Reactive melt blending of PS‐POSS hybrid nanocomposites

Hybrid nanocomposites of polystyrene (PS) and methacryl phenyl polyhedral oligomeric silsesquioxane (POSS) were synthesized by reactive melt blending in the mixing chamber of a torque rheometer using dicumyl peroxide (DCP) as a free radical initiator and styrene monomer as a chain transfer agent. The effects of mixing intensity and composition on the molecular structure and morphology of the PS‐POSS hybrid nanocomposites were investigated. The degree of POSS hybridization (α_POSS) was found to increase with the POSS content, DCP/POSS ratio, and rotor speed. For the PS‐POSS materials processed in the absence of styrene monomer, an increase in the α_POSS led to a reduction in the molecular weight by PS chain scission, as a consequence of the free radical initiation. On the other hand, the use of styrene monomer as a chain transfer agent reduces the steric hindrance in the hybridization reaction between POSS and PS, enhancing the degree of POSS hybridization and avoiding PS degradation. The PS‐POSS morphology consists of nanoscale POSS clusters and particles and microscale crystalline POSS aggregates. PS‐POSS with higher α_POSS values and lower amounts of nonbound POSS showed improved POSS dispersion, characterized by smaller interfacial thickness (t) and greater Porod inhomogeneity lengths (l_p). The processing‐molecular structure–morphology correlations analyzed in this study allow the POSS dispersion level in the PS‐POSS materials to be tuned by controlling the reactive melt blending through the choice of the processing conditions. These insights are very useful for the development of PS‐POSS materials with optimized performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Studies on thermal and dielectric properties of organo clay and octakis (dimethylsiloxypropylglycidylether) silsesquioxane filled polybenzoxazine hybrid nanocomposites

Two types of polybenzoxazine (PBZ) hybrid nanocomposites were prepared from new type of benzoxazine monomer (BZ‐Cy‐OH) and organo‐modified MMT clay (OMMT) and octakis (dimethylsiloxypropylglycidylether) silsesquioxane (OG‐POSS) (up to 7.5 wt%). The new BZ‐Cy‐OH prepared from trans‐4‐aminocyclohexanol hydrochloride and 37% formaldehyde solution with 1,1‐bis (3‐methyl‐4‐hydroxy phenyl) cyclohexane and its structure was conformed by FTIR and NMR (¹H and ¹³C) spectral studies. The thermal properties of the resulting hybrid PBZ nanocomposites were studied by using differential scanning calorimetric and thermogravimetric analysis. Comparative study revealed on the data from the DSC analysis, the newly synthesized BZ‐Cy‐OH started ring opening polymerization at the lower temperature than that of the conventional benzoxazine (Ba‐A). The dispersion of OMMT clay in the PBZ was confirmed by X‐ray diffraction analysis. The homogeneous morphology of the hybrid nanocomposites was studied by using scanning electron microscope and transmission electron microscope analysis. By comparing the dielectric properties of organoclay and POSS filled PBZ nanocomposites, it was observed that the POSS filled PBZ showed low dielectic constant and in the case of organoclay filled PBZ possessed high dielectric constant. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Study of surface‐functionalized nano‐SiO2/polybenzoxazine composites

A series of the surface‐functionalized nano‐SiO₂/polybenzoxazine (PBOZ) composites was produced, and an attempt was made to improve the toughness of PBOZ material, without sacrificing other mechanical and thermal properties. A benzoxazine functional silane coupling agent was synthesized to modify the surface of nano‐SiO₂ particles, which were then mixed with benzoxazine monomers to produce the nano‐SiO₂‐PBOZ nanocomposites. The notched impact strength and the bending strength of the nano‐SiO₂‐PBOZ nanocomposites increase 40% and 50%, respectively, only with the addition of 3 wt % nano‐SiO₂. At the same load of nano‐SiO₂, the nano‐SiO₂‐PBOZ nanocomposites exhibit the highest storage modulus and glass‐transition temperature by dynamic viscoelastic analysis. Moreover, the thermal stability of the SiO₂/PBOZ nanocomposites was enhanced, as explored by the thermogravimetric analysis. The 5% weight loss temperatures increased with the nano‐SiO₂ content and were from 368°C (of the neat PBOZ) to 379°C or 405°C (of the neat PBOZ) to 426°C in air or nitrogen with additional 3 wt % nano‐SiO₂. The weight residue of the same nanocomposite was as high as 50% in nitrogen at 800°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

POSS/PMMA纳米复合材料的制备及性能研究

采用八乙烯基倍半硅氧烷(OV-POSS)通过原位聚合法制备了具有交联网状结构的POSS/PMMA纳米复合材料。通过FT-IR、DSC等方法对纳米复合材料的结构和性能进行了表征。结果表明,通过原位聚合法制备的POSS/PMMA纳米复合材料具有交联网状结构,POSS的引入能明显改善材料介电性能和热学性能,但当OV-POSS含量较高时,热学性能有所下降。当POSS的用量为0.6%时,POSS/PMMA纳米复合材料的介电常数从2.91降低至2.77,介电损耗从0.0088降低至0.0039,复合材料的Tg也上升了。     

Synthesis and characterization of poly(HEMA‐co‐MMA)‐g‐POSS nanocomposites by combination of reversible addition fragmentation chain transfer polymerization and click chemistry

New hybrid poly(hydroxyethyl methacrylate‐co‐methyl methacrylate)‐g‐polyhedral oligosilsesquioxane [poly(HEMA‐co‐MMA)‐g‐POSS] nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry using a grafting to protocol. Initially, the random copolymer poly(HEMA‐co‐MMA) was prepared by RAFT polymerization of HEMA and MMA. Alkynyl side groups were introduced onto the polymeric backbones by esterification reaction between 4‐pentynoic acid and the hydroxyl groups on poly(HEMA‐co‐MMA). Azide‐substituted POSS (POSS? N₃) was prepared by the reaction of chloropropyl‐heptaisobutyl‐substituted POSS with NaN₃. The click reaction of poly(HEMA‐co‐MMA)‐alkyne and POSS? N₃ using CuBr/PMDEATA as a catalyst afforded poly(HEMA‐co‐MMA)‐g‐POSS. The structure of the organic/inorganic hybrid material was investigated by Fourier transformed infrared, ¹H‐NMR, and ²⁹Si‐NMR. The elemental mapping analysis of the hybrid using X‐ray photoelectron spectroscopy and EDX also suggest the formation of poly(HEMA‐co‐MMA)‐anchored POSS nanocomposites. The XRD spectrum of the nanocomposites gives evidence that the incorporation of POSS moiety leads to a hybrid physical structure. The morphological feature of the hybrid nanocomposites as captured by field emission scanning electron microscopy and transmission electron microscopic analyses indicate that a thick layer of polymer brushes was immobilized on the POSS cubic nanostructures. The gel permeation chromatography analysis of poly(HEMA‐co‐MMA) and poly(HEMA‐co‐MMA)‐g‐POSS further suggests the preparation of nanocomposites by the combination of RAFT and click chemistry. The thermogravimetric analysis revealed that the thermal property of the poly(HEMA‐co‐MMA) copolymer was significantly improved by the inclusion of POSS in the copolymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of ethylene/POSS copolymer with rac‐Et(Ind)2ZrCl2 catalyst

The various monovinyl‐functional polyhedral oligomeric silsesquioxane (POSS) monomers had been copolymerized with ethylene (E) using rac‐Et(Ind)₂ZrCl₂ and a modified methylaluminoxane (MMAO) cocatalyst. The unreacted POSS monomer could be removed completely by washing the copolymerization product with n‐hexane. And the copolymers were characterized with ¹H NMR, TEM, DSC, TGA, and GPC to know the composition, thermal properties, molecular weight and its distribution, respectively. According to ¹H NMR data, the monomer reactivity ratios of various POSS monomers were calculated by the Fineman‐Ross and Kelen‐Tudos methods. Thermogravimetric analysis of E/POSS copolymers exhibited an improved thermal stability with a higher degradation temperature and char yields, demonstrating that the inclusion of inorganic POSS nanoparticles made the organic polymer matrix more thermally robust. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS)

A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional benzoxazine POSS (MBZ-POSS) with benzoxazine monomers (Pa and Ba) at various compositional ratios. Octafunctional cubic silsesquioxane (MBZ-POSS) is used as a curing agent, which is synthesized from eight organic benzoxazine tethers through hydrosilylation of vinyl-terminated benzoxazine monomer (VP-a) with octakis(dimethylsiloxy)silsesquioxane () using a platinum complex catalyst (Pt-dvs). Incorporation of the silsesquioxane core into polybenzoxazine matrix could significantly hinder the mobility of polymer chains and enhance the thermal stability of these hybrid materials. For these nanocomposites, increasing the POSS content in the hybrids is expected to improve its thermal properties with respect to the neat polybenzoxazine. The morphology feature is useful to explain the thermal property changes (T_g and T_d) and AFM images show that the presence of POSS aggregation in larger scales occurs at higher POSS contents. The reason of the heterogeneous phase separation may be from the less compatibility of the inorganic silsesquioxane core with organic benzoxazine species and the homopolymerization of MBZ-POSS. In the course of the formation of the polybenzoxazine/POSS hybrids, POSS particles were separated from the polybenzoxazine rich region, leading to POSS rich domains in the range of 50-1000 nm.     

POSS/PMMA纳米复合材料的制备及性能

将笼形纳米粒子八己烯基多面低聚倍半硅氧烷(Oh-POSS)与聚甲基丙烯酸甲酯(PMMA)通过溶液共混法制备无机/有机纳米复合材料.利用FTIR对复合材料的结构进行表征.SEM观察结果显示:当Oh-POSS含量较小时,复合材料薄膜具有较为平整的表面,无机粒子Oh-POSS均匀地分散在PMMA基体之中;随着Oh-POSS含量的增加,Oh-POSS逐步发生聚集现象.TGA、DSC以及拉伸试验结果表明:Oh-POSS含量较低时,Oh-POSS的引入能明显改善材料的热稳定性和力学性能,但当Oh-POSS含量较高时,热学和力学性能下降.     

Preparation of polyacrylate‐clay nanocomposites by in‐situ polymerization and heterocoagulation

Polyacrylate‐clay nanocomposites were prepared by an in situ polymerization method followed by heterocoagulation. In the heterocoagulation method, a cationic polyacrylate emulsion was prepared by emulsion polymerization using a cationic initiator in the presence/absence of free surfactant, cetyl trimethylammonium bromide (CTABr), followed by mixing with an aqueous clay slurry. WAXD results and TEM images suggest that morphologies of these nanocomposites depend on preparation method, mixing method, and the amount of free surfactant. TG‐DTG analyses demonstrate the improvement in thermal stability of these nanocomposites, while DSC results indicate no significant changes in glass transition temperature of these nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3850–3855, 2006     

Preparation and characterization of high char yield polybenzoxazine/polyarylacetylene blends for resin‐transfer molding

Benzoxazine precursors (BOZP), 6,6′‐bis(2,3‐dihydro‐3‐(3‐ethynylphenyl)‐4H‐1,3‐ benzoxazinyl)ketone and 6,6′‐bis(2,3‐dihydro‐3‐(3‐ethynylphenyl)‐4H‐1,3‐benzoxazinyl)ether were synthesized and characterized by Proton nuclear magnetic resonace (¹H‐NMR) and Fourier transform infrared spectroscopy (FTIR). The polyarylacetylene (PAA) was synthesized through thermal polymerization of diethynylbenzene, and characterized by ¹H‐NMR, FTIR, and Differential Scanning Calorimetry (DSC). The BOZP/PAA blends were prepared with different contents of PAA, and their viscosity was measured using NDJ‐79 rotating visometer. The curing behavior of BOZP/PAA blends was characterized by DSC. The thermal stability of cured BOZP/PAA blends was studied using Thermogravimetric Analysis, the results show char yield at 800°C was in the range of 78–84%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterizations of a vinyl-terminated benzoxazine monomer and its blending with polyhedral oligomeric silsesquioxane (POSS)

Benzoxazine was synthesized through the Mannich condensation of phenol, formaldehyde, and primary amines through ring-opening polymerization. Polybenzoxazines are phenolic-like materials that possess dimensional and thermal stability, and they release no toxic byproducts during their polymerization. To further improve the thermal stability of polybenzoxazines, a hydrosilane-functionalized polyhedral oligomeric silsesquioxane (H-POSS) was incorporated into the vinyl-terminated benzoxazine monomer (VB-a) which we then subjected to ring-opening polymerization. In addition, we also prepared hybrids from a non-reactive POSS (IB-POSS) and VB-a. The glass transition temperature (T_g) of a regular polymerized VB-a (i.e. PVB-a) is 307 °C, while the hybrid containing 5 wt% of H-POSS is 333 °C. The IB-POSS modified PVB-a hybrids, in general, results in lower T_g than the pure PVB-a due to poor missibility.     

Kinetics analysis and physical properties of photocured silicate-based thiol-ene nanocomposites: The effects of vinyl POSS ene on the polymerization kinetics and physical properties of thiol-triallyl ether networks

The kinetics and thermal/physical properties of the trithiol-TAE (triallyl ether) system were measured with respect to increasing polyoligomeric silsesquioxane (POSS) concentrations in order to understand how the presence of POSS nanoparticles affects network formation at low loadings. Vinyl POSS monomer (vPOSS-Bu₄) with both vinyl and carboxylate pendant groups was synthesized via a thermally initiated, free-radical reaction to improve the compatibility of the inorganic particles with the trithiol and triallyl ether comomoners. Chemically modified vPOSS-Bu₄ particles were incorporated into the trithiol-TAE polymer networks by a thiol-ene free-radical photopolymerization at molar concentrations of 0, 1, and 5 ene mol%. The polymerization rates were analyzed using real-time FTIR and photo-DSC. The polymerization rates showed no significant changes with increasing vPOSS-Bu₄ concentration. Thermal analyses of the films by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) demonstrated that thermal stability improves without affecting T _g as the POSS concentration increased. Additionally, scratch resistance increased and flame spread decreased markedly with increasing POSS concentration for concentrations up to 5 mol% vPOSS-Bu₄.     

Electrospinning: A Novel Method to Incorporate POSS Into a Polymer Matrix

The effectiveness of electrospinning as a simple approach to disperse POSS into a polymer matrix at a nm‐level has been assessed. Electrospun and cast films were prepared by dissolving CA and epoxycyclohexylisobutyl POSS in the solvent mixture acetone/DMAc. The membranes were characterized by SEM, TEM and WAXD. Whereas films produced by casting showed µm‐sized POSS crystals, thus suggesting a small affinity between the polymer matrix and the POSS molecules, those prepared by electrospinning were characterized by a nanometric POSS distribution. This is explained by considering the peculiar solvent evaporation mechanism, occurring during the electrospinning process, which allows to produce nanofibers characterized by a silsesquioxane dispersion similar to that present in solution.

     

Preparation of poly(styrene‐co‐hexylacrylate)/cellulose whiskers nanocomposites via miniemulsion polymerization

A stable aqueous nanocomposite dispersion containing cellulose whiskers and a poly(styrene‐co‐hexylacrylate) matrix was prepared via miniemulsion polymerization. We were able to prepare a stable dispersion with a 20 wt % solid content and a cellulose whiskers content ranging from 1 up to 5 wt % based on polymer content. To avoid particle agglomeration leading to coagulum formation, the addition of a low amount of reactive silane, i.e., methacryloxypropyl triethoxysilane revealed to efficiently stabilize the dispersion. The nanocomposite dispersion was characterized using dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Films obtained by casting followed by water evaporation and particle coalescence were analyzed by differential scanning calorimetry, dynamic mechanical analysis, and tensile testing. At 5 wt % whiskers loading, an enhancement by 500% of the storage modulus above the glass transition was determined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties

A series of functional polyhedral oligomer silsesquioxnae (POSS)/polyimide (PI) nanocomposites were prepared using a two-step approach, first, the octa(aminophenyl)silsesquioxane (OAPS)/NMP solution was mixed with polyamic acid (PAA) solution prepared by reacting 4,4′-diaminodiphenylmethane and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride in NMP, and second, the polycondensation solution was treated by thermal imidization. The well-defined ‘hard particles’ (POSS) and the strong covalent bonds between the PI and the ‘hard particles’ lead to a significant improvement in the thermal mechanical properties of the resulting nanocomposites. The glass transition temperature dramatically increases while the coefficient of thermal expansion (CTE) decreases, owing to the significant increase of the cross-linking density in the PI-POSS nanocomposites. The thermal stability and mechanical property of the nanocomposites were also improved.     

Preparation and characterization of flame‐retardant melamine cyanurate/polyamide 6 nanocomposites by in situ polymerization

This article focuses on an improved method, i.e., improved in situ polymerization of ε‐caprolactam in the presence of melamine derivatives to prepare flame‐retardant melamine cyanurate/polyamide 6 (MCA/PA6) nanocomposites. The chemical structures of these synthetic flame retardant composites are characterized by Fourier‐transform infrared spectroscopy and X‐ray diffraction. Morphologies, mechanical properties, and thermal properties also are investigated by the use of transmission electron microscopy, mechanical testing apparatus, differential scanning calorimetry, and thermogravimetric analysis, respectively. Through transmission electron microscopy photographs, it can be found that the in situ‐formed MCA nanoparticles with diametric size of less than 50 nm are nanoscaled, highly uniformly dispersed in the PA6 matrix. These nanocomposites, which have good mechanical properties, can reach UL‐94 V‐0 rating at 1.6‐mm thickness even at a relatively low MCA loading level. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of EPDM/organomontmorillonite hybrid nanocomposites

Hybrid nanocomposites based on organophillic montmorillonite (MMT) and ethylene–propylene–diene rubber (EPDM) have been prepared by a melt compounding process. From analysis by X‐ray diffraction and transmission electron microscopy, the rubber molecules were found to be intercalated into the galleries of organoMMT and the silicate layers of organoMMT are uniformly dispersed as platelets of 50–80 nm thickness in the EPDM matrix. Dynamic mechanical studies reveal a strong rubber–filler interaction in the hybrid nanocomposite which is manifested in the lowering of tan δ at the glass transition temperature. The hybrid nanocomposites exhibit great improvement in tensile and tear strength, and modulus, as well as elongation‐at‐break. Moreover, the permeability of oxygen for the hybrid nanocomposite was reduced remarkably. © 2002 Society of Chemical Industry     

Synthesis and characterization of a novel siloxane‐imide‐containing polybenzoxazine

A novel siloxane‐imide‐containing polybenzoxazine based on N,N′‐bis(N‐phenyl‐3,4‐dihydro‐2H‐benzo[1,3]oxazine)‐5, 5′‐bis(1,1′,3,3′‐tetramethyldisiloxane‐1,3‐diyl)‐bis(norborane‐2,3‐dicarboximide) (BZ‐A1) was successfully synthesized. The thermal properties of BZ‐A1 are superior to those of conventional polybenzoxazines lacking siloxane groups. Polymerized BZ‐A1 possesses extremely low surface free energy (γ_s = 15.1 mJ m^?2) after curing at 230 °C for 1 h. Moreover, the surface free energy of polymerized BZ‐A1 is more stable than conventional bisphenol A‐type polybenzoxazine during thermal curing and annealing processes, indicating that polymerized BZ‐A1 is more suitable for applications requiring low surface free energy materials for high temperatures over long periods of time. Copyright © 2010 Society of Chemical Industry     

POSS/聚合物有机-无机杂化材料的研究进展

介绍了笼型倍半硅氧烷(POSS)的特点。综述了POSS/聚合物杂化材料近年来的研究进展(包括POSS/环氧树脂杂化材料、POSS/聚酰亚胺杂化材料、POSS/有机硅杂化材料、POSS/聚乙烯杂化材料、POSS/聚丙烯杂化材料和其他类型含POSS的杂化材料等),并对其应用前景进行了展望。