Small-angle X-ray scattering and linear melt rheologyof poly(tert-butyl acrylate-g-styrene) graft copolymers

The morphology and rheological properties have been studied for poly(tert-butyl acrylate-g-styrene), PtBA-g-S, graft copolymers through the analysis of different samples that varied in the number of grafted repeat units. Small-angle X-ray scattering (SAXS) measurements confirmed phase separation in these samples, and showed the presence of disordered microdomains on those copolymers with a grafting number higher than 7. SAXS results have also shown a significant improvement of microdomain segregation with temperature manifesting considerable changes in both intensity, position and full-width half-maximum of the peak q*, which is attributed to the graft-like nature of these systems. The frequency dependence of the dynamic moduli revealed three relaxation mechanisms. The low-frequency (long time) relaxation was identified with the movement of the whole molecule, the relaxation at intermediate time is related to movement of the grafts, and the high-frequency relaxation is like that found in the transition zone of main chain of poly(tert-butyl acrylate), PtBA. The rheological measurements indicated that the introduction of a small amount of polystyrene, PS, grafts in the PtBA backbone is sufficient to modify mechanical behaviour at low frequencies. Comparison of the rheological properties of the graft copolymers with higher PS content showed that the observed changes in the viscoelastic behaviour under shear seems to be related to both the microphase separated microstructure and the number of grafts present in the copolymers.     

Preparation of poly(tert-butyl acrylate-g-styrene) as precursors of amphiphilic graft copolymers. 1. Kinetic study and thermal properties

Free radical copolymerizations of tert-butyl acrylate and a polystyrene macromonomer carrying a methacryloyloxy group at the chain end have been performed in benzene solution using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator at 70 °C. The estimated values of the ‘lumped’ kinetic constant, k_p/k_t^1/2, have shown a clear dependency on the macromonomer concentration in the reaction medium. The obtained poly(tert-butyl acrylate-g-polystyrene) graft copolymers were characterized by size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). In addition, the thermal behavior of these copolymers was studied by thermogravimetric analysis (TGA). Subsequently, hydrolysis of precursor graft copolymer was performed to afford an amphiphilic graft copolymer. Characterization using FT-IR confirmed total hydrolysis of the ester group.     

Application of poly(acrylic acid-g-gelatin)/polypyrrole gel electrolyte in flexible quasi-solid-state dye-sensitized solar cell

A novel gel polymer electrolyte based on poly(acrylic acid-g-gelatin)/polypyrrole with conductivity of 14.1 mS cm⁻¹ was prepared. Based on the gel electrolyte, a flexible quasi-solid-state dye-sensitized solar cell was fabricated by using a low-temperature filming technique. Owing to high conductivity and the catalytic function of polypyrrole for I⁻/I₃⁻ redox reaction for the gel electrolyte, the flexible quasi-solid-state dye-sensitized solar cell showed a light-to-electric energy conversion efficiency of 1.28%, under a simulated solar light irradiation with intensity of 100 mW cm⁻² (AM 1.5).     

Preparation and characterization of graft copolymers of methyl methacrylate and poly(n-hexyl isocyanate) macromonomers

Living poly(n-hexyl isocyanate) (PHIC) was deactivated with methacryloyl chloride to produce methacryl-terminated poly(n-hexyl isocyanate) (PHIC-MA) rodlike macromonomers. Radical copolymerization of methyl methacrylate (MMA) with PHIC-MA was performed using 2,2′-azobis(isobutyronitrile) as an initiator in benzene at 60 °C to prepare poly(methyl methacrylate)-graft-poly(n-hexyl isocyanate) (PMMA-graft-PHIC) graft copolymers. The monomer reactivity ratios of MMA (M₁) and PHIC-MA (M₂) were evaluated as r₁=11.5 and r₂=∼0, exhibiting remarkably lower reactivity of PHIC-MA macromonomer than that of common macromonomers. The resultant graft copolymers were characterized using gel permeation chromatography equipped with low-angle laser light-scattering to determine the molecular weights, and equipped with a refractive index detector and an ultraviolet light detector to estimate a PHIC weight fraction of PMMA-graft-PHIC at the ith elution volume of the GPC chromatogram. There are 2-3 PHIC grafts per PMMA molecule, and the PHIC rodlike chains might be difficult to introduce into the PMMA main chains having higher molecular weights. A specific dimension of PMMA-graft-PHIC in solution was discussed in detail.     

Synthesis of amphiphilic ethyl cellulose grafting poly(acrylic acid) copolymers and their self-assembly morphologies in water

Amphiphilic ethyl cellulose (EC)-g-poly(acrylic acid) (PAA) copolymers were synthesized by atom transfer radical polymerization (ATRP). Firstly, ethyl cellulose macro-initiators with the degree of the 2-bromoisobutyryl substitution of 0.04 and 0.25 synthesized by the esterification of the hydroxyl groups remained in EC macromolecular chains and the 2-bromoisobutyryl bromides. Secondly, tert-butyl acrylate was polymerized by ATRP with the ethyl cellulose macro-initiator and EC-g-PtBA copolymers were prepared. Finally, the EC-g-PAA copolymers were prepared by hydrolyzing tert-butyl group of the EC-g-PtBA copolymers. The grafting copolymers were characterized by means of GPC, ¹H NMR and FTIR spectroscopies. The molecular weight of graft copolymers increased during the polymerization and the polydispersity was low. A kinetic study showed that the polymerization was first-order. Meanwhile, EC-g-PAA copolymers were self-assembled to micelles or particles with diameters of 5 nm and 100 nm in water (pH = 10) when the concentration was 1.0 mg/ml.     

聚(丙烯酸-丙烯酰胺)接枝辛基酚聚氧乙烯醚丙烯酸酯两亲性共聚物的合成及表征

以辛基酚聚氧乙烯醚丙烯酸酯(C8PhEO10Ac)为大分子单体,丙烯酸(AA)、丙烯酰胺(AM)为共聚单体,采用大分子单体接枝共聚法,制备了一种两亲性接枝共聚物(AA-AM-g-C8PhEO10Ac),用静态光散射(SLS)与GPC联用技术测得接枝共聚物的分子量为9.51×105,用FTIR、1H NMR和TG/DTA等手段对共聚物的结构及性能进行了表征。采用透射电子显微镜(TEM)对聚合物在水溶液中的自组装行为进行了初步研究。结果表明,AA-AM-g-C8PhEO10Ac在水溶液中自组装,形成球型胶束,随着浓度增大,趋向于形成更大的自组装体。     

Synthesis of amphiphilic graft copolymer with hydrophilic poly(acrylic acid) backbone and hydrophobic polystyrene side chains

A series of well-defined amphiphilic graft copolymers consisting hydrophilic poly(acrylic acid) backbones and hydrophobic polystyrene side chains were synthesized by successive atom transfer radical polymerization (ATRP) followed by hydrolysis of poly(methoxymethyl acrylate) (PMOMA) backbone. Grafting-from strategy was employed for the synthesis of graft copolymers with narrow molecular weight distribution. Hydrophobic side chains were connected to the backbone through stable C-C bonds. The backbone can be easily hydrolyzed with HCl without affecting hydrophobic side chains. This family of amphiphilic graft copolymers can form stable micelles in water. The critical micelle concentration was determined by fluorescence spectroscopy. The micellar morphologies and sizes were studied using transmission electron microscopy (TEM) and dynamic light scattering (DLS). The sizes of micelles were dependent on ionic strength, pH value and preparation conditions.     

Synthesis and characterization of pH-sensitivity semi-IPN hydrogel based on hydrogen bond between poly(N-vinylpyrrolidone) and poly(acrylic acid)

A novel spherically shaped semi-interpenetrating network (semi-IPN) hydrogel, which is based on hydrogen bond between chemical crosslinked poly(N-vinylpyrrolidone) (PVP) and linear poly(acrylic acid) (PAA), was prepared. The semi-IPN hydrogel was synthesized by three steps: (1) linear PAA with different molecular weights were obtained by a reaction of free radical polymerization used 2,2′-azo-bis-iso-butyronitrile (AIBN) as an initiator; (2) crosslinked PVP bead was obtained by a reaction of N-vinylpyrrolidone with AIBN used as an initiator and N,N′-methylene-bis-acrylamide (NNMBA) used as a crosslinker by the way of suspension polymerization; (3) complexation occurred between suitable amount of aqueous solution of PAA and the porous PVP bead and was stabilized by multiple frost-defrost, from this step the semi-IPN hydrogel was obtained. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) proved the presence of the hydrogen bond in the hydrogel. The swelling behaviour of the hydrogel was studied in buffer solution with different pH and NaCl aqueous solution. The results showed that the semi-IPN hydrogel had excellent pH-sensitivity in the range of pH from 2.25 to 4.00 and the small molecule salt had little influence on the swelling behaviour of the semi-IPN hydrogel over the range of concentration of NaCl aqueous solution investigated. The results were confirmed further by scanning electron microscope (SEM). The mechanism of swelling and deswelling was discussed.     

Synthesis and characterization of amphiphilic graft copolymer poly(ethylene oxide)-graft-poly(methyl acrylate)

A novel well-defined amphiphilic graft copolymer of poly(ethylene oxide) as main chain and poly(methyl acrylate) as graft chains is successfully prepared by combination of anionic copolymerization with atom transfer radical polymerization (ATRP). The glycidol is protected by ethyl vinyl ether first, then obtained 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) is copolymerized with EO by initiation of mixture of diphenylmethyl potassium and triethylene glycol to give the well-defined poly(EO-co-EPEE), the latter is deprotected in the acidic conditions, then the recovered copolymer [(poly(EO-co-Gly)] with multi-pending hydroxyls is esterified with 2-bromoisobutyryl bromide to produce the ATRP macroinitiator with multi-pending activated bromides [poly(EO-co-Gly)_(ATRP)] to initiate the polymerization of methyl acrylate (MA). The object products and intermediates are characterized by NMR, MALDI-TOF-MS, FT-IR, and SEC in detail. In solution polymerization, the molecular weight distribution of the graft copolymers is rather narrow (M_w/M_n < 1.2), and the linear dependence of Ln [M₀]/[M] on time demonstrates that the MA polymerization is well controlled.     

Crystallization and vitrification effect in a poly(styrene)-g-poly(ethylene oxide) graft copolymer

Crystallization and solid state structure of a poly(styrene)-graft-poly(ethylene oxide) (PS-g-PEO) graft copolymer with crystallizable side chains were studied using simultaneous small angle X-ray scattering/wide angle X-ray scattering/differential scanning calorimetry (SAXS/WAXS/DSC). It is found that the glass transition temperature (T_g) of PS main chain is remarkably higher than that of PS homopolymer. The start cooling temperature (T_o) has a great influence on crystallization of the PEO side-chain. When the graft copolymer is cooled from the temperature above T_g, phase separation is suppressed due to the low mobility of the PS main chain and the homogeneous melt is vitrified. The unfavorable conformation of the rigid main chain results in a single crystallization peak and lower crystallinity. When PS-g-PEO is only heated to a temperature lower than the T_g and then cooled, phase separation is retained. Both the PEO side chains with high and low crystallizability can crystallize in the phase-separated state, leading to double crystallization peaks and higher crystallinity. The effect of solvent on crystallization of the graft copolymer was also examined. It is observed that addition of toluene reduces the T_g of the PS main chain and leads to the disappearance of the vitrification effect.     

N-1-alkylitaconamic acids-co-styrene copolymers. Surface characterization

A serie of six N-1-alkylitaconamic acids-co-styrene copolymers with alkyl groups varying in side chain length from 3 to 12 was used in this study. The surface behaviour of the copolymers has been studied as function of the side chain length. Contact angle data for two of these copolymer surfaces were obtained in water and several liquids. From this information the surface energy was determined. Differences in the wettability of N-1-alkylitaconamic acid-co-styrene are found. The results are discussed in terms of hydrophobic and polar effect of the copolymers. Results on spread monolayers characteristics of these copolymers on water surfaces are also reported. Surface pressure-area (π-A) isotherms on a pure water subphase exhibit a transition region depending on the length of the alkyl side chain of the itaconamic acid moiety. It was also analyzed the phase transition in the monolayer at the air/water interface by brewster angle microscopy (BAM). Molecular mechanics approach was used to obtain predictions about the local interaction energies between segments. It was possible to conclude that the local interaction energies of propyl and decyl derivatives are quite similar while the hexyl derivative has higher interaction energy. The analysis of the coulombic energies together with the dispersion van der Waals energies (VDW) would be indicative, in first approximation, that carbonyl groups are more exposed in the case of propyl than in the other copolymers studied.     

Aggregation of biodegradable amphiphilic poly(succinimide-co-N-propyl aspartamide) and poly(N-dodecyl aspartamide-co-N-propyl aspartamide) in aqueous medium and its preliminary drug-released properties

Two series of biodegradable amphiphilic copolymers, poly(succinimide-co-N-propyl aspartamide) (PSI-PA) and poly(N-dodecyl aspartamide-co-N-propyl aspartamide) (PDDA-PA) were synthesized by partial and total aminolysis of polysuccinimide (PSI), respectively. PSI-PA copolymers could self-aggregate in water directly under ultrasonication at room temperature. Differing from PSI-PA copolymers, the aggregates of PDDA-PA need to add PDDA-PA DMF solution into an excessive amount of water. The aggregative properties of PSI-PA and PDDA-PA copolymers have been investigated by dynamic light scattering (DLS) and surface tension measurements. Hydrophilicity of these two copolymers was attributed to the N-propyl aspartamide segments. Due to the stiff structure, succinimide segments preferred to form irregular hydrophobic microdomains, and some aggregates of PSI-PA are bimodal size distribution in water medium, while the more flexible PDDA-PA copolymer chains preferred to form monodispersed spherical aggregates. Elevated temperature could reduce the aggregate size of both PSI-PA and PDDA-PA copolymers due to the breaking of the hydrogen bonding and the releasing of the bonded water molecules. PSI-PA copolymers were surface active, while the surface tension of PDDA-PA copolymers was independent on concentration. The drug-loaded aggregates of PSI-PA also have been prepared and the preliminary release properties have been studied in vitro.     

Nanostructures from photo-cross-linked amphiphilic poly(ethylene oxide)-b-alkyl diblock copolymers

Poly(ethylene oxide) monomethylether was functionalized by alkyl chains of various lengths (l=10-19 methylene groups) bearing a polymerizable methacrylate moiety. Each synthesis step on the polymer gives quantitative functionalization rates. The self-assembly of the amphiphilic polymers in water was studied by light scattering for various end-groups. Sterical and polar effects were shown to influence the micellization step. The cores of the micelles formed by PEO-C_l-methacrylate were irreversibly cross-linked by UV irradiation. Star polymers that are stable under dilution in good solvent are obtained after 1-min irradiation. The hydrodynamic radius and the molar mass of the nanoparticles depend on the amount of photoinitiator introduced in the cores.     

Synthesis of amphiphilic poly(phthalazinone ether sulfone ketone)‐graft‐poly(ethylene glycol) graft copolymers via Williamson etherification

Amphiphilic graft copolymers consisting of poly(phthalazinone ether sulfone ketone) (PPESK) backbones and poly(ethylene glycol) (PEG) side chains were synthesized via reaction of chloromethylated PPESK (CMPPESK) with a sodium alkoxide of methoxyl PEG (PEG‐ ONa). The reactive precursor, CMPPESK, was prepared by the chloromethylation of PPESK with chloromethylether (CME) using concentrated H₂SO₄ as reaction medium. FTIR spectroscopy, ¹H‐NMR and Solid‐state ¹³C CP‐MAS NMR analysis confirmed the covalent linking of PEG with PPESK backbones. The PEG content in the graft copolymers from ¹H‐NMR analysis varied from 21.0 to 37.2 wt %, which was approximately in agreement with that calculated from TGA tests. The graft products have good solubility in many aprotic polar solvents and can be slightly swelled by water and ethanol, but water insoluble. Contact angle measurements revealed that the hydrophilicity of PPESK was significantly improved by the introduction of PEG graft chains, indicating the graft copolymer is a potential hydrophilic additive for PPESK membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Synthesis and characterization of amphiphilic graft copolymers with poly(ethylene glycol) and cholesterol side chains

Amphiphilic graft copolymers comprising monomeric units of methoxy poly(ethylene glycol) (mPEG)-acrylate, 2-hydroxyethyl methacrylate (HEMA)–cholesterol conjugates and HEMA were synthesized and their properties characterized. The value of the critical micelle concentration (CMC) for these copolymers is linearly proportional to the ratio of the number of mPEG–acrylates to that of the HEMA–cholesterol conjugates per macromolecule (N_PEG/N_c), which is the most important parameter which influences the formation of polymeric micelles. The latter show excellent colloidal stability and their sizes decrease with increasing CMC. Based on the quenching of pyrene fluorescence, the relatively high levels of the loading capacity of pyrene are attributed to the elevated hydrophobicity of the micelle core. The loading capacity of pyrene decreases with increasing CMC. The weight-average partition coefficient for pyrene in polymeric micelles increases with increasing polymer concentration because more micelles are available for accommodating pyrene. Copyright © 2004 Society of Chemical Industry     

两亲性聚乙烯醇-b-聚苯乙烯嵌段共聚物的合成及表征

采用原子转移自由基聚合(ATRP)法合成了具有两亲性的聚乙烯醇-b-聚苯乙烯嵌段共聚物P(VA-b-St)。首先利用调聚反应制备了带三氯甲基端基的聚醋酸乙烯大分子引发剂。以联二吡啶作配体、氯化亚铜为催化剂,引发苯乙烯单体聚合,得到结构明确的P(VAc-b-St)嵌段共聚物,而后通过皂化反应将其水解,从而得到两亲性嵌段共聚物P(VA-b- St);产物采用FT-IR、1H NMR、GPC等方法进行结构表征。P(VA-b-St)在不同浓度溶剂中的自组装行为用TEM进行了观察,结果表明:P(VA-b-St)可在DMF溶剂中形成球状囊泡结构,其尺寸达到纳米级。     

Studies on water-swellable elastomers. II. Thermal properties and crystalline behavior of amphiphilic graft copolymers with poly(ethylene glycol) side chains

The thermal properties and crystalline structure of the amphiphilic graft copolymers CR-g-PEG600, CR-g-PEG2000, and CR-g-PEG6000 using chloroprene rubber (CR) as the hydrophobic backbone and poly (ethylene glycol) (PEG) with different molecular weights as the hydrophilic side chains were studied by DSC and WAXD. The results showed that a distinct phase-separated structure existed in CR-g-PEGs because of the incompatibility between the backbone segments and the side-chain segments. For all the polymers studied, T_m2, which is the melting point of PEG crystalline domains in CR-g-PEG, decreased compared to that of the corresponding pure PEG and varied little with PEG content. For CR-g-PEG600 and CR-g-PEG2000, T_m1, which is the melting point of the CR crystalline domains, increased with increasing PEG content when the PEG content was not high enough, and at constant PEG content, the longer were the PEG side chains the higher was the T_m1. The crystallite size L_o11 of CR in CR-g-PEGs increased compared to that of the pure CR and decreased with increasing PEG content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2441–2447, 1997     

Synthesis and characterization of an amphiphilic graft copolymer with a poly(acrylic acid) backbone and n-octylphenyl polyoxyethylene side chains

A novel, well-defined, amphiphilic graft copolymer was synthesized by the free-radical copolymerization of acrylic acid and an amphiphilic macromonomer, n-octylphenyl polyoxyethylene acrylate. This acrylic copolymer was characterized by IR and ¹H-NMR. The number-average molecular weight was determined by gel permeation chromatography to be 4.37 × 10⁴ (weight-average molecular weight/number-average molecular weight = 1.23). The graft copolymer exhibited good solubility in water and high surface activity at much lower concentrations. The molecules of the AA–C₈PhEO₁₀Ac copolymer formed polymolecular micelles at 3.0 × 10⁻⁴ g/mL. The aggregation of the copolymer was examined in aqueous solution by measurement of the fluorescence of 2-p- toluidinylnaphthalene 6-sulfonate as a fluorescent probe. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of acrylic acid grafted poly(ethylene terephthalate) fabric

The preirradiation grafting of acrylic acid (AA) onto poly(ethylene terephthalate) (PET) had been found to affect the thermal and physical characteristics of fabric. The grafted fabrics with various graft levels were characterized by thermal gravimetric analysis (TGA), ATR‐FTIR spectroscopy, contact angle, differential scanning calorimetry (DSC), X‐ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The initial decomposition temperature and T₅₀ were increased with the increase in degree of grafting. The percentage crystallinity was decreased as the degree of grafting increases. The detailed elemental analysis was done by X‐ray photoelectron spectroscopy (XPS). The atomic ratio (O_1s/C_1s) was found to increase significantly with increasing the degree of grafting and reached 0.64 at 14.5% grafting from 0.38 for virgin PET. The surface topography and morphology was strongly influenced as the degree of grafting was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization behavior and morphological characterization of poly(ether ether ketone)

The crystal structure and morphology of poly(ether ether ketone) (PEEK) was investigated using standard differential scanning calorimetry (DSC), flash DSC, optical microscopy, atomic force microscopy, and small angle X-ray scattering tools. The flash DSC results suggested that the double melting peaks phenomenon observed in conventional DSC work originated from the reorganization of PEEK crystals, which was due to the much faster recrystallization rate of PEEK than the DSC heating and cooling rate. A refined crystallization model to describe PEEK crystal structure formation was proposed. The refined crystallization model could help reconcile the discrepancy found between the bulk crystallinity measured by DSC and the linear crystallinity obtained from SAXS experiments by taking into account possible variation in crystal perfection within the lamellar structure. Simplified molecular dynamic modeling was carried out to support this model. Implications of the above findings to the fundamental understanding of structure–property relationships in PEEK were discussed.