High temperature organic/inorganic addition cure polyimide composites,part 1: Matrix thermal properties

Structure‐thermal property interrelationships are characterized and reported for organic/inorganic addition cure polyimide composite matrices based on 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, the reactive terminal group 4‐phenylethynyl phthalic anhydride, and stoichiometric controlled diamine ratios of 1,3‐phenylenediamine, 1,4‐phenylenediamine, or 4,4′‐(1,3‐phenylenediisopropylidene) bisaniline, combined with bis(p‐aminophenoxy) dimethyl silane or an α, ω‐bis(3‐aminopropyl) polydimethylsiloxane oligomer. Polymerization of monomer reactants resin solutions, carbon fiber prepregs and composites, and imidized oligomers are characterized to relate molecular chemical structure and morphology to glass transition temperature, processing characteristics, thermodynamic properties, and thermal stability. Glass transition temperature, thermal decomposition temperature, and char yield were found to increase with increasing siloxane block length in the imide backbone. As the concentration of inorganic component in the imide oligomer backbone increased, the cured glass transition temperature decreased. Char yield and thermal decomposition temperature were observed to decrease as the inorganic component concentration increased. Incorporation of bis(p‐aminophenoxy) dimethyl silane into the imide oligomer structure did not provide any significant advantages over traditional polyimides relative to thermal properties or composite processing, but aminosiloxanes improved composite toughness, prepreg tack, and composite processability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of sulfonated poly(siloxane imide)s bearing dimethyl siloxane oligomers for fuel cell applications

A series of sulfonated poly(siloxane imide)s (SPSIs) were synthesized from 4,4′‐ketone dinaphthalene 1,1′,8,8′‐tetracarboxylic dianhydride (KDNTDA), a dimethyl siloxane oligomer‐based diamine, and a sulfonated diamine. The reduced viscosities ranged from 1.0 to 3.5 dL/g at 35°C in the triethylamine (TEA) salt form. The SPSIs showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity, thermal stability and good mechanical properties. The KDNTDA‐based SPSIs showed good solubility in common aprotic solvents not only in TEA salt form but also in proton form. The ¹H‐NMR results indicated that the molar content of the dimethyl siloxane oligomer in the SPSIs was 50–80% of that in the feed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermally initiated cationic polymerization and properties of epoxy siloxane

Difunctional epoxy siloxane monomers containing disiloxane, trisiloxane, and tetrasiloxane were prepared by hydrosilylation of an α,ω‐difunctional Si? H‐terminated siloxane with a vinyl‐functional epoxide. Cationic polymerization of these monomers using 3‐methyl‐2‐butenyltetramethylenesulfonium hexafluoroantimonate and their reactivities were examined. The reactivity order was disiloxane > trisiloxane > tetrasiloxane. Thermal discoloration of these polymers increased with catalyst concentration and also with the length of dimethyl siloxane. UV discoloration was also accelerated by catalyst. From the thermo gravimetric analysis, it was found that the thermal stabilities of polymers increased with increasing the length of dimethyl siloxane chain. Mechanical properties of polymers were also tested by thermal mechanical analysis and dynamic mechanical analysis, and it was found that the flexibility of polymers was increased with increasing siloxane chain length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2010–2019, 2006     

Synthesis and characterization of pyridine‐containing poly(imide‐siloxane)s and their adhesion to copper foil

A series of pyridine‐containing poly(imide‐siloxane) (PIS) copolymers with different amounts of PDMS with various segmental lengths were synthesized from 2,6‐diaminopyridine (DAP), α,ω′‐aminopropylpoly(dimethylsiloxane) (PDMS), 1,3‐bis(4‐aminophenoxy)benzene (APB), and 4,4′‐oxydiphthalic dianhydride (ODPA). A modified synthetic approach was applied instead of approaches commonly reported in the literature, to ensure the incorporation of DAP and PDMS. The effects of the content and the segmental length of PDMS on the thermal glass transition temperature (T_g), dielectric constant, and surface electrical resistivity of the copolymer are investigated. The copolymers were attached to copper foil by hot‐pressing, and changes in wettability caused the peel strength of the laminates to increase with the PDMS content, but to decrease as the DAP content increased. Furthermore, X‐ray photoelectron spectroscopy was employed to determine the loci of failures (LOF) of the laminates and to monitor the movement of LOF, which varies with the PDMS content. For those laminates with good peel strengths, the LOF occur in the interior of PIS layer, indicating that the adhesion is cohesive rather than adhesive. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis,characterization, and comparison of properties of novel fluorinated poly(imide siloxane) copolymers

Four new poly(imide siloxane) copolymers were prepared by a one‐pot solution imidization method at a reaction temperature of 180°C in ortho‐dichlorobenzene as a solvent. The polymers were made through the reaction of o‐diphthaleic anhydride with four different diamines—4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl, 4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl, 2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, and 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene—and aminopropyl‐terminated poly dimethylsiloxane as a comonomer. The polymers were named 1a , 1b , 1c , and 1d , respectively. The synthesized polymers showed good solubility in different organic solvents. The resulting polymers were well characterized with gel permeation chromatography, IR, and NMR techniques. ¹H‐NMR indicated that the siloxane loading was about 36%, although 40 wt % was attempted. ²⁹Si‐NMR confirmed that the low siloxane incorporation was due to a disproportionation reaction of the siloxane chain that resulted in a lowering of the siloxane block length. The films of these polymers showed low water absorption of 0.02% and a low dielectric constant of 2.38 at 1 MHz. These polyimides showed good thermal stability with decomposition temperatures (5% weight loss) up to 460°C in nitrogen. Transparent, thin films of these poly(imide siloxane)s exhibited tensile strengths up to 30 MPa and elongations at break up to 103%, which depended on the structure of the repeating unit. The rheological properties showed ease of processability for these polymers with no change in the melt viscosity with the temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of polyurethane modified with aminoethylaminopropyl poly(dimethyl siloxane)

A series of polyurethanes with different siloxane contents were synthesized, which were based on 4,4′‐methylene diphenyl diisocyanate (MDI), poly(tetramethylene oxide) (PTMO), aminoethylaminopropyl poly(dimethyl siloxane) (AEAPS), and butanediol (BD). The chemical compositions, structures, and bulk and surface properties were investigated using an infrared surface quantitative analysis technique (FTIR‐ATR), surface contact angle, electron spectroscopy for chemical analysis (ESCA), stress–strain analysis, and dynamic mechanical thermal analysis (DMTA). It was shown that siloxane concentration on the surface region of the elastormers was higher than that in the bulk for a resulting surface enrichment of the siloxane, and the tensile properties of these elastomers were not changed significantly with the AEAPS modification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2552–2558, 1999     

Effects of phosphate and polysiloxane on flame retardancy and impact toughening behavior of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO)‐based compounds containing resorcinol bis(diphenyl phosphate) (RDP) and poly(dimethyl‐diphenyl siloxane) (PDMDPS) were prepared through melt extrusion, and their flammability characteristics and mechanical properties were evaluated. The incorporation of RDP enhanced the flame retardancy of PPO compounds, but hardly made them obtain the UL 94 V‐0 rating unless RDP and PDMDPS were combined. Studies on the residual chars after vertical burning test suggested that the excellent flame retardancy be correlated with the retention from the combination effects of silica and phosphate in the char, whose cross‐linked silica enhanced the formation of a compact char to retard combustion. Thermogravimetric analysis indicated that the presence of PDMDPS and RDP improved the char yielding as well as the decomposition temperature of PPO compounds. Moreover, the Izod impact strength was improved significantly in the presence of RDP and PDMDPS, and this toughening effect was attributed to the deformation and multiple cracks induced by PDMDPS, which enhances the impact energy absorption of the matrix. This work provides a very effective flame retarding formulation for PPO compounds with improved impact toughness. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis and characterization of poly (imide–benzimidazole) hybrid nanocomposites using nano‐cluster of octa‐amino functionalized polyhedral oligomeric silsesquioxane

Poly (imide–benzimidazole)/polyhedral oligomeric silsesquioxane (POSS), nanocomposites were prepared by the reaction of the heterocyclic diamine monomer 2,2‐(1,2‐phenylene)‐bis(5‐aminobenzimidazole), octa(aminophenyl)silsesquioxane(OAPS), and benzophenonetetra carboxylic dianhydride (BTDA). The structure of the prepared monomers was confirmed by FTIR and NMR (²⁹Si, ¹H, and ¹³C) spectral studies. The thermal stability behavior of the poly (imide–benzimidazole) and poly (imide–benzimidazole)–POSS nanocomposite films were studied by differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). Dynamic mechanical analysis shows that the glass transition temperatures of the polyhedral oligomeric silsesquioxane (POSS) containing poly (imide–benzimidazole) nanocomposites are higher than that of the corresponding neat poly (imide–benzimidazole) systems. Decrease in the dielectric constant was observed with an increase in the determined amount of amino‐functionalized POSS in the poly (imide–benzimidazole) matrix. Further, the morphological studies were carried out by X‐ray diffraction and transmission electron microscopy. POLYM. COMPOS., 34:825–833, 2013. © 2013 Society of Plastics Engineers     

Mechanical and surface properties of polysulfide‐based polyurea modified with aminoethylaminopropyl poly(dimethylsiloxane)

A series of polysulfide‐based polyureas with different siloxane contents were synthesized, and they were based on isophorone diisocyanate, liquid polysulfide oligomer, aminoethylaminopropyl poly(dimethyl siloxane) (AEAPS), and 2,5‐diamino‐3,6‐dimethylmercapto‐toluene. The mechanical and surface properties were investigated with attenuated total reflectance Fourier transform infrared spectroscopy, surface contact angles, electron spectroscopy for chemical analysis, and stress–strain analysis. Siloxane was enriched on the surfaces of these elastomers, and the tensile properties of the elastomers did not change markedly with the AEAPS modification. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 584–588, 2003     

Anionic block copolymerization of cyclotetrasiloxanes initiated by 4,4'‐bis(dimethyllithiioxylsilyl)diphenyl ether

The anionic copolymerization of cyclotetrasiloxanes initiated by 4,4′‐bis(dimethyllithiioxylsilyl)diphenyl ether (BDMOLiPE) was carried out for the preparation of poly(diphenyl‐dimethyl‐diphenyl)siloxane block copolymers (PMP). To reduce redistribution reaction, the lithium‐based dianionic initiator (BDMOLiPE) was first used for the copolymerization of the cyclotetrasiloxane monomers without solvent, with dimethyl formamide (DMF) as a promotor. The cyclotetrasiloxanes used involved octamethylcyclotetrasiloxane (D₄), octaphenylcyclotetrasiloxane (P₄), and tetramethyl‐tetravinylcyclotetrasiloxane (V₄). The copolymers obtained were characterized withproton nuclear magnetic resonance spectroscopy, infrared spectroscopy, intrinsic viscosity([η]) determination, transmission electron microscopy, and wide‐angle X‐ray diffraction analysis. The results illustrate that the products should belong to block copolymers but not be too perfect because the block copolymers were scrambled to a certain extent during the copolymerization process. However, we can approximately express them as PMP and PMVP, according to the different order of the feeding in raw materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1203–1210, 2001     

New arylidene–siloxane polyethers: Liquid‐crystalline and photosensitive properties

By polycondensation reactions, starting from α, ω‐bis(chloromethyl)polydimethylsiloxanes with different molecular weights and 2,6‐bis(4‐hydroxybenzylidene)cyclohexanone, new polyethers were obtained. The structure of resulting polymers was confirmed by IR and ¹H‐NMR spectroscopy and their thermal properties and mesophase behavior were studied by TGA, DSC, and polarizing light microscopy. Depending on the length of the siloxane spacer, some of the obtained compounds exhibited thermotropic liquid‐crystalline properties. A possible smectic texture was investigated by X‐ray diffraction measurements at room temperature. A decrease of the transition temperatures values was observed as the spacer length increased. The photochemical behavior of the siloxane polyethers was studied by ultraviolet absorption spectroscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3093–3099, 2003     

Preparation and characterization of crosslinked polyurethane‐block‐poly(trifluoropropylmethyl)siloxane elastomers with potential biomedical applications

A series of crosslinked polyurethane‐block‐poly(trifluoropropylmethyl)siloxane elastomers were prepared via two steps. First, poly(trifluoropropylmethyl)siloxane polyurethane (FSPU) prepolymers were synthesized with α,ω‐bis(3‐aminopropyldiethoxylsilane) poly(trifluoropropylmethyl)siloxane (APFS) and toluenediisocyanate (TDI) and then capped with butanediol to generate the macromolecular FSPU diol extender. Second, polyurethane prepolymers synthesized from poly(tetramethylene oxide) and TDI were reacted with FSPU diol extenders with different ratios. The copolymers formed films through moisture curing and were characterized by Fourier transform infrared spectroscopy, DSC, dynamic mechanical analysis, TGA, mechanical testing etc. It is found that the equivalent ratio of reactants gives rise to a high molecular weight of copolymers and that low molecular weight APFS in the copolymers can form a certain number of silicon–oxygen crosslinks resulting from silicon alkoxy to produce higher tensile strength elastomers. The material thus has higher thermal stability and a more stable surface performance. The copolymers are then good candidates for biomedical applications.© 2013 Society of Chemical Industry     

Preparation and properties of crosslinked network coatings based on perfluoropolyether/poly(dimethyl siloxane)/acrylic polyols for marine fouling–release applications

α,ω‐Triethoxysilane terminated poly(dimethyl siloxane) (PDMS) oligomer, α,ω‐triethoxysilane terminated perfluoropolyether (PFPE) oligomer, and acrylic polyols were first synthesized via an addition reaction and free‐radical polymerization. Then, crosslinked network coatings based on PFPE/PDMS/acrylic polyols for marine fouling‐release applications were prepared by a condensation reaction. The structure of the crosslinked network coating was characterized by Fourier transform infrared spectroscopy. The chemical composition of the coating surface was characterized by X‐ray photoelectron spectroscopy. The thermal properties, surface energy, mechanical properties, adhesion, and antiseawater immersion performance of the coatings were systematically studied. The antibiofouling properties of the crosslinked network coating were evaluated by laboratory biofouling assays with the bacteria Escherichia coli and the fouling diatom Navicula. The results from the preliminary study suggested that this crosslinked network coating had good adhesion and promising antifouling properties that were comparable to a silicone standard. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41860.     

Effect of TiO2 on thermal and adhesive characteristics of poly(imide siloxane)/TiO2 hybrid films

A novel poly(imide siloxane)/titania (PIS/TiO₂) hybrid film was fabricated by sol‐gel process via in situ formation of TiO₂ within PIS matrix. Poly(amic acid siloxane) (PAAS) was prepared from 4,4′‐oxydiphthalic anhydride, 2,2‐bis [4‐(4‐aminophenoxy) phenyl] propane, and α,ω‐bis(3‐aminopropyl)polydimethylsiloxane (APPS). Chelating agent, acetylacetone, and catalyst‐free polymerization were used to reduce the rate of hydrolysis of titanium alkoxide in the PAAS. X‐ray photoelectron spectroscopy data showed that the presence of APPS promotes the Ti surface composition of PIS/TiO₂ hybrid film. The effects of TiO₂ and APPS contents on the characteristics of surface, thermostability, coefficient of thermal expansion (CTE), and the strength of adhesion were investigated. The presence of TiO₂ on the surface of the hybrid films enhanced the adhesive strength at the interface of PIS/TiO₂ hybrid film and copper foil. When more TiO₂ was incorporated into the PIS matrix, the PIS/TiO₂ hybrid film exhibited lower CTE while retaining favorable mechanical and thermal properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Formation of honeycomb‐patterned microporous films based on a fluorinated poly(siloxane imide) segmented copolymer

The preparation of honeycomb‐patterned microporous films from a soluble fluorinated poly(siloxane imide) segmented copolymer (PSI) by means of water‐droplet templating is reported first in this article. The fluorinated PSI was synthesized from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, and diamine‐terminated poly(dimethyl siloxane) by condensation polymerization. The obtained copolymer had good solubility in chlorinated solvents (chloroform, dichloromethane, and 1,2‐dichloroethane), good thermal stability, and a microphase‐separated amorphous structure. The effects of the copolymer concentration, atmospheric humidity, and solvent properties on the pattern formation were investigated. The results show that the film fabricated from the copolymer solution with chloroform as the solvent at a humidity of 90% and a concentration of 0.5 g/L had the most regular honeycomb‐patterned micropores. We could tailor the pore shape and size by changing the copolymer concentration or the atmospheric humidity. The prepared regular honeycomb‐patterned microporous PSI films have potential applications in cell culture and tissue engineering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New photosensitive poly(amid‐imide)s containing chalcone moiety and hydantoin derivatives in the main chain: Synthesis and characterization

Six new poly(amid‐imide)s containing chalchone and hydantoin moieties in the main chain were synthesized through the polycondensation reaction of 1,3‐bis[4,4′‐bis(trimellityimido)phenyl]‐2‐propenone 6 with six hydantoin derivatives 7a‐f in a medium consisting of triphenyl phosphite, calcium chloride, pyridine, and N‐methyl‐2‐pyrrolidone. The polycondensation reaction produced a series of novel poly(amid‐imide)s 8a‐f in high yields with inherent viscosities between 0.26 and 0.42 dL/g. The resulting polymers were characterized by elemental analysis, viscosity measurements, solubility test, thermo gravimetric analysis (TGA and DTG), FTIR, and UV‐Vis spectroscopy. 1,3‐bis[4,4′‐bis(trimellityimido)phenyl]‐2‐propenone 6 was prepared from a three‐step reaction by using 4‐nitro benzaldehyde 1 and 4‐nitro acetophenone 2 as precursors. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and physical properties of poly(l‐lactic acid)‐poly(dimethyl siloxane) multiblock copolymers prepared by direct polycondensation

Multiblock copolymers consisting of poly(l ‐lactic acid) and poly(dimethyl siloxane) were prepared by the polycondensation of oligo(l ‐lactic acid) (OLLA) with dihydroxyl‐terminated oligo(dimethyl siloxane) and dicarboxyl‐terminated oligo(dimethyl siloxane). Copolymers with number‐average molecular weights of 18,000?33,000 Da and various content ratios of oligo(dimethyl siloxane) (ODMS) unit were obtained by changing the feed ratio of these oligomers. A film prepared from the copolymer with an ODMS content ratio of 0.37 exhibited two independent peaks at ?107°C and 37°C in the mechanical loss tangent for temperature dependence, suggesting the formation of microphase separation between the OLLA and ODMS segments. The film had a tensile strength of 3.2 MPa and a high elongation of 132%. The film also exhibited a high strain recovery even after repeated straining. The incorporation of dimethyl siloxane units as multiblock segments was confirmed to improve the flexibility of poly(l ‐lactic acid). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40211.     

Synthesis and Characteristics of Novel Poly(Imide Siloxane) Segmented Copolymers

New poly(imide siloxane) copolymers for possible use as tough environmentally stable structural matrix resins and structure adhesives have been prepared. Thus, 3,3'-4,4'-benzophenone tertracarboxylic dianhydride was reacted with various Mn aminopropyl-terminated polydimethylsiloxane oligomers and a meta-substituted diamine “chain-extender” such as 3,3'-diaminodiphenyl sulfone or 3,3'-diaminobenzophenone to produce the siloxane-modified poly(amic acid). Thin films were cast from the reaction mixtures and subsequent thermal dehydration produced the poly(imide siloxane) block or segmented copolymers. Upper “cure” temperatures of 300°C were used to insure complete imidization. By varying the amount and molecular weight of the siloxane oligomer, a variety of novel copolymers of controlled composition have been synthesized. Tough, transparent, flexible soluble films were produced by this method. The thermal and bulk properties of films having low to moderate siloxane content closely resemble those of the unmodified polyimide controls. However, toughness and surface behavior can be enhanced.     

Fast and eco‐friendly synthesis of novel soluble thermally stable poly(amide‐imide)s modified with siloxane linkage with reduced dielectric constant under microwave irradiation in TBAB,TBPB and MeBuImCl via isocyanate method

A new series of poly(amide‐imide)s (PAI) modified with a siloxane linkage was synthesized under microwave radiation in ionic liquids and organic salts via the isocyanate method. The polymerization reactions of a novel siloxanic diacid monomer with 4,4′‐methylene‐bis(4‐phenylisocyanate) MDI were studied in ammonium, phosphonium, and imidazolium‐type organic salts. These poly(amide‐imide‐siloxane)s (PAI‐Si)s were obtained with high yields and good inherent viscosities ranging from 0.30 to 0.55 dL/g. The normally high softening temperatures and poor solubility of PAIs in organic solvents were improved via the incorporation of the flexible siloxane segments into the polymer backbone. The PAI‐Sis showed glass transition temperatures around 100°C and their 10% mass loss was about 300°C. They have a char yield in the range of 30–40% at 800°C. Calculated limiting oxygen index values of the polymers were about 30; therefore, they can be considered as self‐extinguishing. The dielectric constants of these silane‐containing PAIs (2.5) are lower than common siloxane‐free polyimides (～ 3). Their good thermal stability, enhanced solubility, and low dielectric constants suggest they may function as electrical insulators. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphologies and applied properties of PSI/PA composite particles synthesized at low temperature

Latex with a poly(dimethyl‐siloxane) core and a poly(methylmethacrylate‐ butylacrylate‐ 2‐hydroxypropyl acrylate) shell have been prepared at low temperature with potassium‐persulphate (KPS), sodium formaldehyde sulfoxylate (SFS) and 2,2′‐azobis [2‐(2‐imidazolin‐ 2‐yl)propane] dihydrochloride (VA‐044) as composite initiators by staged emulsion polymerization. Reactive surfactants were used to significantly improve the applied properties such as water adsorption ratio and thermo‐properties. Transmission electron microscopy (TEM) results indicated that increasing the amount of 2‐hydroxypropyl acrylate (HPA) and butylacrylate (BA) was favorable to form the core/shell particles. Particle size distribution results showed with increasing the dosages of surfactants, initiators, and seed‐latex, particle size decreased. Differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA) results indicated the high temperature‐reserved of copolymer was improved in the presence of polysiloxane. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers