS), poly(ethylene oxide) (PEO), and heparin segments were synthesized by coupling reactions between end-functionalized oligomers. These multiblock copolymers were characterized to examine bulk properties using ¹H-NMR, FTIR, end-group analysis, and sulfur elemental analysis. Block copolymers were further characterized in bulk using differential scanning calorimetry and X-ray diffraction measurements. The PDMS glass transition remains unchanged with increasing PEO content, indicating coexistence of pure PDMS with mixed phases. Furthermore, endothermic melting of the block copolymers shifts to higher temperatures and becomes more intense with increasing PEO molecular weight. Additionally, the crystallinity of the PEO segment in the block copolymers increases with increasing PEO molecular weight. The PEO melting endotherm peak shifts from near 318 to 323 K with annealing. In the cooling thermogram, the block copolymers exhibit two crystallization exotherms, one near 303 K and the other near 193 K, attributed to PEO and PDMS recrystallization and nucleation, respectively. © 1994 John Wiley & Sons, Inc.     

Synthesis of graft copolymer polyethylene‐ graft‐poly(ethylene oxide) by a new anionic graft‐from polymerization

A series of amphiphilic graft copolymers, PE‐graft‐PEO, containing hydrophobic polyethylene (PE) as the backbone and hydrophilic poly(ethylene oxide) (PEO) as the side‐chain, have been synthesized by a novel route. The graft structure and the molecular weight, as well as the molecular weight distribution of the graft copolymer can easily be controlled. The molecular weight of the side‐chain PEO is proportional to the reaction time and the monomer concentration, which indicates the ‘living’ character of the anionic polymerization of ethylene oxide. The produced copolymers PE‐graft‐PEO were characterized by ¹H NMR and DSC measurements. Copyright © 2004 Society of Chemical Industry     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Preparation and characterization of amphiphilic block copolymer of polyacrylonitrile‐block‐poly(ethylene oxide)

The synthesis of polyacrylonitrile‐block‐poly(ethylene oxide) (PAN‐b‐PEO) diblock copolymers is conducted by sequential initiation and Ce(IV) redox polymerization using amino‐alcohol as the parent compound. In the first step, amino‐alcohol potassium with a protected amine group initiates the polymerization of ethylene oxide (EO) to yield poly(ethylene oxide) (PEO) with an amine end group (PEO‐NH₂), which is used to synthesize a PAN‐b‐PEO diblock copolymer with Ce(IV) that takes place in the redox initiation system. A PAN‐poly(ethylene glycol)‐PAN (PAN‐PEG‐PAN) triblock copolymer is prepared by the same redox system consisting of ceric ions and PEG in an aqueous medium. The structure of the copolymer is characterized in detail by GPC, IR, ¹H‐NMR, DSC, and X‐ray diffraction. The propagation of the PAN chain is dependent on the molecular weight and concentration of the PEO prepolymer. The crystallization of the PAN and PEO block is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1753–1759, 2003     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Synthesis of biocompatible tadpole-shaped copolymer with one poly(ethylene oxide) (PEO) ring and two poly(ɛ-caprolactone) (PCL) tails by combination of glaser coupling with ring-opening polymerization

The biocompatible tadpole-shaped copolymers [cyclic-poly(ethylene oxide) (PEO)]-b-[linear poly(?-caprolactone) (PCL)]₂ [(c-PEO)-b-PCL₂] with one PEO ring and two PCL tails were synthesized by combination of glaser coupling with ring-opening polymerization (ROP). First, a linear PEO precursor with two alkyne groups at the chain terminal and two hydroxyl groups at the chain middle was prepared by ROP of EO monomer and the following transformation of functional groups. Then, cyclic PEO with two hydroxyl groups at the same site was obtained by the “Glaser” cyclization. Finally, the hydroxyl groups on cyclic PEO directly initiated the ROP of ?-CL monomer to produce the target copolymers (c-PEO)-b-PCL₂. The target copolymers and intermediates were all well characterized by GPC, MALDI-TOF MS, ¹H NMR and FT-IR.     

Synthesis and characterization of thermo‐ and pH‐sensitive block copolymers bearing a biotin group at the poly(ethylene oxide) chain end

A poly(ethylene oxide)‐block‐poly(dimethylamino ethyl methacrylate) block copolymer (PEO‐b‐PDMAEMA) bearing an amino moiety at the PEO chain end was synthesized by a one‐pot sequential oxyanionic polymerization of ethylene oxide (EO) and dimethylamino ethyl methacrylate (DMAEMA), followed by a coupling reaction between its PEO amino and a biotin derivative. The polymers were charac terized with ¹H NMR spectroscopy and gel permeation chromatography. Activated biotin, biotin‐NHS (N‐hydroxysuccinimide), was used to synthesize biotin‐PEO‐PDMAEMA. In aqueous media, the solubility of the copolymer was temperature‐ and pH‐sensitive. The particle size of the micelle formed from functionalized block copolymers was determined by dynamic light scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3552–3558, 2006     

Synthesis of water‐soluble polyphenol‐graft‐poly(ethylene oxide) copolymers via enzymatic polymerization and anionic polymerization

Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and ¹H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry     

Nonaqueous emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol. I. Evaluation of stabilizing efficiency for PEO‐PS‐PEO triblock copolymers

Sixteen poly(ethylene oxide)–polystyrene–poly(ethylene oxide) (PEO‐PS‐PEO) triblock copolymers were synthesized by anionic polymerization. They were characterized by gel permeation chromatography and proton NMR. The molecular weight of these 16 PEO‐PS‐PEO triblock copolymers ranged from 5100 to 13,300. The polystyrene (PS) block length was between 13 and 41. The PEO block length was between 41 and 106. The polydispersity index for these PEO‐PS‐PEO triblock copolymers were 1.05 ± 0.02. When using these stabilizers in the emulsion copolymerization of ethyl methacrylate and lauryl methacylate in propylene glycol, only a narrow window of stability was observed. Stable latexes were formed only when the molecular weights of the PEO blocks were within the range of 5300–7700 and the molecular weights of the PS blocks were 2000–4000. The stabilizer ability for these triblock copolymers was correlated with their molecular weight and conformation in propylene glycol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1951–1962, 2001     

Biodegradable polymers for use in surgery — poly(ethylene oxide)/poly(ethylene terephthalate) (PEO/PET) copolymers: 2. In vitro degradation

The degradation mechanism of a series of poly(ethylene oxide)/poly(ethylene terephthalate) (PEO/PET) copolymers, synthesized as described in Part 1¹, has been studied in vitro. The need for the development of in vitro test methods for candidate biomaterials is set down. The effect of time, temperature, pH and selected enzymes on the rate and mechanism of degradation is elucidated. The degradation products are identified. The degree of degradation was monitored molecularly by gel permeation chromatography (g.p.c.) and end-group titration techniques. The composition of the copolymers was obtained using infra-red (i.r.) and nuclear magnetic resonance (n.m.r.) spectroscopy. Mass loss and water uptake data are also given. The mechanism of degradation is shown to be by hydrolysis. The effect of ethylene oxide (EO) and ⁶⁰Co γ-irradiation sterilization on the copolymers was investigated.     

Synthesis of novel amphiphilic graft copolymers composed of poly(ethylene oxide) as backbone and polylactide as side chains

A well-defined amphiphilic comb-like copolymer of poly(ethylene oxide)(PEO) as main chain and polylactide (PLA) as side chain was successfully prepared via a combination of anionic polymerization and coordination-insertion ring-opening polymerization. The anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out using potassium 2-(2-methoxyethoxy)ethoxide as initiator, and then ethoxyethyl groups of EEGE units of the copolymers obtained were removed by hydrolysis. Two copolymers of methoxypoly(ethylene oxide-co-glycidol) [mpoly(EO-co-Gly)] were formed with multiple hydroxyl sites (the molar ratio values of Gly to EO in copolymers: 1/10.6 and 1/5.2; Mn: 10,100 and 5,020 respectively), and them were used further to initiate the ring-opening polymerization of lactide in the presence of stannous octoate, and a well-defined comb-like copolymer of PEO as main chain and PLA as side chain was obtained. The intermediate and final products of PEO-g-PLA were characterized by GPC and NMR in detail.     

Water vapor transmission of poly(ethylene oxide)‐based segmented block copolymers

This article discusses the rate of water vapor transmission (WVT) through monolithic films of segmented block copolymers based on poly(ethylene oxide) (PEO) and monodisperse crystallisable tetra‐amide segments. The polyether phase consisted of hydrophilic PEO or mixtures of PEO and hydrophobic poly(tetramethylene oxide) (PTMO) segments. The monodisperse tetra‐amide segments (T6T6T) were based on terephthalate units (T) and hexamethylenediamine (6). By using monodisperse T6T6T segments the crystallinity in the copolymers was high (～ 85%) and, therefore, the amount of noncrystallised T6T6T dissolved in the polyether phase was minimal. The WVT was determined by using the ASTM E96BW method, also known as the inverted cup method. By using this method, there is direct contact between the polymer film and the water in the cup. The WVT experiments were performed in a climate‐controlled chamber at a temperature of 30°C and a relative humidity of 50%. A linear relation was found between the WVT and the reciprocal film thickness of polyether‐T6T6T segmented block copolymers. The WVT of a 25‐μm thick film of PTMO₂₀₀₀‐based copolymers was 3.1 kg m^?2 d^?1 and for PEO₂₀₀₀‐based copolymers 153 kg m^?2 d^?1. Of all the studied copolymers, the WVT was linear related to the volume fraction of water absorbed in the copolymer to the second power. The results were explained by the absorption‐diffusion model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Segmented block copolymers based on liquid natural rubber

Segmented block copolymers were prepared from hydroxyl-terminated liquid natural rubber (HTNR) and poly(ethylene oxide) (PEO). Toluene 2,4 diisocyanate (TDI) was used as the coupling agent for combining both types of segments. Keeping the molecular weight of HTNR constant, a series of materials were prepared using PEO with varying molecular weights. Their thermal and mechanical properties were evaluated. With increasing the PEO content, the properties vary from soft to rigid elastomers and rubber-toughened plastics. This variation in properties is caused by the changes in the sample morphology, which depends on the relative fractions of the hard and soft segments. Water absorption capability of these block copolymers was determined. Hydrogels with water content approximately up to 80% were obtained.     

Preparation and characterization of polystyrene–poly(ethylene oxide) amphiphilic block copolymers via atom transfer radical polymerization: Potential application as paper coating materials

Poly(ethylene oxide) (PEO) monochloro macroinitiators or PEO telechelic macroinitiators (Cl‐PEO‐Cl) were prepared from monohydroxyfunctional or dihydroxyfunctional PEO and 2‐chloro propionyl chloride. These macroinitiators were applied to the atom transfer radical polymerization of styrene (S). The polymerization was carried out in bulk at 140°C and catalyzed by Copper(I) chloride (CuCl) in the presence of 2,2′‐bipyridine (bipy) ligand (CuCl/bipy). The amphiphilic copolymers were either A‐B diblock or A‐B‐A triblock type, where A block is polystyrene (PS) and B block is PEO. The living nature of the polymerizations leads to block copolymers with narrow molecular weight distribution (1.072 < M_w/M_n < 1.392) for most of the macroinitiators synthesized. The macroinitiator itself and the corresponding block copolymers were characterized by FTIR, ¹H NMR, and SEC analysis. By adjusting the content of the PEO blocks it was possible to prepare water‐soluble/dispersible block copolymers. The obtained block copolymers were used to control paper surface characteristics by surface treatment with small amount of chemicals. The printability of the treated paper was evaluated with polarity factors, liquid absorption measurements, and felt pen tests. The adsorption of such copolymers at the solid/liquid interface is relevant to the wetting and spreading of liquids on hydrophobic/hydrophilic surfaces. From our study, it is observed that the chain length of the hydrophilic block and the amount of hydrophobic block play an important role in modification of the paper surface. Among all of block copolymers synthesized, the PS‐b‐PEO‐b‐PS containing 10 wt % PS was found to retard water absorption considerably. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4304–4313, 2006     

Preparation of silica/poloxamer composite by sol-gel process and pore control of silica gel obtained from the composite

Silica gels that controlled the pore size were prepared by calcination of silica/organic polymer (50/50 wt %) composites prepared by the sol-gel process. Poly(ethylene oxide) (PEO)-poly(propyrene oxide) (PPO)-PEO triblock copolymers, which are called poloxamers, were used as an organic polymer. The pore control of the silica gels was carried out by changing the molecular weight of PEO or PPO in the poloxamers. The silica gels obtained by the above procedure had a dual pore size of around 4 nm and below 2 nm in diameter, and the specific surface area was 500–1000 m²/g. The poloxamer molecules were supposed to be dispersed monomolecularly in the composites. Therefore, the pore structure of the silica gels reflected the structure of the poloxamer and, particularly, the radius of gyration of PPO in the composites. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 763–768, 1997     

Synthesis and properties of styrene–butadiene–oxyethylene multiblock polymers

Multiblock copolymers of styrene, butadiene, and ethylene oxide were synthesized by coupling together telechelic dihydroxyl polystyrene, telechelic dihydroxyl polybutadiene, and poly(ethylene glycol), using 2,4-toluene diisocyanate as coupling agent. The copolymers were purified by extractions and characterized by infrared (IR), ¹H nuclear magnetic resonace (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), membrane osmometry, and dynamic viscoelastometry. The multiblock copolymers are amphiphilic, exhibiting very good emulsifying properties. They possess a good phase transfer catalytic ability in Williamson reaction, and their LiClO₄ complexes exhibit a conductivity above 1 × 10⁻⁴ S/cm at 35°C. © 1996 John Wiley & Sons, Inc.     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

PEO-b-PS两亲性嵌段共聚物的合成与表征

以PEO-Br为大分子引发剂,CuBr/2-2’-联吡啶为催化体系,采用原子转移自由基聚合(ATRP)方法制得了一系列分子量可控且分子量分布窄的两亲性嵌段共聚物,通过1H-NMR、GPC、DSC等测试手段对其进行了表征,研究结果表明嵌段共聚物随着聚氧乙烯含量的降低,结晶度(Xc)、结晶熔融温度(Tm)、结晶温度(Tc)降低;当共聚物中聚氧乙烯的含量降为45%时,嵌段共聚物已无结晶现象。     

Synthesis and characterization of amphipathic poly(methyl methacrylate)-b-poly(ethylene oxide) diblock copolymers

Summary This paper describes the synthesis and characterization of amphipathic diblock copolymers of poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO). The synthesis involved the coupling of acyl chloride-terminated PMMA block with methoxy poly(ethylene oxide) (MPEO). Carboxylic acid chloride-terminated PMMA was generated by treating with thionyl chloride the parent carboxylic PMMA, which was prepared by free radical polymerization of methyl methacrylate (MMA) using benzoyl peroxide (BPO) as the initiator and -mercaptopropionic acid (MPA) as the chain transfer agent. The proposed mechanism of MMA polymerization is in good agreement with the experimental results which indicate that as a side reaction nonfunctional (aromatic) counterpart is produced in a small quantity. The coupling of the acyl chloride-terminated PMMA with MPEO was quantitative.