Chemical modification of butyl rubber. II. Structure and properties of poly(ethylene oxide)-grafted butyl rubber

Poly(ethylene oxide)-grafted butyl rubbers (IIR-g-PEOs), which were synthesized from potassium salt of polyethylene glycol monomethyl ether (PEGM) and chlorinated butyl rubber, were found to behave like thermoplastic elastomers. The poly(ethylene oxide) (PEO) content of these amphiphilic polymers was ca. 10 wt %, and their PEO lengths were 750, 2000, and 5000, respectively. The grafted segments of PEO in butyl rubber (IIR) aggregated to form the PEO domains in IIR matrix. At constant PEO content, the longer the PEO segment length, the larger the size and the crystallinity of PEO domains became. This PEO domain worked as a cross-linking site and a reinforcing filler. The degree of swelling in water of IIR-g-PEO film that was prepared from PEGM-5000 was largest, but its emulsification ability was smallest among them. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of poly(ethylene oxide)‐grafted polyethylene copolymer and terpolymer

A series of graft copolymers were synthesized based on ethylene‐co‐m,p‐methylstyrene (EMS) (backbone copolymer), ethylene‐1‐hexene‐m,p‐methylstyrene (EHMS) (backbone terpolymer), and polyethylene glycol monomethyl ethers (PEGM) (grafts) in this study. The PEGMs with molecular weights of 750 and 2000 were used. The chemical composition of the graft copolymers was analyzed by NMR and DSC measurements. The graft copolymers exhibited a phase‐separated morphology with the backbone and the methoxy polyethylene glycol (MPEG) grafts forming separate crystalline phases. The MPEG phase had a melting temperature lower than the corresponding MPEG homopolymer, as determined by DSC. The melting point of the crystalline phase formed by the EMS and EHMS main chains was lower than that of pure polymer backbone. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemical modification of butyl rubber. III. Butyl rubber with D-maltose derivative as pendant groups

A new type of amphiphilic elastomer was synthesized, which consisted of butyl rubber and a D-maltose derivative as a backbone and side groups, respectively. The synthesis was accomplished by the sequence of the three following reactions: (1) Hydroxyl groups of D-maltonolactone were protected by a trimethylsilyl group. (2) The resulting maltonolactone derivative was subjected to a reaction with chemically modified butyl rubber having pendant amino groups. (3) The protecting trimethylsilyl groups on the maltose residues were removed by treating with tetra-n-butylammonium fluoride. This new amphiphilic elastomer behaved as a thermoplastic elastomer and showed good mechanical properties. The saccharide seg-ments aggregated in the hydrophobic butyl rubber matrix to form a microphase-separated structure, as confirmed by differential scanning calorimetry, transmission electron mi-croscopy, small-angle x-ray scattering, and dynamic mechanical measurements. The ag-gregated saccharide domains are estimated to function both as crosslinking sites and rein-forcing fillers in the rubber matrix. © 1995 John Wiley & Sons, Inc.     

Hydrophilic polyisophthalamides containing poly(ethylene oxide) side chains: Synthesis,characterization, and physical properties

Novel polyisophthalamides containing pendent poly(ethylene oxide) (PEO) sequences were prepared by grafting PEO onto poly(5‐hydroxy‐isophthalamide)s (HO‐PIPAs). First, an optimized method of synthesis was applied to prepare HO‐PIPAs, following the rules of the direct polyamidation reaction promoted by triphenyl phosphite and catalyzed by pyridine. Next, the modification of HO‐PIPAs was performed by a nucleophilic substitution reaction with chlorine‐terminated PEO monomethyl ether of average molecular weight 100, 550, and 1000 g/mol. The modification (grafting) reaction was optimized to assure virtually 100% yield. Polymers behaved as graft or brush‐like copolymers of polyisophthalamide (PIPA) and PEO, covering a wide range of ratios of PIPA/PEO. Physical properties, such as solubility, glass transition temperature, and thermal resistance were determined. Special attention was paid to the affinity of the novel copolymers for water. It was realized that with a high content of PEO, the materials could absorb water in amounts exceeding their own weight. Gravimetric methods and water contact angle measurements were used to quantify the hydrophilicity of the current PIPA‐g‐PEO copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide). I. Miscibility and thermal properties

The miscibility and thermal properties of polyethylene oxide(PEO)/oligoester resin (OER) blends and PEO/crosslinked polyester (PER) blends were studied by differential scanning calorimetry (DSC). The effect of quenching process on the crystallization behavior of PEO for these two systems were investigated and discussed in details. It has been found that a single, composition dependent glass transition temperature (T_g) was observed for all the blends, indicating that the two systems are miscible in the amorphous state at overall compositions. From the melting point depression of PEO, the interaction parameter χ₁₂ for PEO/OER blends and that for PEO/PER blends were found to be −1.29 and −2.01, respectively. The negative values of χ₁₂ confirmed that both PEO/OER blends and PEO/PER blends are miscible in the molten state. Quenching process has a greater hindrance on the crystallization of PEO/OER blends than on that of PEO/PER blends. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3161–3168, 1997     

Synthesis and characterization of poly(ethylene oxide)/polylactide/poly(ethylene oxide) triblock copolymer

Poly(ethylene oxide/polylactide/poly(ethylene oxide) (PEO/PL/PEO) triblock copolymers, in which each block is connected by an ester bond, were synthesized by a coupling reaction between PL and PEO. Hydroxyl‐terminated PLs with various molecular weights were synthesized and used as hard segments. Hydroxyl‐terminated PEOs were converted to the corresponding acid halides via their acid group and used as a soft segment. Triblock copolymers were identified by Fourier transform infrared spectroscopy, ¹H NMR, and gel permeation chromatography. Differential scanning calorimetry (DSC) and X‐ray diffractometry of PEO/PL/PEO triblock copolymers suggested that PL and PEO blocks were phase‐separated and that the crystallization behavior of the PL block was markedly affected by the presence of the PEO block. PEO/PL/PEO triblock copolymers with PEO 0.75k had two exothermic peaks (by DSC), and both peaks were related to the crystallization of PL. According to thermogravimetric analysis, PEO/PL/PEO triblock copolymer showed a higher thermal stability than PL or PEO. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2545–2555, 2002     

Thermal oxidation of blends of poly(ethylene oxide) and poly(methyl methacrylate)

Thermal oxidation of poly(ethylene oxide) (PEO) and its blends with poly(methyl methacrylate) (PMMA) were studied using oxygen uptake measurements. The rates of oxidation and maximum oxygen uptake contents were reduced as the content of PMMA was increased in the blends. The results were indicative of a stabilizing effect by PMMA on the oxidation of PEO. The oxidation reaction at 140°C was stopped at various stages and PMMA was separated from PEO and its molecular weights were measured by gel permeation chromatography (GPC). The decrease in the number-average molecular weight of PMMA was larger as the content of PEO increased in the blends. The visual appearance of the films suggested that phase separation did not occur after thermal oxidation. The activation energy for the rates of oxidation in the blends was slightly increased compared to pure PEO. © 1992 John Wiley & Sons, Inc.     

Synthesis of new amphiphilic diblock copolymers containing poly(ethylene oxide) and poly(α‐olefin)

This article discusses an effective route to prepare amphiphilic diblock copolymers containing a poly(ethylene oxide) block and a polyolefin block that includes semicrystalline thermoplastics, such as polyethylene and syndiotactic polystyrene (s‐PS), and elastomers, such as poly(ethylene‐co‐1‐octene) and poly(ethylene‐co‐styrene) random copolymers. The broad choice of polyolefin blocks provides the amphiphilic copolymers with a wide range of thermal properties from high melting temperature ～270 °C to low glass‐transition temperature ～?60 °C. The chemistry involves two reaction steps, including the preparation of a borane group‐terminated polyolefin by the combination of a metallocene catalyst and a borane chain‐transfer agent as well as the interconversion of a borane terminal group to an anionic (? O^?K⁺) terminal group for the subsequent ring‐opening polymerization of ethylene oxide. The overall reaction process resembles a transformation from the metallocene polymerization of α‐olefins to the ring‐opening polymerization of ethylene oxide. The well‐defined reaction mechanisms in both steps provide the diblock copolymer with controlled molecular structure in terms of composition, molecular weight, moderate molecular weight distribution (M_w/M_n < 2.5), and absence of homopolymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3416–3425, 2002     

Synthesis and characterization of a vinyl‐terminated benzoxazine monomer and its blends with poly(ethylene oxide)

A vinyl‐terminated benzoxazine (VB‐a), which could be polymerized through ring‐opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB‐a monomer was then subjected to blending with poly(ethylene oxide) (PEO), followed by thermal curing, to form poly(VB‐a)/PEO blends. The specific interactions, miscibility, morphology, and thermal properties of these blends were investigated with Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). Before curing, we found that PEO was miscible with VB‐a, as evidenced by the existence of a single composition‐dependent glass transition temperature (T_g) for each composition. The FTIR spectra revealed the presence of hydrogen‐bonding interactions between the hydroxyl groups of poly(VB‐a) and the ether groups of PEO. Indeed, the ring‐opening reaction and subsequent polymerization of the benzoxazine were facilitated significantly by the presence of PEO. After curing, DMA results indicated that the 50/50 poly(VB‐a)/PEO blend exhibited two values of T_g: one broad peak appeared in the lower temperature region, whereas the other (at ca. 327 °C, in the higher temperature region) was higher than that of pristine poly(VB‐a) (301 °C). The presence of two glass transitions in the blend suggested that this blend system was only partially miscible. Moreover, SEM micrographs indicated that the poly(VB‐a)/PEO blends were heterogeneous. The volume fraction of PEO in the blends had a strong effect on the morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 644–653, 2007     

Swelling-assisted modification of poly(ethylene terephthalate) by methacrylic acid

When a poly(ethylene terephthalate), PET, film is heated in an aqueous solution of methacrylic acid in the presence of hydrogen peroxide as an initiator, it is found that the weight of the film is increased. The amount of methacrylic acid that may be added onto the film is dependent upon the concentration of the monomer, the initiator, and the temperature at which the reaction occurs. Pretreatment of the film with 1,1,2,2,tetrachloroethane causes swelling and the amount of add-on is increased as the swelling level increases. Methacrylic-acid-modified PET films hydrolyze at room temperature in aqueous sodium hydroxide; the rate of hydrolysis is dependent upon the amount of add-on and the concentration of the base. This procedure leads to a chemically induced blend of polymethacrylic acid and poly(ethylene terephthalate), and grafting of the monomer onto the polymer film does not occur. © 1995 John Wiley & Sons, Inc.     

Poly(ethylene oxide)/poly(methyl methacrylate) (semi-)interpenetrating polymer networks: Synthesis and phase diagrams

Interpenetrating polymer networks (IPNs) of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) were prepared by simultaneous network formation. The PEO network was produced by acid-catlayzed self-condensation of α,ω-bis(triethoxysilane)-terminated PEO in the presence of small amounts of water. The PMMA network was formed by free radical polymerization of MAA in the presence of divinylbenzene as crosslinker. The reaction conditions were adjusted to obtain similar crosslinking kinetics for both reactions. An attempt was made to construct a phase diagram of the IPNs by measuring the composition of the IPNs at the moment of the appearance of the phase separation, as indicated by the onset of turbidity. This composition could be determined because the siloxane crosslinks of the PEO network could be hydrolyzed in aqueous NaOH with the formation of linear, soluble PEO chains. The phase diagram was compared with phase diagrams of blends of linear polymers and of semi-IPNs (crosslinked PMMA and linear PEO), obtained under similar conditions, i.e. polymerization of MMA in the presence of varying amounts of PEO. It was observed that the form of the phase diagrams of the linear polymers is similar to that of the IPNs, but is quite different from that of the semi-IPNs. Thus, homogeneous transparent materials containing up to 60% of PEO could be prepared in the blends and the IPNs, but in the semi-IPNs, phase separation occurred with PEO contents as low as 10%.     

分散聚合制备聚苯乙烯/聚氧乙烯两亲磁性高分子微球

采用分散聚合法，以乙醇／水为介质，在Fe3O4磁流体存在下，通过苯乙烯与聚氧乙烯大分子单体共聚制备休磁性高分子微球。 研究了聚合条件对微球粒径的影响。通过改变聚合条件，可以得到平均粒径为5μm-100μm的两亲磁性高分子微球。     

Complexation of poly(ethylene oxide) and urea

The complexation of ultrahigh-molecular-weight poly(ethylene oxide) (PEO) with urea in both the solid and molten states was studied by infrared spectroscopy. Information about the temperature dependences of the absorption bands in the 3600–2600 and 1300–600 cm^?1 region on heating and cooling was obtained. Some conclusions concerning the interaction between PEO and urea were also made. The formation of a high temperature, metastable molecular complex between PEO and urea, which is susceptible to undercooling, was confirmed spectroscopically. Heating to 85–90°C resulted in a molecular complex stable at room temperature.© 1994 John Wiley & Sons, Inc.     

Studies of photooxidative degradation of poly(vinyl chloride)/poly(ethylene oxide) blends

The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004     

Clustering of poly(ethylene oxide) in water revisited

The dynamic light scattering results presented in this letter demonstrate that the clustering of poly(ethylene oxide) (PEO) can be observed even in ultrapure, freshly double‐distilled and filtered deionized water. It is confirmed that the filtration of solutions removes the clustering structure and that a steady‐state amount of PEO in clusters is reformed in filtered solutions within 24 h. Adding a drop of chloroform to unfiltered aqueous solutions of PEO temporarily alters the clustering structure, but it prevents the clustering of PEO in filtered solutions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 135–138, 2003     

Effect of poly(ethylene oxide) on the structure and properties of poly(vinyl alcohol)

To improve the drawability of poly(vinyl alcohol) (PVA) thermal products, poly(ethylene oxide) (PEO), a special resin with good flexibility, excellent lubricity, and compatibility with many resins, was applied, and the Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WXRD) were adopted to study the hydrogen bonds, water states, thermal properties, crystal structure, and nonisothermal crystallization of modified PVA. It was found that PEO formed strong hydrogen bonds with water and PVA, thus weakened the intra‐ and inter‐hydrogen bonds of PVA, changed the aggregation states of PVA chains, and decreased its melting point and crystallinity. Moreover, the interactions among PVA, water, and PEO retarded the water evaporation and made more water remain in the system to plasticize PVA. The existence of PEO also slowed down the melt crystallization process of PVA, however, increased the nucleation points of system, thus made more and smaller spherulites formed. The weakened crystallization capability of PVA and the lubrication of PEO made PVA chains to have more mobility under the outside force and obtain high mechanical properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1946–1954, 2010     

Preparation,characterization, and dilute solution properties of four-branched cage-shaped poly(ethylene oxide)

A four-branched cage-shaped poly(ethylene oxide) (4C-PEO) was prepared by a coupling reaction at very dilute condition between two kinds of end-functional four-armed star-shaped PEOs having amino and N-hydroxysuccinimide groups on their four ends, followed by purification using α-cyclodextrin (α-CD). The raw coupling reaction product shows multiple peaks including various high molecular weight multimeric products in size-exclusion chromatography measurements, while the product after α-CD purification shows a single peak eluted slightly earlier than the precursor star PEOs. Moreover, the final product obtained has about twice higher molecular weight than the star precursors. These results suggest that the targeted 4C-PEO polymer was successfully isolated through the α-CD purification. Small-angle neutron scattering (SANS) measurements of the final product in dilute solution were conducted, and its chain conformation was evaluated from the scattering profile in comparison with linear and star polymers. It has been found that the cage-shaped sample exhibits a distinct peak at lower q-region in the Kratky plot, which is in strong contrast with the linear counterpart. This result must be originated from the characteristic cage-shaped architecture, that is, having branched and closed-loop configurations, and hence having higher segmental density than simple linear and star molecules. In fact, the present experimental result is consistent with the recent Monte Carlo simulation reported by Uehara and Deguchi.     

Miscibility and spherulite growth kinetics in the poly(ethylene oxide)/poly(benzyl methacrylate) system

This study for the first time discovered miscibility in the binary blend of semicrystalline poly(ethylene oxide) (PEO) with amorphous poly(benzyl methacrylate) (PBzMA). Differential scanning calorimetry, optical and scanning electron microscopy, and infrared spectroscopy were performed to characterize and demonstrate miscibility in the PEO/PBzMA system. The glass‐transition behavior and Fourier transform infrared results suggest that the intermolecular interactions between the pairs were likely nonspecific and at best comparable to those among the same constituent component. The melting‐point depression study yielded χ = −0.1, indicating a relatively low interaction strength. It is concluded that the phase behavior of the blend was miscibility with nonspecific interactions, mostly a matched polar–polar intermolecular attraction. PEO spherulitic crystallization in the blend is discussed to support the miscibility behavior. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 562–572, 2000     

Effects of the conductivity of sulfonated poly(phenylene oxide) lithium by the complexation of poly(ethylene oxide)

In the present paper, the structure and conductivity for the complex of sulfonated poly(phenylene oxide) lithium (SPPOLi) and poly(ethylene oxide) (PEG) were studied. Glass transition temperature change determined by differential scanning calorimeter analysis desmonstrated that the two components had some compatibility. X-ray diffraction showed that PEG could decrease the regularity of SPPOLi to some extent. The compatibility and PEG's effect on the regularity may be due to the interaction between the lithium ions of SPPOLi and the oxygen atoms of PEG. Under polarization by electric field, the bands between lithium ions and sulfonation groups relaxed. Meanwhile, the complexation of oxygen atoms could enhance the dissociation of the polymeric lithium salts. Then lithium ions were transported in the process of alternate complexing and decomplexing. The action between lithium ions and oxygen atoms could explain the improvement on the conductivity of SPPOLi.     

Study of the Crystallization Kinetics. Poly(ethylene oxide) and a blend of poly(ethylene oxide) and poly(bisphenol A-co-epichlorohydrin)

A kinetic study of the crystallization of poly(ethylene oxide) (PEO) and of a blend of PEO+poly(bisphenol A-co-epichlorohydrin) (PBE) was performed by using DSC in a non-isothermal program at constant cooling rates. The curves obtained were analyzed by the Kissinger, Ozawa and Friedman methods, with determination of the kinetic parameters in each case. As a consequence of the presence of PBE, the kinetic parameters were altered, leading to the conclusion that PBE has some influence on the crystallization of PEO, modifying its mechanism. This revised version was published online in July 2006 with corrections to the Cover Date.