The synthesis, characterization and biocompatibility of poly(ester urethane)/polyhedral oligomeric silesquioxane nanocomposites

The primary goal of this study is to develop a facile and inexpensive synthesis method for a new biodegradable and biocompatible poly(ester urethane) (PEU)/polyhedral oligomeric silesquioxanes (POSS) nanocomposite via in situ homogeneous solution polymerization reaction into prescribed macromolecular structure and properties including improved biocompatibility, thermal and hydrolytic stability, and stiffness and strength. Cell culture studies, nuclear magnetic resonance spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetry, and dynamic mechanical analysis measurements were used to confirm the structure and property improvements. The results show that the targeted PEU/POSS nanocomposites (which are remarkably different from conventional polymers, polymer nanocomposites and microcomposites) have significant improvements in mechanical properties and degradation resistance at small POSS concentrations (≤6 wt%). The nanocomposites exhibited excellent support for cell growth without any toxicity. POSS concentration did not affect cell adhesion or cell growth, but it significantly changed the surface structure of the PEU into a 3-dimensional matrix with regular pores that may allow cells to better access the growth factors/nutrients, waste exchange, and tissue remodeling. The PEU/POSS nanocomposites were resistant to degradation over a period of six months when exposed to a buffer solution. These desirable characteristics suggest that the nanocomposites may hold great promise for future high-end uses such as in biomedical devices, especially at cardiovascular interfaces.     

Mechanical Properties, Biodegradation and Water Vapor Permeability of Blend Films of Soy Protein Isolate and Poly (vinyl alcohol) Compatibilized by Glycerol

Summary Novel blend films of soy protein isolate (SPI) and poly(vinyl alcohol) (PVA) compatibilized by glycerol were fabricated by preparing a solution, and then casting it on a Teflon-coated metal sheet. Mechanical, biodegradation and water vapor permeability of the blend properties were systematically investigated with various methods. SEM analysis results release that the SPI/PVA/glycerol film degrades at a slower rate than pure SPI. The mechanical test showed that the stress at yield point, stress at break point and Young’s modulus were decreased and percentage elongation at yield point and percentage elongation at break point and of SPI/PVA were increased obviously than pure SPI films. The blend plastics were softened and became semi-rigid contributing to the plasticization of glycerol and the crystalline partion of PVA was destroyed by glycerol. Water vapor permeability of SPI/PVA/glycerol showed the minimum at the component of SPI/PVA (100/35) compatibilized by 3.5% of glycerol.     

Degradation and stabilization of cosmetic polyetherurethane in alcoholic solution

A polyetherurethane (PEU) was synthesized for potential cosmetic applications by coupling poly(tetramethylene oxide) (PTMO, M_n = 2000 g mol^?1) and poly(ethylene oxide) (PEO, M_n = 2000 g mol^?1) with 4,4′‐diphenylmethane diisocyanate (MDI), without using a chain extender. The PEU polymer, synthesized with PEO and PTMO in the ratio of 1:3 by weight, was soluble in ethanol–water mixed solvents. The solution formed a thin film in situ on the skin by coating, which was flexible and elastomeric with appropriate skin adhesiveness. However, PEU was susceptible to degradation when it was exposed to an ethanol–water (80/20 v/v %) mixed solvent and stored in an air‐filled and sealed bottle at 60°C for 4 weeks. These conditions resulted in deterioration of PEU molecular weight (M_n), viscosity, and mechanical properties. Peak analysis of the Fourier transform infrared spectrum of the aged PEU revealed that >97% of the urethane carbonyl bonds remained, whereas ether bonds were significantly reduced (～82% of initial value). The degraded PEU contained ester bonds, which were confirmed by proton and carbon‐13 nuclear magnetic resonance spectroscopy. This observation suggests that oxidative chain cleavage rather than hydrolysis was the dominant reaction in the degradation process. Two approaches were adopted to minimize oxidative degradation of PEU dissolved in an ethanol–water (80/20 v/v %) mixed solvent; they were, applying a nitrogen environment and adding an antioxidant (1.8 wt % dry PEU). The results indicate that reduction of oxidative degradation produced a synergistic effect. Vitamin E was a more effective antioxidant than butylated hydroxytoluene (BHT), which is a typical antioxidant for commercial polyurethanes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2270–2276, 2003     

Morphology and size control of inorganic particles in polyimide hybrids by using SiO2-TiO2 mixed oxide

Polyimide/inorganic hybrids were prepared by sol-gel reaction starting from tetraethoxysilane (TEOS), and tetrabutyl titanate (TBT) in the solution of polyamic acid in N,N-dimethylformamide. The hybrid films were obtained by the hydrolysis-polycondensation of TEOS and TBT in polyamic acid solution, followed by the elimination of solvents and imidization process. Binary polyimide/SiO₂ and polyimide/TiO₂ hybrids, as well as ternary polyimide/SiO₂-TiO₂ hybrids (with varied ratio of SiO₂ to TiO₂) were prepared to study the effects of the recipes and inorganic components on the morphologies of the polyimide hybrids. Transparent films with much higher inorganic content can be obtained in ternary polyimide hybrids, while lower inorganic content in binary hybrids. The results also indicate that the inorganic particles are much smaller in the ternary systems than in the binary systems, the shape of the inorganic particles and the compatibility for polyimide and inorganic moieties are varied with the ratio of the inorganic moieties in the hybrids. The completely imidization temperature of the polyamic acid was delayed, and furthermore, the thermal stability of polyimide was enhanced through the incorporation of the inorganic moieties in the hybrid materials.     

Poly(ethylene-oxide)/clay/silica nanocomposites: Morphology and thermomechanical properties

Poly(ethylene-oxide) PEO/clay/silica nanocomposites were prepared via solution intercalation by exploiting phase separation based on the bridging of particles by polymer chains. The intercalated morphology of nanocomposites was confirmed by XRD. Vibrational modes of the ether oxygen of PEO in the hybrids are shifted due to the coordination of the ether oxygen with the sodium cations of clay and the H-bonding interactions of the ether oxygen with the surface silanols of hydrophilic fumed silica. Based on SEM, the overall density of nanoparticle aggregates in the interspherulitic region was observed to be higher compared to that inside spherulites. PEO/clay/silica hybrids show significant property improvements compared to PEO/clay hybrids and pure PEO. The system containing 10 wt.% clay and 5 wt.% silica has substantially higher modulus and much lower crystallinity compared to the 15 wt.% clay system. The physics behind the reinforcement effect and the reduction of crystallinity as a function of fumed silica loading is discussed based on the morphological characterization of the hybrids. Lastly, PEO/clay/silica hybrids display good thermal stability and are much stiffer compared to pure PEO and PEO/clay nanocomposites.     

A novel biodegradable multiblock poly(ester urethane) containing poly(l-lactic acid) and poly(butylene succinate) blocks

A novel biodegradable multiblock poly(ester urethane) (PEU), consisting of poly(l-lactic acid) (PLLA) and poly(butylene succinate) (PBS) blocks, has been successfully synthesized via chain-extension reaction of dihydroxyl terminated PLLA (PLLA-OH) and PBS prepolymers (PBS-OH) using toluene-2,4-diisocyanate (TDI) as a chain extender. The chemical structures and molecular weights of PEUs, containing different block lengths and weight fractions of PLLA and PBS, were characterized by ¹H NMR and GPC. The effects of the structures on the physical properties of PEUs were systematically studied by means of DSC, TGA, WAXD and tensile testing. The DSC results indicated that PLLA segment was compatible well with PBS segment in amorphous phase and the crystallization of PEU was predominantly caused by PBS segment, which was also confirmed by WAXD. The results of tensile testing showed that the extensibility of PLLA was largely improved by incorporating PBS segment. The PEU can be used as a potential substitute for some petroleum-based thermoplastics.     

Blend membranes prepared from cellulose and soy protein isolate in NaOH/thiourea aqueous solution

We have successfully prepared a series of blend membranes from cellulose and soy protein isolate (SPI) in NaOH/thiourea aqueous solution by coagulating with 5 wt % H₂SO₄ aqueous solution. The structure and properties of the membranes were characterized by Fourier transform infrared spectroscopy, ultraviolet‐visible spectrometry, dynamic mechanical thermal analysis, scanning electron microscopy (SEM), transmission electron microscopy, and tensile testing. The effects of SPI content (W_SPI) on the structure and properties of the blend membranes were investigated. The results revealed that SPI and cellulose are miscible in a good or a certain extent when the SPI content is less than 40 wt %. The pore structure and properties of the blend membranes were significantly improved by incorporation of SPI into cellulose. With an increase in W_SPI from 10 to 50 wt %, the apparent size of the pore (2r_e) measured by SEM for the blend membranes increased from 115 nm to 2.43 μm, and the pore size (2r_f) measured by the flow rate method increased from 43 to 59 nm. The tensile strength (σ_b) and thermal stability of the blend membranes with lower than 40 wt % of W_SPI are higher than that of the pure cellulose membrane, owing to the strong interaction between SPI and cellulose. The values of tensile strength and elongation at break for the blend membranes with 10 wt % of W_SPI reached 136 MPa and 12%, respectively. The blend membranes containing protein can be used in water because of keeping σ of 10 to 37 MPa. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 748–757, 2004     

Silicone-containing polymer blend electrolyte membranes for fuel cell applications

Polymer electrolyte membranes are developed from blends of chemically durable silicone-containing epoxy (Si-Epoxy) and proton conducting sulfonic polyimide (SPI). A charge-transfer (CT) complex is formed between electron-donating dihydroxynaphthalene units in Si-Epoxy, and electron-accepting naphthalenediimide units in SPI, as confirmed via X-ray diffraction and visible spectroscopy. The blend membranes show comparable mechanical strength to Nafion 211, but the elongation to break is much lower, indicating better resistance to deformation under strain stress, attributed to CT complex formation. The chemical durability of the blend membranes was much higher than pure SPI according to Fenton's test, also attributed to CT complex formation. Meanwhile, the proton conductivity is dependent on the sulfonic acid content of the SPI, which in turn affects the fuel cell performance. The maximum proton conductivity was measured to be 23.1 mS cm⁻¹ at 80°C and 90 %RH for a 1:1 blend, and the membranes were successfully incorporated into PEFCs.     

Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPO substituted organophosphorus oligomer

A series of flame-retardant epoxy resins (EP) with different content of poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) (PFR) were prepared. The PFR was synthesized via the polycondensation between 10-(2,5-dihydroxyl phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-BQ) and pentaerythritol diphosphonate dichloride (SPDPC). The structure of PFR was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance (¹H NMR). The flame retardancy and the thermal stability of the EP/PFR hybrids were investigated by limiting oxygen index (LOI) test and thermogravimetric analysis (TGA) in air. The results showed that the incorporation of PFR into EP can improve the thermal stability dramatically. The mechanical results demonstrated that PFR enhanced failure strain slightly accompanied by a decrease in tensile strength. The thermal oxidative degradation mechanisms of the EP/PFR hybrids were investigated by real time Fourier transform infrared spectra (RTFTIR) and direct pyrolysis/mass (DP-MS) analysis. X-ray photoelectron spectroscopy (XPS) was used to explore chemical components of the residual char of EP and EP/PFR hybrid. DP-MS analysis showed that the degradation process of EP/PFR hybrid was divided into two characteristic temperature regions, attributed to the decomposition of phosphate and aromatic structure.     

Polyacrylate/silica hybrids prepared by emulsifier-free emulsion polymerization and the sol–gel process

Polyacrylate/silica hybrids were prepared by emulsifier-free emulsion polymerization and the sol–gel process. The influence on the properties of polyacrylate/silica hybrids of the synthetic conditions, such as the dosage of polyvinyl alcohol, the ratio of the monomers, the dosage of tetraethoxysilane and the dosage of γ-methacryloxypropyltrimethoxysilane, was investigated. The hybrid material was characterized by Fourier transform infrared, differential scanning calorimeter, thermal gravimetric analyzer and dynamic light scattering. The results indicated that there were chemical bonds between SiO₂ and polyacrylate, that the thermal stability and the average diameter of polyacrylate emulsion particle increased with the incorporation of SiO₂, and that the glass transition temperature (T _g) of polyacrylate/SiO₂ was 8 °C higher compared with that of pure polyacrylate.     

Mechanical and surface properties of polyurethane/fluorinated multi‐walled carbon nanotubes composites

To improve the mechanical and surface properties of poly(etherurethane) (PEU), multi‐walled carbon nanotubes (MWCNTs) were surface grafted by 3,3,4,4, 5,5,6,6,7,7,8,8,8‐tridecafluoro‐1‐octanol (TDFOL) (MWCNT‐TDFOL) and used as reinforcing agent for PEU. Fourier‐transform infrared spectroscopy revealed the successful grafting of MWCNTs. PEU filled with MWCNT‐TDFOL could be well dispersed in tetrahydrofuran solution, and tensile stress–strain results and dynamic mechanical analysis showed a remarkable increase in mechanical properties of PEU by adding a small amount of MWCNT‐TDFOL. Contact angle testing displayed a limited improvement (just 9°) in the hydrophobicity of PEU surface by solution blending with MWCNT‐TDFOL. However, a large improvement of surface hydrophobicity was observed by directly depositing MWCNT‐TDFOL powder on PEU surface, and the water contact angle was increased from 80° to 138°. Our work demonstrated a new way for the modification of carbon nanotubes and for the property improvement of PEU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Catalytic and reinforcing effects of polyhedral oligomeric silsesquioxane (POSS)-imidazolium modified clay in an anhydride-cured epoxy

In this article, we report novel epoxy-based hybrids prepared via incorporating 1,2-dimethyl-3-(benzyl-heptaisobutyl-POSS) imidazolium chloride (POSS-IMC) and POSS-IMC-modified clay (POSS-MMT) into the resin based on 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECHM) and hexahydrophthalic anhydride (HHPA). We demonstrate that both POSS-IMC and POSS-MMT can reduce the cure temperature of the epoxy/anhydride system, and the catalyzing effect involves chemical reactions between POSS-IMC and ECHM/HHPA, which may lead to the attachment of POSS cages at chain ends. The incorporation of the POSS-IMC, free and ionically bonded in clay, gives rise to dissimilar morphologies that affect the thermo-mechanical properties of the hybrids. The ECHM/HHPA/POSS-IMC resin exhibits a slight improvement in glassy modulus as compared with the neat ECHM/HHPA resin, which is attributed to the formation of sub-micron and nano-sized POSS domains that act as physical cross-link points hindering polymer chain motions. The much enhanced reinforcing effect of POSS-MMT is ascribed to the effective stress transfer between the matrix and clay layers that may originate from the strong interactions between the pendent POSS in the network and POSS attached to the clay surfaces. Reduction in coefficient of thermal expansion (CTE) was also found for the hybrids.     

Copolymers of unsaturated and saturated poly(ether ester amide)s: Synthesis,characterization, and biodegradation

A series of biodegradable random unsaturated/saturated poly(ether ester amide)s copolymers (USPEEAs) were synthesized by an active solution polycondensation of unsaturated and saturated dicarboxylic acid‐based diester monomers with diamine salts of phenylalanine and saturated oligo(ethylene glycol) (OEG). These USPEEA copolymers were obtained with fairly good yields in DMA solvent. The chemical structures of the USPEEA copolymers were confirmed by both IR and NMR spectra. The molecular weights (M_n and M_w) of USPEEAs measured by GPC ranged from 3 to 27 kg/mol with the molecular weight distribution (MWD) ranging from 1.52 to 2.13. USPEEA copolymers obtained had T_g lower than that of the pure UPEEAs but higher than that of pure saturated poly(ether ester amide)s (SPEEA). An increase in the unsaturated component in USPEEAs led to an increase in their T_g. A preliminary in vitro biodegradation property of USPEEA copolymers were investigated in both pure PBS buffer and α‐chymotrypsin solutions. The USPEEA copolymers showed a pronounced weight loss in enzyme solutions, but a smaller weight loss in a pure PBS. The biodegradation rates of USPEEA copolymers in α‐chymotrypsin solution were much slower than those of pure PEEAs. Therefore, upon adjusting monomers feed ratio, USPEEA copolymers could have controlled chemical, physical, and biodegradation properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Role of Star‐Like Hydroxylpropyl Lignin in Soy‐Protein Plastics

Summary: Star‐like hydroxypropyl lignin (HL) was compounded into soy protein isolated (SPI) to develop a potential biodegradable plastic with better mechanical performance than pure sheet‐SPI. The structure and properties of the composite materials were characterized by WAXD, DSC, SEM, TEM and tensile tests. The addition of just 2 wt.‐% HL resulted in tensile strength (σ_b) of 16.8 MPa, 2.3 times that of pure sheet‐SPI, with no accompanying decrease in elongation at break as a result of strong interaction and with good miscibility among components. As the HL content increased, the HL molecules could self‐aggregate as oblate supramolecular domains, while the stronger interactions between HL and glycerol resulted in the detaching of glycerol from the SPI matrix. It can be concluded that the insertion of HL as single molecules into the SPI matrix would provide materials with optimum mechanical properties. Compared with other lignin/SPI composites, the stretching chains on HL play a key role in the improvement of mechanical properties because of a stronger adhesion of HL onto the SPI matrix as well as the interpenetration of SPI into supramolecular HL domains.

Schematic illustration of the supramolecular domain created by the aggregation of hydroxypropyl lignin, which can interpenetrate with soy protein isolate.     

Properties of soy protein isolate/poly(vinyl alcohol) blend “green” films: Compatibility,mechanical properties,and thermal stability

Blend films from nature soy protein isolates (SPI) and synthetical poly(vinyl alcohol) (PVA) compatibilized by glycerol were successfully fabricated by a solution‐casting method in this study. Properties of compatibility, mechanical properties, and thermal stability of SPI/PVA films were investigated based on the effect of the PVA concentration. XRD tests confirm that the SPI/PVA films were partially crystalline materials with peaks of 2θ = 20°. And, the addition of glycerol will insert the crystalline structure and destroy the blend microstructure of SPI/PVA. Differential scanning calorimetry (DSC) tests show that SPI/PVA blend polymers have a single glass transition temperature (T_g) between 80 and 115.0°C, which indicate that SPI and PVA have good compatibility. The tension tests show that SPI/PVA films exhibit both higher tensile strength (σ_b) and percentage elongation at break point (P.E.B.). Thermogravimetric analysis (TGA) and water solubility tests show that SPI/PVA blend polymer has more stable stability than pure SPI. All the results reflect that SPI/PVA/glycerol blend film provides a convenient and promising way to prepare soy protein plastics for practical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of ciprofloxacin hydrochloride loaded poly(ethylene glycol)/chitosan scaffold as wound dressing

A novel ciprofloxacin hydrochloride loaded chitosan/poly(ethylene glycol) (PEG) composite scaffold was developed for wound dressing application. PEG incorporation in chitosan scaffold showed enhanced loading up to 5.4 % and increased cumulative release of the drug up to 35 % as compared to pure chitosan scaffold (20 %). The drug loading and control release of the drug has been explained by the morphological features and drug–polymer/polymer–polymer interactions revealed by SEM, FTIR and DSC. Bacterial growth inhibition evaluation using Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus confirmed the efficacy of released drug from the scaffolds (pure and PEG mixed chitosan). Swelling study, bacterial penetration, moisture vapour transmission rate, haematocompatibility and biodegradation profile supported the suitability of scaffold used as wound dressing materials. In-vivo study on mice finally validated the controlled rate of drug release showing the effectiveness of PEG incorporation into the scaffold for quicker and regulated wound healing.     

Bio‐inspired “green” nanocomposite using hydroxyapatite synthesized from eggshell waste and soy protein

Eco‐friendly and inexpensive “ green” nanocomposites with enhanced functional performances were developed by combining nanoscale hydroxyapatite (HA) synthesized from eggshell waste (nEHA) and protein‐based polymer extracted from defatted soybean residues. nEHA was synthesized from chicken eggshells using an energy efficient microwave‐assisted wet chemical precipitation method. Transmission electron microscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy studies confirmed the nanometer scale (diameter: 4–14 nm and length: 5–100 nm) of calcium‐deficient (Ca/P ratio ～1.53) needle‐like HA. Uniform dispersion of nEHA in soy protein isolate (SPI) solution was obtained by modifying nEHA surface using a polyelectrolyte (sodium polyacrylate) dispersant via irreversible adsorption. Green nanocomposite films were prepared from SPI and surface‐modified nEHA with the help of a natural plasticizer “glycerol” by solution casting. Significant improvements in tensile modulus and strength were achieved owing to the inclusion of uniformly dispersed nEHA in SPI sheets. Overall, this work provides a green pathway of fabricating nanocomposites using naturally occurring renewable polymer and inorganic moieties from eggshell waste that emphasizes the possibilities for replacing some petroleum‐based polymers in packaging and other applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43477.     

Synthesis of polyaniline/montmorillonite nanocomposites with an enhanced anticorrosive performance

Polyaniline/montmorillonite (PANI/Mt) nanocomposites (1–7% (w/w) Mt based on the aniline content) were synthesized by in situ chemical oxidative polymerization with a 73.4–75.8% monomer conversion level. Fourier-transform infrared and scanning electron microscopy analyses confirmed the presence of Mt incorporation into PANI, whilst X-ray diffraction analysis revealed the exfoliated structure and that PANI was intercalated between the Mt layers. Thermogravimetric analysis revealed that the thermal properties of PANI and PANI/Mt composites were enhanced with increasing Mt levels.     

Synthesis of clay-armored coatable sulfonated polyimide nanocomposites as robust polyelectrolyte membranes

Herein, coatable sulfonated polyimide (SPI) and clay-reinforced SPI membranes SPI-clay 3%, SPI-clay 5%, and SPI-clay 7% were successfully fabricated by one-step high temperature via direct imidization method. The membranes were cast as a coatable thin film using a solution casting method and grafted vermiculite clay nanoparticle were incorporated into the neat SPI as reinforcement by the sonication method. Three different formulated nanocomposite membranes were investigated using different characterization techniques such as Fourier transform infrared spectroscopy as peaks at 1166 and 1227 cm⁻¹ confirmed successful sulfonation. In Proton (¹H) NMR synthesis of SPI confirmed as aromatic proton at 7.3–8.8 ppm depicts successful sulfonation and X-ray diffraction results confirmed the crystalline structure of clay, as its content increased (7%) clear diffraction peak arises at 6 and 25°. Scanning electron microscopy (SEM) provides information about surface morphology of clay reinforced SPI membranes, and SEM micrographs shown uniform dispersion of clay nanofillers and developed easy transfer of electron. Thermogravimetric analysis was performed to investigate the thermal stability of synthesized films, results of thermographs shown degradation in the range of 510–600°C. Different physicochemical parameters employed and their results show the effectiveness of synthesized clay reinforced SPI membranes. Water uptake (WU%) about 0.96%, hydrolytic about 98 h and oxidative stability up to 80°C, ions exchange capacity about 3.16 mmol/g for synthesized clay reinforced SPI membranes. Measurement regarding Dimensional changes was also investigated and dimensional changes (1.557 ∆t/∆l). All these results reveal that the clay-reinforced coatable SPI membranes are a promising material for polymer electrolyte membranes to be used in fuel cell energy applications.     

Synthesis and characterization of polypropylene-based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)

Isotactic polypropylene-based polymer hybrids linking poly(methyl methacrylate) (PMMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) were successfully synthesized by a graft copolymerization from maleic anhydride-modified polypropylene (PP-MAH). PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the thus obtained PP-OH was treated with 2-bromoisobutyryl bromide and converted to a 2-bromoisobutyryl group containing polypropylene (PP-Br). The metal-catalyzed radical polymerization of MMA with PP-Br was performed using a copper catalyst system in o-xylene solution at 100 °C to give the PP-based polymer hybrids linking PMMA segments (PP-PMMA hybrids). Thus obtained PP-PMMA hybrids demonstrated higher melting temperature than PP-Br and microphase-separation morphology at the nanometer level owing to the chemical linkage between both segments. On the other hand, the polymer hybrids linking PHEMA segment (PP-PHEMA hybrids) were also obtained by the radical polymerization of HEMA with PP-Br in o-xylene slurry at 25 °C. TEM observation suggested that the polymerization mainly initiated on the surface of the PP-Br powder, led to the peculiar core-shell-like morphology. These PP-PHEMA hybrid powders showed a good affinity with water due to the hydrophilicity of the PHEMA segments.