Modification of the structure and properties of poly(vinylidene fluoride–trifluoroethylene) 56/44 mol % copolymer by a proton‐irradiation treatment

The effects of high‐energy proton irradiation on the structure and properties of 56/44 mol % poly(vinylidene fluoride–trifluoroethylene) copolymer were studied with differential scanning calorimetry (DSC), X‐ray diffraction (XRD), relative permittivity, and polarization hysteresis measurements. Copolymer films prepared by hot compression molding were irradiated with a broad range of proton dosages (10–107 Mrad) at room temperature. The DSC results showed that the ferroelectric transition was strongly affected by the proton dosages. The XRD data indicated the reduction of polar ordering in the copolymer by the proton‐irradiation treatment. From the relative permittivity and polarization behavior, the copolymer film was found to be converted from a normal ferroelectric material to a relaxor ferroelectric material as the proton dosage was increased to 50 Mrad. The electrostrictive coefficient of the 56/44 mol % copolymer was enhanced after irradiation, and the optimized proton dosage for attaining the highest electrostrictive strain response was determined. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2334–2339, 2005     

Poly(ethylene terephthalate) copolymers containing 5‐nitroisophthalic units. II. Crystallization studies

The microstructure and crystallization behavior of a set of poly(ethylene terephthalate‐co‐5‐nitroisophthalate) copolymers (PETNI) containing 5‐nitroisophthalic units in the 10–50 mol % range were examined and compared to those of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) copolymers. A ¹³C NMR analysis of PETNI copolymers in a trifluoroacetic acid solution indicates that they are random copolymers with average sequence lengths in accordance with ideal polycondensation statistics. Differential scanning calorimetry (DSC) studies show that PETNI containing 5‐nitroisophthalic units up to 20 mol % are able to crystallize and that crystallization takes place in these copolymers at much slower rates than in PET. Wide‐angle X‐ray diffraction from powder and fibers reveals that crystallizable PETNI adopts the same triclinic crystal structure as PET, with the nitroisophthalate units being excluded from crystallites. Fourier transform infrared in combination with cross‐polarization/magic‐angle spinning ¹³C NMR spectroscopy demonstrates the occurrence of a gauche–trans conversion encompassing the crystallization process. A correlation between DSC and spectroscopic data leads us to conclude that the content of trans conformer in the noncrystallized phase of PETNI is higher than in both PET and PETI copolymers and suggests that secondary crystallization in the homopolymer must proceed by a mechanism different than that in copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1553–1564, 2001     

Thin poly(ionic liquid) and poly(vinylidene fluoride) blend films with ferro‐ and piezo‐electric polar γ‐crystals

Ferro‐ and piezo‐electric poly(vinylidene fluoride) (PVDF) thin film is reported to be obtained by using a poly(ionic liquid) (PIL) [poly(2‐(dimethylamino)ethyl methacrylate) methyl chloride quaternary salt] through solution route. The short range interactions between localized cationic ions of PIL and polar >CF₂ of PVDF are responsible for modified polar γ‐PVDF (T₃GT₃Ḡ) formation. Modification in chain conformation of PVDF is confirmed by FTIR, XRD, and DSC studies suggesting the miscible PVDF–PIL (PPIL) blend. Up to 40 wt % loading of PIL in PVDF matrix enhances relative intensity of γ‐phase up to 50% in the entire crystalline phase. The P‐E hysteresis loop of PVDF‐PIL blends at 25 wt % PIL loading (PPIL‐25) thin film at sweep voltage of ±50 V shows excellent ferroelectric property with nearly saturated high remnant polarization ∼6.0 µC cm⁻² owing to large proportion of γ‐PVDF. However, non‐polar pure PVDF thin film shows unsaturated hysteresis loop with 1.4 µC cm⁻² remnant polarization. The operation voltage decreases effectively because of the polar γ‐phase formation in PPIL blended film. High‐sensitivity piezo‐response force microscopy shows electromechanical switching property at low voltages in PPIL‐25 thin films through local switching measurements, making them potentially suitable as ferroelectric tunnel barriers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 795–802     

Ferroelectric behavior and structural change of poly(trimethylene terephthalate) induced by external electric field

The ferroelectric behavior and structural change induced by the external electric field were observed for poly(trimethylene terephthalate) (PTT), which has nonpolar crystalline structure with carbonyl groups aligned antiparallel to each other. The displacement‐electric field hysteresis curves of PTT films showed hysteresis above 140 °C, which indicated the polarization reversal of PTT. The pyroelectric constant and thermally stimulated depolarization current suggest the depolarization of the polar structure of PTT induced by the external electric field above 150 °C. An endothermic peak caused by the depolarization was also observed in the differential scanning calorimetry for the PTT film poled at 30 MV/m. The change of the crystalline structure and the orientation of carbonyl groups induced by the electric filed were investigated by X‐ray diffraction patterns and infrared spectra. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1991–1996, 2009     

Crystallization behavior and morphology of poly(ethylene‐co‐trimethylene terephthalate)s

The melt crystallization behaviors and crystalline structures of poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate), and poly(ethylene‐co‐trimethylene terephthalate) (PETT) were investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction at various crystallization temperatures (T_cs). The PETT copolymers were synthesized via the polycondensation of terephthalate with ethylene glycol and trimethylene glycol (TG) in various compositions. The copolymers with 69.0 mol % or more TG or 31.0 mol % or less TG were crystallizable, but the other copolymers containing 34–56 mol % TG were amorphous. The DSC isothermal results revealed that the addition of a small amount of flexible TG (up to 21 mol %) to the PET structure slightly reduced the formation of three‐dimensional spherulites. A greater TG concentration (91–100%) in the copolyesters changed the crystal growth from two‐dimensional to three‐dimensional. The DSC heating scans after the completion of isothermal crystallization at various T_cs showed three melting endotherms for PET, PETT‐88, PETT‐84, and PETT‐79 and four melting endotherms for PETT‐9 and PETT. The presence of an additional melting endotherm could be attributed to the melting of thinner and imperfect copolyester crystallites. Analyses of the Lauritzen–Hoffman equation demonstrated that PETT‐88 had the highest values of the product of the lateral and folding surface free energies, and this suggested that the addition of small amounts of flexible trimethylene terephthalate segments to PET disturbed chain regularity, thus increasing molecular chain mobility. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4255–4271, 2004     

Micro‐phase‐separation behavior of amphiphilic polyurethanes involving poly(ethylene oxide) and poly(tetramethylene oxide)

The temperature dependence of thermal, morphological, and rheological properties of amphiphilic polyurethanes was examined with differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), rheological measurements, and Fourier transform infrared spectroscopy. Multiblock (MPU) and triblock (TPU) polyurethanes were synthesized with two crystallizable segments—poly(ethylene oxide) (PEO) as a hydrophilic block and poly(tetramethylene oxide) (PTMO) as a hydrophobic block. DSC and WAXS measurements demonstrated that the microphase of MPUs in the solid state is dominantly affected by the PEO crystalline phase. However, high‐order peaks were not observed in the SAXS measurements because the crystallization of the PEO segments in MPUs was retarded by poor sequence regularity. The microphase in the melt state was induced by the hydrogen bonding between the N? H group of hexamethylene diisocyanate linkers and the ether oxygen of PEO or PTMO blocks. As the temperature increased, the smaller micro‐phase‐separated domains were merged into the larger domains, and the liquidlike ordering was eventually disrupted because of the weakening hydrogen bonding. However, the fully homogeneous state of an MPU with a molar ratio of 5/5 PEO/PTMO (MPU55) was not confirmed even at much higher temperatures with both SAXS and rheological measurements. However, the SAXS patterns of TPU showed weak but broad second‐order peaks below the melting temperature of the PEO block. Compared with MPU55, the ordering of the TPU crystalline lamellar stacks was enhanced because of the high sequence regularity and the low hydrogen‐bonding density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2365–2374, 2003     

Self‐organized liquid‐crystalline polyethers obtained by grafting tapered mesogenic groups onto poly(epichlorohydrin): Toward biomimetic ion channels

A set of high‐molecular‐weight new side‐chain liquid‐crystalline polyethers was obtained by chemical modification of poly(epichlorohydrin) with potassium 3,4,5‐tris(dodecyloxy)benzoate. The degree of modification ranged from 48 to 70% depending on the reaction conditions, and the upper value was an apparent modification plateau. NMR characterization indicated that no side reactions of any kind occurred (e.g., deshydrohalogenation). All copolymers had a nematic columnar mesophase whose range of stability depended on the modification degree. X‐ray diffraction experiments performed on mechanically oriented samples showed that tapered groups were tilted with respect to the column axes. Also X‐ray experiments and density measurements demonstrated that the number of disks per unit cell decreased as the modification degree increased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2918–2929, 2003     

Side‐chain crystallization behavior of graft copolymers consisting of amorphous main chain and crystalline side chains: Poly(methyl methacrylate)‐graft‐poly(ethylene glycol) and poly(methyl acrylate)‐graft‐poly(ethylene glycol)

Graft copolymers consisting of amorphous main chain, poly(methyl methacrylate) (PMMA), or poly(methyl acrylate) (PMAc), and crystalline side chains, poly(ethylene glycol) (PEG), have been prepared by copolymerization of PEG macromonomers with methyl methacrylate or methyl acrylate (MMAx or MACx, respectively). Because of the compatibility of PMMA/PEG and PMAc/PEG, from small‐angle X‐ray scattering results, the main and side chains in graft copolymers were suggested to be homogeneous in the molten state. Differential scanning calorimetry (DSC) cooling scans revealed that PEG side chains for graft copolymers with large PEG fractions were crystallized when the sample was cooled, with a cooling rate of 10 °C/min. The spherulite pattern observed by a polarized optical microscope suggested the growth of PEG crystalline lamellae. Crystallization of PEG in MMAx was more restrained than in MACx. From these results, we have concluded that the crystallization behavior of the grafted side chains is strongly influenced by the glass transition of a homogeneously molten sample as well as dilution of the crystallizable chains. Domain spacings for isothermally crystallized graft copolymers were described by interdigitating chain packing in crystalline–amorphous lamellar structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 79–86, 2005     

Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004     

(2‐Hydroxy isobutyric) acid containing poly(glycolic acid): Structure–properties relationship

Poly(glycolic acid) (PGA) and a series of novel random copolymers of PGA containing 2‐hydroxyisobutyrric acid (PGAPHIB) (HIB unit content from 1.5 to 7.4 mol %) were synthesized and characterized in terms of chemical structure and molecular weight. Afterward, the polyesters were examined by thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction techniques. The copolymers, which displayed a better thermal stability than PGA, at room temperature appeared as semicrystalline materials: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of the melting temperature with respect to homopolymer PGA. Baur's equation described well the T_m‐composition data. X‐ray diffraction measurements allowed the identification of the PGA crystalline structure in all cases. After melt quenching, semicrystalline samples were obtained with the exception of PGAPHIB7.4 copolymer. The introduction of HIB units decreased the crystallization rate compared with pure PGA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1901–1910, 2010     

Investigation by combined solid‐state NMR and SAXS methods of the morphology and domain size in polystyrene‐b‐polyethylene oxide‐b‐polystyrene triblock copolymers

The microphase structure of a series of polystyrene‐b‐polyethylene oxide‐b‐polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid‐state NMR, DSC, wide and small angle X‐ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene‐oxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and ¹H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 55–64, 2010     

Synthesis and characterization of biodegradable triblock copolymers based on bacterial poly[(R)‐3‐hydroxybutyrate] by atom transfer radical polymerization

Biodegradable poly(tert‐butyl acrylate)–poly[(R)‐3‐hydroxybutyrate]–poly (tert‐butyl acrylate) triblock copolymers based on bacterial poly[(R)‐3‐hydroxybutyrate] (PHB) were synthesized by atom transfer radical polymerization. The chain architectures of the triblock copolymers were confirmed by ¹H NMR and ¹³C NMR spectra. Gel permeation chromatography analysis was used to estimate the molecular weight characteristics and lengths of the PHB and poly(tert‐butyl acrylate) blocks of the copolymers. The thermal properties of the copolymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA showed that the triblock copolymers underwent stepwise thermal degradation and had better thermal stability than their respective homopolymers, whereas DSC analyses showed that a microphase‐separation structure was formed only in the triblock copolymers with the longer PHB block. As a similar result, from wide‐angle X‐ray diffraction experimentation, the crystalline phase of PHB could not be seen evidently in the triblock copolymers with the shorter PHB block. The enzymatic hydrolysis of the copolymer films was carried at 37 °C and pH 7.4 in a potassium phosphate buffer with an extracellular PHB depolymerase from Penicillum sp. The biodegradability of the triblock copolymers increased with an increase in the PHB block content. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4857–4869, 2005     

Effect of incorporated CdS nanoparticles on the crystallinity and morphology of poly(styrene‐b‐ethylene oxide) diblock copolymers

Surface‐modified CdS nanoparticles selectively dispersed in hexagonally packed poly(ethylene oxide) (PEO) cylinders of poly(styrene‐b‐ethylene oxide) (PSEO) block copolymers were prepared. The photoluminescence and ultraviolet–visible characteristics of the presynthesized CdS nanoparticles in N,N‐dimethylformamide and in PEO domains of the PSEO block copolymers were determined. Because of strong interactions between the CdS nanoparticles and PEO chains, as shown by Fourier transform infrared spectroscopy, the incorporation of the CdS nanoparticles prevented the PEO cylinders from properly crystallizing; this was confirmed by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. The intercylinder distance between the swollen and reduced‐crystallinity CdS/PEO cylinders in turn increased, as confirmed by small‐angle X‐ray scattering and transmission electron microscopy. At a high CdS concentration (43 wt % or 8.3 vol % with respect to PEO), however, the hexagonally packed cylindrical nanostructure of the PSEO diblock copolymers was destroyed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1220–1229, 2005     

Real‐time SAXS and WAXS study of the multiple melting behavior of poly(ε‐caprolactone)

The multiple melting behavior of poly(ε‐caprolactone) (PCL) was investigated by real‐time small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) measurements coupling with differential scanning calorimetry (DSC). Semicrystalline specimens prepared by a continuous cooling process showed lengthening of the Bragg period during the progress of double melting. A model of variable thickness of lamella was proposed to fit to the SAXS patterns and revealed that both the crystalline lamella and the amorphous layer contributed to the increase in Bragg period while the later dominated the contribution. The model of variable thickness although satisfied the SAXS data was unable to compromise the data from other probing tools. A modification of the model proposed that each lamella piling up to construct the stacks in the crystallites was itself nonuniform in thickness. The modification with the parallel occurrence of the mechanism of surface melting and crystallization successfully compromised the observations from SAXS, DSC, and optical microscopy and provided a new perspective for the explanation to lengthening of the Bragg period related to multiple melting behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1777–1785, 2010     

Biodegradable electrospun mat: Novel block copolymer of poly (p‐dioxanone‐co‐L‐lactide)‐block‐poly(ethylene glycol)

Ultrafine fibers of a laboratory‐synthesized new biodegradable poly(p‐dioxanone‐co‐L ‐lactide)‐block‐poly(ethylene glycol) copolymer were electrospun from solution and collected as a nonwoven mat. The structure and morphology of the electrospun membrane were investigated by scanning electron microscopy, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and a mercury porosimeter. Solutions of the copolymer, ranging in the lactide fraction from 60 to 80 mol % in copolymer composition, were readily electrospun at room temperature from solutions up to 20 wt % in methylene chloride. We demonstrate the ability to control the fiber diameter of the copolymer as a function of solution concentration with dimethylformamide as a cosolvent. DSC and WAXD results showed the relatively poor crystallinity of the electrospun copolymer fiber. Electrospun copolymer membrane was applied for the hydrolytic degradation in phosphate buffer solution (pH = 7.5) at 37 °C. Preliminary results of the hydrolytic degradation demonstrated the degradation rate of the electrospun membrane was slower than that of the corresponding copolymers of cast film. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1955–1964, 2003     

Synthesis and characterization of electrically conducting poly(o‐/m‐toluidine‐co‐o‐/m‐aminoacetophenone) copolymers

A series of poly(o‐/m‐toluidine‐co‐o‐/m‐aminoacetophenone) copolymers combining the features of high conductivity and processibility are synthesized and characterized by a number of techniques including ¹H NMR; thermogravimetry; IR, Raman, and UV–visible spectroscopy; scanning electron microscopy; and X‐ray diffraction. The copolymers are synthesized by the emulsion and inverse emulsion methods using conventional ammonium persulfate and a new oxidant, benzoyl peroxide, respectively. The influence of the polymerization conditions such as the monomer feed ratios, solvent, and the nonsolvent is investigated. The composition of the resulting copolymers is determined by ¹H NMR analysis. The conductivity of the copolymers varies with the aminoacetophenone content in the feed and the polymerization conditions. It is interesting that the conductivity of the copolymers is higher than that of the corresponding homopolymers. The results are rationalized on the basis of the effect of the ? COCH₃ substituent on the polymer structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4300–4310, 2004     

All hydrocarbon main‐chain thermotropic liquid crystalline polymers,poly(1,1′‐biphenylene‐4,4′‐alkenediyl)s,prepared by the ADMET method and their hydrogenated polymers,poly(1,1′‐biphenylene‐4,4′‐alkanediyl)s

A series of poly(4,4′‐biphenylenealkenylene)s and copolymers were prepared by the acyclic diene metathesis (ADMET) polymerization of 4,4′‐bis(alkenylene)1,1′‐biphenyls. Unsaturated polymers thus prepared were then hydrogenated to produce the corresponding saturated polymers. All the polymers were found to be thermotropic and to form solidlike smectic phases in melt. Their liquid crystallinity (LC) was studied by differential scanning calorimetry (DSC), X‐ray diffractometry, and polarizing microscopy. We observed that one of the phenylene units of the biphenyl structure could selectively be hydrogenated at an elevated temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1335–1349, 2004     

Synthesis and characterization of new segmented polyurethanes with side‐chain,liquid‐crystalline chain extenders

Liquid‐crystalline, segmented polyurethanes with methoxy–biphenyl mesogens pendant on the chain extender were synthesized by the conventional prepolymer technique and esterification reaction. Two, side‐chain, liquid‐crystalline (SCLC) polyurethanes with mesogens having spacers of six and eight methylene units were prepared. The structures of the mesogenic units and SCLC polyurethanes were confirmed by Fourier transform infrared spectroscopy and ¹H NMR. Polymer properties were also examined by solubility tests, water uptakes, and inherent viscosity measurements. Differential scanning calorimetry studies indicated that the transition temperature of the isotropic to the liquid‐crystalline phase decreased with increasing spacer length. Wide‐angle X‐ray diffraction (WAXD) studies revealed the existence of liquid‐crystalline phases for both SCLC polyurethanes. Polarized optical microscopic investigations further confirmed the thermotropic liquid‐crystalline behaviors and nematic mesophases of both samples. Thermogravimetric analysis displayed better thermal stabilities for both SCLC polymers and indicated that the presence of mesogenic side chains may increase the thermal stability of segmented polyurethanes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 290–302, 2004     

Synthesis of semifluorinated block copolymers by atom transfer radical polymerization

Two sets of styrene‐based semifluorinated block copolymers, one with a perfluoroether pendant group and another with a perfluoroalkyl group, were synthesized by atom transfer radical polymerization. Microphase separation of the block copolymers was established by small‐angle X‐ray scattering and differential scanning calorimetry (DSC). DSC measurements also showed that the perfluoroether‐based polymer had a low glass‐transition temperature (?44 °C). Contact‐angle measurements indicated that the semifluorinated block copolymers had low surface energies (ca. 13 mJ/m²). These materials hold promise as low‐surface‐energy additives or surfactants for supercritical CO₂ applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 853–861, 2004     

Synthesis and characterization of a poly(GMA)‐graft‐poly(Z‐L‐lysine) graft copolymer with a rod‐like structure

This study applied the macromonomers and glycidyl methacrylate (GMA) to synthesize a series of the graft copolymers, poly(GMA)‐graft‐poly(Z‐L ‐lysine), and investigated the conformation of the graft copolymer. The graft copolymers were synthesized with different GMA monomer ratios (28 to 89%) and different degrees of polymerization (DP) (8 to 15) of the poly(Z‐L ‐lysine) side chain to analyze secondary structure relationships. Atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and both wide angle and small angle X‐ray scattering spectroscopy (WAXS, SAXS) were used to investigate the relationship between the microstructure and conformation of the graft copolymers and the different monomer ratios and side chain DP. In AFM images, n8‐G89 (the graft copolymer containing 89% GMA units and the macromonomer DP is 8) showed tiny and uniform rod‐like structures, and n14‐G43 (the graft copolymer containing 43% GMA units and the macromonomer DP is 14) showed uniform rod‐like structures. FTIR spectra of the graft copolymers showed that the variations of α‐helix and β‐sheet secondary structures in the graft copolymers relate to the monomer ratios of the graft copolymers. However, the X‐ray scattering patterns indicated that the graft copolymer conformations were mainly dependent on the poly(Z‐L ‐lysine) side chain length, and these results were completely in accordance with the AFM images. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4655–4669, 2009