Structure–property relationships of low dielectric constant,nanoporous, thermally stable polyimides via grafting of poly(propylene glycol) oligomers

Synthesis of high temperature polyimide foams with pore sizes in the nanometer range was developed. Foams were prepared by casting graft copolymers comprising a thermally stable block as the matrix and a thermally labile material as the dispersed phase. The copolyimides as the matrix material were prepared via polycondensation reactions of pyromellitic dianhydride with three new diamines (4BAP, 3BAP, and BAN) through the poly(amic acid) precursors. Functionalized poly(propylene glycol) (PPGBr‐1000 and PPGBr‐2500) as the labile oligomer was prepared via reaction of poly(propylene glycol) monobutyl ether with 2‐bromoacetyl bromide. Graft copolymers were prepared by the reaction of the poly(amic acid)s with these thermally labile constituents. Upon thermal treatment the labile blocks were subsequently removed leaving pores with the size and shape of the original copolymer morphology. The polyimides and foamed polyimides were characterized by some conventional methods including FTIR, H‐NMR, DSC, TGA, SEM, TEM, and dielectric constant. The average pore size of the polyimide nanofoams was in the range of 5–20 nm. The structure–property relationships of the prepared nanofoams were investigated based on the diamine structures and also molecular weights of labile groups. Copyright © 2008 John Wiley & Sons, Ltd.     

Microporous polycyanurate networks

A general means of generating nanofoams from thermosetting materials was investigated. Foams were prepared from a thermosetting monomer copolymerized with a thermally labile material, such that the thermally labile coblock is the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis, leaving pores where the size and shape are dictated by the initial morphology. For this investigation the thermosetting resin was prepared from a cyanate monomer (4,4′-(hexafluoroisopropylidene) diphenyl-cyanate), with either poly(propylene oxide) or a propylene oxide–urethane copolymer as the thermally labile block. The propylene oxide-based oligomers were molecularly miscible with the cyanate resin over the entire range of compositions, and molecular weights investigated, but developed a two-phase structure upon reaction to form the polycyanurate thermoset. The molecular weight and composition of propylene oxide chemically incorporated into the polycyanurate was varied along with the curing condition, solvents, and catalyst. Dynamic mechanical and small-angle x-ray scattering measurements demonstrated a two-phase morphology in the cured networks wherein the propylene oxide domains are dispersed in the polycyanurate matrix. Upon decomposition of the propylene oxide component, however, the foam was found to collapse. Samples with the larger void size retained, to a large extent, their void composition upon the thermolysis of the propylene oxide component. © 1996 John Wiley & Sons, Inc.     

Perfectly alternating segmented polyimide-polydimethyl siloxane copolymers via transimidization

New strategies for the synthesis of perfectly alternating segmented polyimide-polydimethyl siloxane copolymers were developed by utilizing a transimidization method. Imide oligomers endcapped with 2-aminopyrimidine were reacted with aminopropyl terminated (dimethyl siloxane) oligomers to afford perfectly alternating segmented imide siloxane copolymers. The polymerization was conducted in solvents such as chlorobenzene and chlorofrom. High molecular weight, fully imidized perfectly alternating segmented imide siloxane copolymers were obtained within 2 h at temperatures of 60-110°C. The mechanism of the reaction was further elucidated via model compounds and NMR characterization. The block copolymers exhibited two T_gs due to the microphase separation of the polyimide and polysiloxane phases. The T_g of the polyimide phase was a function of the length of the polyimide block. However, partial phase mixing was also evident from the DSC results on the imide siloxane copolymers prepared with low molecular weight polyimide segments. Thermooxidative stability and tensile properties of the perfectly alternating segmented imide siloxane copolymers were found to be principally dependent on the amount of poly (dimethyl siloxane) incorporated in the copolymer and did not correlate with the poly (dimethyl siloxane) or polyimide block lengths. The stress-strain behavior of both solvent cast films or molded films is also reported. © 1994 John Wiley & Sons, Inc.     

Breadth of glass transition temperature in styrene/acrylic acid block,random, and gradient copolymers: Unusual sequence distribution effects

Block, random, and gradient copolymers of styrene (S) and acrylic acid (AA) are synthesized by conventional or controlled radical polymerization, and their glass transition temperature (T_g) behaviors are compared. The location and breadth of the T_gs are determined using derivatives of differential scanning calorimetry heating curves. Each S/AA random copolymer exhibits one narrow T_g, consistent with a single phase of limited compositional nanoheterogeneity. Block copolymers exhibit two narrow T_gs originating from nanophase separation into ordered domains with nearly pure S or nearly pure AA repeat units. Each gradient copolymer exhibits a T_g response with a ～50–56 °C breadth that extends beyond the upper T_g of the block copolymers. For copolymers of similar composition, the maximum value in the gradient copolymer T_g response is consistent with that of a random copolymer, which has an enhanced T_g relative to poly(acrylic acid) due to more effective hydrogen bonding when AA units are separated along the chain backbone by S units. These results indicate that gradient copolymers with ordered nanostructures can be rationally designed, which exhibit broad glass transitions that extend to higher temperature than the T_gs observed with block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2842–2849, 2007     

Study of molecular motion of block copolymers in solution by high-resolution proton magnetic resonance

Molecular motions of hydrophobic–hydrophilic water-soluble block copolymers in solution were investigated by high-resolution proton magnetic resonance (NMR). Samples studied include block copolymers of polystyrene–poly(ethylene oxide), polybutadiene–poly(ethylene oxide), and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide). NMR measurements were carried out varying molecular weight, temperature, and solvent composition. For AB copolymers of polystyrene and poly(ethylene oxide), two peaks caused by the phenyl protons of low-molecular-weight (M?_n = 3,300) copolymer were clearly resolved in D₂O at 100°C, but the phenyl proton peaks of high-molecular-weight (M?_n = 13,500 and 36,000) copolymers were too broad to observe in the same solvent, even at 100°C. It is concluded that polystyrene blocks are more mobile in low-molecular-weight copolymer in water than in high-molecular-weight copolymer in the same solvent because the molecular weight of the polystyrene block of the low-molecular-weight copolymer is itself small. In the mixed solvent D₂O and deuterated tetrahydrofuran (THF-d₈), two peaks caused by the phenyl protons of the high-molecular-weight (M?_n = 36,000) copolymer were clearly resolved at 67°C. It is thought that the molecular motions of the polystyrene blocks are activated by the interaction between these blocks and THF in the mixed solvent.     

Phenylquinoxaline–Aryl ester block copolymers

Phenylquinoxaline–aryl ester block copolymers were synthesized using well-defined phenolic hydroxyl terminated oligomers via a monomers/oligomer approach. Phenylquinoxaline oligomers with molecular weights of 5600 and 12,900 g/mol were prepared from the condensation of 1,4-bis(phenylglyoxalyl)benzene and 3,3′-diaminobenzidine in the presence of 4-hydroxylbenzil. The oligomers were copolymerized with isophthaloyl chloride and bisphenol A in tetrachloroethane to afford the desired phenylquinoxaline–aryl ester block copolymers. Copolymers with polyester compositions ranging from 15–50 wt % were prepared by controlling the monomers/oligomer stoichiometry. The majority of the materials displayed single phase morphologies with T_gs intermediate to the T_gs for the poly (phenylquinoxaline) and polyester homopolymers. Plots of the reciprocal of the T_g of the copolymers versus composition agreed well with values predicted by the Fox equation. A multiphase morphology was obtained for the copolymer with the highest polyester block length (? 13,000 g/mol), which displayed a T_g at 190 and 300°C indicative of a glassy–glassy system. Significant improvement in the elongations were observed for the copolymers relative to the poly(phenylquinoxaline) homopolymer. The improved elongations were obtained with minimal sacrifice to the modulus. These materials represent the first example of poly(phenylquinoxaline) block copolymers from well-defined phenylquinoxaline oligomers.     

Synthesis and mechanochemical properties of biobased ABCBA-type pentablock copolymers comprising poly-d-lactide (A), poly-l-lactide (B) and poly(1,2-propylene succinate) (C)

The ABCBA pentablock copolymers (p-d -l -PPS) comprising poly(d -lactide) (PDLA: A), poly(l -lactide) (PLLA: B) and poly(propylene succinate) (PPS: C) were successfully synthesized by two-step ring-opening polymerization (ROP) of d - and l -lactide using a dihydroxy-terminated PPS as a macro-initiator. The pentablock copolymers revealed the high stereocomplex (sc) crystallinity, thermal stability and elastomeric property in their solution-cast films. It was found that the T_g was found to be proportional to the PPS content, whereas the T_m was proportional to their average block length. The thermal resistivity of the copolymer films was found to be as high as 202°C owing to their sc formation. The copolymers also showed improved stereocomplexibility compared to the enantiomeric mixtures of triblock copolymers (PLLA-PPS-PLLA and PDLA-PPS-PDLA) having similar PLLA and PDLA chain lengths. These pentablock copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% bio-based content, showing high heat-resistive property.     

2H NMR spin relaxation study of the soft segment motion in alternating ethylene–propylene copolymers

We synthesized three partially deuterated polymer samples, namely a poly(ethylene‐alt‐propylene) (EP) alternating copolymer, a poly(styrene‐b‐EP) diblock copolymer (SEP) and a poly(styrene‐b‐EP‐b‐styrene) triblock copolymer (SEPS). The ²H spin–lattice relaxation time, T₁, of EP soft segments above their glass transition temperature was measured by solid‐state ²H NMR spectroscopy. It was found that the block copolymers had a fast and a slow T₁ component whereas EP copolymer had only a fast component. The fast T₁ components for SEP and SEPS are similar to the T₁ value of EP above ca 20°C. The slow T₁ component for SEP and SEPS exhibited a minimum at 60°C and approached the value of the fast component near the T_g of polystyrene. The motional behavior of the EP units for SEP is similar to that of SEPS over the entire range of temperature. Copyright © 2001 John Wiley & Sons, Ltd.     

Melting behavior of ethylene oxide–propylene oxide (sym-PEP) block copolymers

Melting points and lamellar thicknesses have been measured for ethylene oxide–propylene oxide block copolymers (sym-PEP) with central poly(ethylene oxide) block lengths of 70–100 chain units and end poly(propylene oxide) block lengths of 0–30 chain units. Melting points of the block copolymers are lower than those of the corresponding poly(ethylene oxide) homopolymer by an amount (up to 15°C) which increases as the poly(propylene oxide) block length increases. Most samples have more than one melting transition, which can be assigned to variously folded chain crystals. End interfacial free energies σ_e for the various crystals have been estimated by use of Flory's theory of melting of block copolymers. For a given crystal type (e.g., once-folded-chain) σ_e is higher the longer the chain length of the end poly(propylene oxide) blocks. For a given copolymer σ_e is lower, the more highly folded the poly(ethylene oxide) chain.     

Properties of ethylene–propylene–vinyl chloride graft copolymers. I. Viscoelasticity of ethylene–propylene copolymers

The viscoelastic behavior of two different ethylene–propylene copolymers was studied as a function of the molar ratios of the components and the distribution of the lengths of the ethylene and propylene sequences. The glass transition temperatures T_g agree with the values calculated from relations between T_g and component ratio established by other authors. The copolymer with longer ethylene and propylene sequences was found to exhibit a relaxation spectrum with a slope less steep than ?0.5. This broadening is explained by the broader distribution of friction factors of the statistical segments in this copolymer and by differences in crystallike nearest-neighbor packing.     

Synthesis of polystyrene-polysiloxane side-chain liquid crystalline block copolymers

The synthesis of a new liquid crystalline block copolymer consisting of a polystyrene block and a side-chain liquid crystalline siloxane block is reported. The synthetic approach described is based on the anionic polymerization of styrene and cyclic trimethyltrivinyltrisiloxane monomers, followed by functionalization of the siloxane block with side chain mesogens. The siloxane block has a T_g well below 25°C and is designed to exhibit a chiral smectic C^* phase at room temperature. These block copolymers are the first side-chain liquid crystalline block copolymers which contain both a high T_g glassy block and a low T_g liquid crystalline block.     

Functionalization Conditions of PLGA-PEG-PLGA Copolymer with Itaconic Anhydride

Summary: Biodegradable thermosensitive triblock copolymers based on poly(ethylene glycol) and poly(lactic-co-glycolic acid) (PLGA-PEG-PLGA) prepared via ring opening polymerization were modified by itaconic anhydride (ITA), which gives copolymer both reactive double bonds and functional carboxylic acid groups essential for the reaction with biological active material. Functionalization conditions comprising ITA purification, temperature, time and presence of solvent were optimized with the respect to amount of end-capped ITA. Maximum of 76.6 mol. % of bonded ITA were reached via “one pot” reaction in a bulk at 110 °C after 1.5 h. ITA functionalization thermally stabilized the original copolymer by increasing the initial degradation temperature T_d from 284 °C to 294 °C and changing the negative glass transition temperature (T_g = -1.8 °C) to positive one up to 2.4 °C. The novel functionalized macromonomer can be cross-linked either chemically or physically in order to produce new functionalized hydrogel network applicable as biomedical material in tissue engineering.     

Poly(ethylene oxide)-poly(styrene oxide)-poly(ethylene oxide) copolymers: Micellization, drug solubilization, and gelling features

Two new poly(ethylene oxide)-poly(styrene oxide) triblock copolymers (PEO-PSO-PEO) with optimized block lengths selected on the basis of previous studies were synthesized with the aim of achieving a maximal solubilization ability and a suitable sustained release, while keeping very low material expense and excellent aqueous copolymer solubility. The self-assembling and gelling properties of these copolymers were characterized by means of light scattering, fluorescence spectroscopy, transmission electron microscopy, and rheometry. Both copolymers formed spherical micelles (12-14 nm) at very low concentrations. At larger concentration (>25 wt%), copolymer solutions showed a rich phase behavior, with the appearance of two types of rheologically active (more viscous) fluids and of physical gels depending on solution temperature and concentration. The copolymer behaved notably different despite their relatively similar block lengths. The ability of the polymeric micellar solutions to solubilize the antifungal drug griseofulvin was evaluated and compared to that reported for other structurally-related block copolymers. Drug solubilization values up to 55 mg g⁻¹ were achieved, which are greater than those obtained by previously analyzed poly(ethylene oxide)-poly(styrene oxide), poly(ethylene oxide)-poly(butylene oxide), and poly(ethylene oxide)-poly(propylene oxide) block copolymers. The results indicate that the selected SO/EO ratio and copolymer block lengths were optimal for simultaneously achieving low critical micelle concentrations (cmc) values and large drug encapsulation ability. The amount of drug released from the polymeric micelles was larger at pH 7.4 than at acidic conditions, although still sustained over 1 day.     

Compatibility studies of styrene and hydroxyl containing styrene copolymers with poly(ethylene oxide)

Copolymers of styrene with vinylphenyl trifluoromethyl carbinol, p-vinylphenyl trifluoromethyl carbinol, vinylphenyl hexafluorodimethyl carbinol, and p-vinylphenol are conditionally compatible with poly(ethylene oxide), depending on their composition and blending ratios, whereas copolymers of styrene and vinylphenyl methyl carbinol are much less compatible with poly(ethylene oxide), as determined by T_g criteria and differential scanning calorimetry. The crystallinity of poly(ethylene oxide) is changed in the copolymer/poly(ethylene oxide) blends, as indicated by depressions of the poly(ethylene oxide) melting point. Hydrogen-bond formation has been studied in two selected blends by infrared (IR) spectroscopy. Hydrogen bonding dissociation and reassociation as a function of temperature are reported. The conformation changes of poly(ethylene oxide) in the blends, the interaction between copolymer and poly(ethylene oxide) as well as in the reference blend, polystyrene/poly(ethylene oxide), are also investigated.     

Two‐sided comb poly(amic ester)–poly(propylene oxide) graft copolymers as porous polyimide precursors

New step‐growth graft block copolymers were synthesized. These two‐sided comb copolymers consisted of a poly(amic ester) (PAE) backbone and pendant poly(propylene oxide) (PPO) grafts. The copolymers were made via a macromonomer approach, in which the 4,6‐bischlorocarbonyl isophthalic acid bis[poly(propylene oxide)] ester macromonomer was synthesized through the reaction of hydroxyl‐terminated PPO oligomers with pyromellitic dianhydride and oxalyl chloride. This macromonomer was subsequently used in step‐growth polymerization with comonomers 4,6‐bischlorocarbonyl isophthalic acid diethyl ester, 2,5‐bischlorocarbonyl terephthalic acid diethyl ester, and 2,2‐bis[4‐ (4‐aminophenoxy)phenyl] hexafluoropropane, and this yielded PPO‐co‐PAE graft copolymers. Accordingly, we report the synthesis and characterization of the PPO oligomer, the PPO macromonomer, and their corresponding PPO‐co‐PAE graft copolymers. Graft copolymers with PPO concentrations of 3–26 wt % were synthesized. These polymers were thermally cured to produce polyimide/PPO composites. The thermolysis of these polyimide/PPO composites yielded porous polyimide films with porosities ranging of 4–22.5%. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2266–2275, 2005     

Copolymers of methyl methacrylate with N‐trifluorophenyl maleimides: High glass transition temperature and low birefringence polymers

Copolymers of methyl methacrylate (MMA) with 2,3,4‐ and 2,4,6‐trifluorophenyl maleimides (TFPMIs) were synthesized by a free radical initiator, azobisisobutyronitrile, in 1,4‐dioxane and also in bulk. The refractive indexes of the copolymers were in the range of 1.49–1.52 at 532 nm. The T_gs were 133–195 °C depending on copolymer compositions. In addition, the copolymers were thermally stable, T_d > 350 °C. The orientational and photoelastic birefringence of the copolymers were also investigated. As both of the orientational and photoelastic birefringences of PMMA are negative, whereas those of poly(TFPMI)s are positive, we could obtain nearly zero orientational and photoelastic birefringence polymers when the ratios of 2,3,4‐TFPMI/MMA were 15/85 and 5/95 mol %, respectively. For 2,4,6‐TFPMI, zero orientational and photoelastic birefringences could be obtained when the ratios of 2,4,6‐TFPMI/MMA were 12/88 and 3/97 mol %, respectively. The T_gs of those copolymers with zero birefringences were in the range of 135–140 °C. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of gradient copolymers with simultaneously tailor‐made chain composition distribution and glass transition temperature by semibatch ATRP: From modeling to application

Recent studies have demonstrated that gradient copolymers exhibit unique thermal properties. Although these properties can be determined by copolymer composition, other factors such as chain and sequence lengths and their distributions can also influence them. Accordingly, the synthesis of gradient copolymers requires simultaneously tailor‐made chain structure and thermal properties. In this work, we carried out a systematic study on the preparation of poly(methyl methacrylate‐grad‐2‐hydroxyethyl methacrylate) [poly(MMA‐grad‐HEMA)] with synchronously tailor‐made chain composition distribution and glass transition temperature (T_g) through semibatch atom transfer radical polymerization. First, a comprehensive model for simultaneously predicting gradient copolymer microstructure and T_g was presented using the concept of pseudo‐kinetic rate coefficients and Johnston equation. The model was validated by comparing simulation results with the classical reference data. Furthermore, the model was used to guide the experimental synthesis of the poly(MMA‐grad‐HEMA) gradient copolymers potentially as excellent damping material. The thermal properties of these gradient copolymer samples were evaluated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of copolymers of methyl methacrylate with 2,3,4,5,6‐pentafluoro and 4‐trifluoromethyl 2,3,5,6‐tetrafluoro styrenes: An intrachain interaction between methyl ester and fluoro aromatic moieties

2,3,4,5,6‐Pentafluoro and 4‐trifluoromethyl 2,3,5,6‐tetrafluoro styrenes were readily copolymerized with methyl methacrylate (MMA) by a free radical initiator. The copolymers were soluble in tetrahydrofuran and acetone. The films obtained were transparent and flexible. The glass transition temperatures (T_gs) of the copolymers were found positively deviated from the Gordon–Taylor equation. The positive deviation could be accounted for by dipole–dipole intrachain interaction between the methyl ester group of MMA and the highly fluorinated aromatic moiety, which resulted in a decrease in the segmental mobility of the polymer chains and the enhanced T_g values of the copolymers. The water absorption of PMMA was greatly decreased by copolymerization of MMA with the highly fluorinated styrenes. With as little as 10 mol % of pentafluoro styrene content in the copolymer, the water absorption was decreased to one‐third of that for pure PMMA. The fluorinated styrenes‐MMA copolymers were thermally stable up to 420 °C under air and nitrogen atmospheres. With 50 mol % of MMA in the copolymer, the copolymer was still stable up to 350 °C. Since these copolymers contain a large number of fluorine atoms, the light absorption in the region of the visible to near infrared is decreased in comparison with nonfluorinated polymers. Thus, these copolymers may be suitable for application in optical devices, such as optical fibers and waveguides. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of graft copolymers of poly(vinyl chloride) with styrene and (meth)acrylates by atom transfer radical polymerization

Graft copolymers of poly(vinyl chloride) with styrene and (meth)acrylates were prepared by atom transfer radical polymerization. Poly(vinyl chloride) containing small amount of pendent chloroacetate units was used as a macroinitiator. The formation of the graft copolymer was confirmed with size exclusion chromatography (SEC), ¹H NMR and IR spectroscopy. The graft copolymers with increasing incorporation of butyl acrylate result in an increase of molecular weight. One glass transition temperature (T_g) was observed for all copolymers. T_g of the copolymer with butyl acrylate decreases with increasing content of butyl acrylate.