Preparation of novel soluble poly(ester imide)s containing a trimellitimide moiety and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(ester imide)s, prepared by the reaction of phthalic anhydride, N‐(4‐carboxyphenyl) trimellitimide and 1,2‐ethanediol, were used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone (DDS). The poly(ester imide)s include poly(ethylene phthalate‐co‐ethylene N‐(1,4‐phenylene) trimellitimide dicarboxylate)s (PESIs) having 10, 20 and 30 mol% trimellitimide (TI) units, respectively. PESIs having 10 and 20 mol% TI units were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PESI (20 mol% TI unit, M _W 19300 g mol^?1) led to a 55% increase in the fracture toughness (K_IC) of the cured resin (with an increase in flexural strength and modulus) and the modified resin had a particulate morphology. PESI having 30 mol% TI units was not effective because of degradation of the modifier by DDS. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviour of the modified epoxy resin system. © 2001 Society of Chemical Industry     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Modification of cyanate ester resin by poly(ethylene phthalate) and related copolyesters

Aromatic polyesters were prepared and used to improve the brittleness of the cyanate ester resin. The aromatic polyesters include poly(ethylene phthalate) (PEP) and poly(ethylene phthalate‐co‐1,4‐phenylene phthalate). The polyesters were effective modifiers for improving the brittleness of the cyanate ester resin. For example, inclusion of 20 wt % PEP (MW 19,800) led to a 120% increase in the fracture toughness (K_IC) with retention in flexural properties and a slight loss of the glass transition temperature compared to the mechanical and thermal properties of the unmodified cured cyanate ester resin. The microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resins was lower than that of the unmodified resin as determined by thermogravimetric analysis. The water absorptivity of the modified resin increased significantly, compared to that of the unmodified cured cyanate ester resin. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified cyanate ester resin system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 208–219, 2000     

Modification of bismaleimide resin by poly(propylene phthalate), poly(butylene phthalate) and related (co)polyesters

Aromatic polyesters were prepared and used to decrease the brittleness of the bismaleimide resin composed of 4,4′-bismaleimidediphenyl methane (BMI) and o,o′-diallyl bisphenol A (DBA) (Matrimid 5292 resin). The aromatic polyesters included poly(propylene phthalate) (PPP), poly(2,2-dimethylpropylene phthalate) (PDPP), poly(butylene phthalate) (PBP) and poly(butylene phthalate-co-butylene terephthalate) (50mol% terephthalate unit) (PBPT). The polyesters were effective modifiers for decreasing the brittleness of the bismaleimide resin. For example, inclusion of 20wt% PPP (MW 18700) led to 50% increase in the fracture toughness (K_IC) with retention of flexural properties and a slight loss of the glass transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Micro-structures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resins was slightly lower than that of the unmodified resin as determined by thermogravimetric analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified bismaleimide resin system. © 1998 SCI.     

Modification of bismaleimide resin by poly(ethylene phthalate‐co‐ethylene terephthalate), poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate), and poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)

Aromatic polyesters were prepared and used to improve the brittleness of bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane and o,o′‐diallyl bisphenol A (Matrimid 5292 A/B resin). The aromatic polyesters included PEPT [poly(ethylene phthalate‐co‐ethylene terephthalate)], with 50 mol % of terephthalate, PEPB [poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate)], with 50 mol % of 4,4′‐biphenyl dicarboxylate, and PEPN [poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)], with 50 mol % 2,6‐naphthalene dicarboxylate unit. The polyesters were effective modifiers for improving the brittleness of the bismaleimide resin. For example, inclusion of 15 wt % PEPT (MW = 9300) led to a 75% increase in fracture toughness, with retention in flexural properties and a slight loss of the glass‐transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism was assessed as it related to the morphological and dynamic viscoelastic behaviors of the modified bismaleimide resin system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2352–2367, 2001     

Toughening of bismaleimide resin by modification with poly(ethylene phthalate) and poly(ethylene phthalate-co-ethylene isophthalate)

Aromatic polyesters were prepared and used to improve the brittleness of the bismaleimide resin composed of 4,4′-bismaleimidediphenyl methane and o,o′-diallyl bisphenol A. The aromatic polyesters contain poly(ethylene phthalate) (PEP) and poly(ethylene phthalate-co-ethylene isophthalate) (10 mol % isophthalate unit) (PEPI). PEP and PEPI were effective modifiers for improving the brittleness of the bismaleimide resin. The most suitable composition for the modification of the bismaleimide was inclusion of 20 wt % PEP (MW 18,200), which led to an 80% increase in the fracture toughness with retention of flexural properties and a slight decrease in the glass transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin (Matrimid resin). Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resin was slightly lower than that of the unmodified resin by thermogravimetric analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behavior of the modified bismaleimide resin system. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1349–1357, 1997     

Novel dibutyltin oxide‐tributyl phosphate condensate as accelerator for the curing of the epoxy resin/4,4′‐diamino diphenyl sulfone system. II. Toughening of the resin with hydroxyl‐terminated poly(tetramethylene) glycols

When a crystalline Bu₂SnO‐Bu₃PO₄ condensate was used as a catalyst for the curing of the Epon 828/DDS system, the addition of hydroxyl group to epoxy group took place. On the basis of this reaction, direct employment of poly(tetramethylene) glycols (PTMG) as toughener for the epoxy resin system was successful. Morphology of the modified resin depended on the molecular weight and the concentration of PTMG. With the incorporation of a small amount of PTMG, the critical fracture energy of the cured resin was improved greatly, while the flexural strength and the modulus were less influenced. A slight enhancement in glass transition temperature (T_g) of the modified resin was found up to the PTMG concentration of 5 phr; further increase of the PTMG concentration caused a significant lowering of T_g. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1237–1242, 2001     

Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

The study on poly(ether sulfone) modified cyanate ester resin and epoxy resin cocuring blends

Poly(ether sulfone) terminated with phenolic hydroxyl groups modified cyanate ester resin and epoxy resin cocuring blends were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, rheometry, and mechanical properties measurement. The results suggested that poly (ether sulfone) (PES) could accelerate the polycyclotrimerization reaction of cyanate ester and cocuring processes between cyanate ester and epoxy of modified blends because of the presence of phenolic hydroxyl groups at the end of the PES molecules. It was found that the evolution of the morphologies and complex viscosities of the modified blends sensitive to molecular weight and content of PES, the tensile strength and elongation at break of the modified blends were correlated with the morphologies of modified blends. Moreover, the evolution of complex viscosities of the modified blends also showed an exponential growth at the early stage of phase separation, which demonstrated experimentally that the coarsening processes of droplets of bisphenol‐A dicyanate and diglycidyl ether of bisphenol A and the final morphologies obtained in the blends modified with PES were affected by viscoelastic behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445     

Preparation and swelling properties of solution crosslinked poly(cis‐1,4‐butadiene) gels

Poly(cis‐1,4‐butadiene) (PCB) gels were prepared by the crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto unvulcanized butadiene rubber with a solution polymerization technique with benzoyl peroxide (BPO) as an initiator. The effects of the reaction conditions, such as the amount of the solvent, the amount of DVB and tBS, and the initiator (BPO), on the equilibrium swelling ratio (Q_e) were also investigated. The highest oil absorbencies of crosslinked gels in xylene and cyclohexane were 51.35 and 32.98 g/g, respectively. A swelling kinetic equation was proposed for this system: Q_t = Q_e ? {Kt + [1/(Q_e ? Q₀)]}^?1, where Q_t is the swelling ratio at time t, Q₀ is the initial swelling ratio, and K is the swelling kinetic constant. This equation fit the experimental results quite well. The diffusion of organic solvents in PCB gels was Fickian. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2241–2245, 2003     

Modification of three‐component bismaleimide resin by poly(phthaloyl diphenyl ether) and related copolymers

A three‐component bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane (BDM), o,o′‐diallyl bisphenol A (DBA), and o,o′‐dimethallyl bisphenol A (1.0/0.3/0.7 eq ratio) was used as a parent bismaleimide resin. Modification of the three‐component bismaleimide resin was examined by blending it with poly(ether ketone ketone)s. Poly(ether ketone ketone)s include poly(phthaloyl diphenyl ether) (PPDE), poly(phthaloyl diphenyl ether‐co‐isophthaloyl diphenyl ether) (PPIDE), and poly(phthaloyl diphenyl ether‐co‐terephthaloyl diphenyl ether) (PPTDE). The PPIDE (51 mol % isophthaloyl) and PPTDE (44 mol % terephthaloyl) were more effective as modifiers for the bismaleimide resin than was PPDE. For example, the fracture toughness (K_IC) for the modified resin increased 30% with no deterioration in the flexural strength and modulus with a 15 wt % inclusion of PPTDE (MW 23,400) compared to the parent three‐component bismaleimide resin: the K_IC increased 95% compared to the value for the Matrimid 5292 resin composed of BDM and DBA. The morphologies of the modified resins changed from particulate to cocontinuous phase structures, depending on the modifier structure and concentration. Toughening of the cured bismaleimide resin could be achieved because of the cocontinuous phase structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2991–3000, 2001     

Fluorinated poly(aryl thioether)s and poly(aryl sulfone)s derived from 2,3,4,5,6‐pentafluorobenzoic acid

Poly(aryl thioether)s (F‐PTEs) containing 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety and polar moiety, such as 1,3,4‐ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4′‐thiobisbenzenthiol. F‐PTEs were amorphous with good thermal properties including high glass transition temperature (T_g) and thermal stability, solubility, and hydrophobicity. F‐PTEs were transformed into poly(aryl sulfone)s (F‐PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T_gs of the F‐PSs were 30–40°C higher than those of the corresponding F‐PTEs. F‐PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F‐PTEs and F‐PSs were a new class of high‐performance polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a poly(ether–ester) copolymer from poly(2,6 dimethyl‐1,4‐phenylene oxide) and poly(ethylene terephthalate)

A series of poly(ether–ester) copolymers were synthesized from poly(2,6 dimethyl‐1,4‐phenylene oxide) (PPO) and poly(ethylene terephthalate) (PET). The synthesis was carried out by two‐step solution polymerization process. PET oligomers were synthesized via glycolysis and subsequently used in the copolymerization reaction. FTIR spectroscopy analysis shows the coexistence of spectral contributions of PPO and PET on the spectra of their ether–ester copolymers. The composition of the poly(ether–ester)s was calculated via ¹H NMR spectroscopy. A single glass transition temperature was detected for all synthesized poly(ether–ester)s. T_g behavior as a function of poly(ether–ester) composition is well represented by the Gordon‐Taylor equation. The molar masses of the copolymers synthesized were calculated by viscosimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of styrene–maleic anhydride random copolymer and its compatibilization to poly(2,6‐dimethyl‐1,4‐phenylene ether)/brominated epoxy resin

Styrene–maleic anhydride random copolymer (R‐SMA_7.5), with a low content of maleic anhydride (MAH) of about 7.5 mol%, has been prepared, and the copolymer was characterized by fourier‐transform infrared (FTIR) and ¹³C NMR techniques showing that the product contained only random copolymer without blocks. The miscibility between poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) and R‐SMA, was investigated by differential scanning calorimetry (DSC), showing that PPE was miscible with R‐SMA synthesized in our laboratory over the entire composition with low MAH content. A blend of R‐SMA₁₈ (MAH content is about 18 mol%) and PPE was also studied by DSC, which showed that PPE was immiscible when R‐SMA was the major component, although it was miscible with limited composition. FTIR investigation showed that R‐SMA could react with bromide epoxy (BEP) resin at high temperature (180°). The heat‐resistance and mechanical properties of R‐SMA/PPE/BEP systems were tested and analyzed, and results indicated that R‐SMA could improve the miscibility of PPE and BEP with increasing T_g of the BEP phase and decreasing the T_g of the PPE slightly, improving the breaking elongation and breaking energy, which resulted from good miscibility between PPE and BEP with R‐SMA as the compatibilizer. Finally, the properties of the composites (copper clad laminate) with R‐SMA_7.5 are studied and discussed. Copyright © 2003 Society of Chemical Industry     

Miscibility and specific interactions in blends of poly(vinyl phenyl ketone hydrogenated) with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The miscibility behavior of poly(vinyl phenyl ketone hydrogenated) (PVPhKH) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) are studied by differential scanning calorimetry, thermomechanical analysis, and FTIR spectroscopy. Two miscibility windows between 10 to 40 and 60 to 90 wt % PPO are detected. Only the blend with 50 wt % PPO is immiscible. The best fit of the Gordon–Taylor equation of the experimental glass‐transition temperatures for miscible PVPhKH/PPO blends is shown. A study by FTIR spectroscopy suggests that hydrogen bonding interactions are formed between the hydroxyl groups of PVPhKH and the ether groups of PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1887–1892, 2004     

Preliminary investigation of poly(ether sulfone)/poly(aryl ether ketone) containing 1,4‐naphthalene blends

The blends of poly(ether sulfone) and poly(aryl ether ketone) containing 1,4‐naphthalene were prepared by melt mixing in a Brabender‐like apparatus. The specimens for measurements were made by compression molding under pressure and then were water‐quenched at room temperature. The tensile strength, tensile modulus, elongation at break, thermal analysis, and scanning electron microscopy were each measured. The dependence of tensile strength, tensile modulus, and elongation at break on blend systems was obtained. The effects of composition and miscibility on the mechanical properties are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 472–476, 2006     

Synthesis and characterization of the two novel liquid crystalline epoxy resins based on bisphenol‐s mesogen

Two novel liquid crystalline epoxy resins (LCER) based on bisphenol‐S mesogen, 4,4′‐Bis‐(2,3‐epoxypropyloxy)‐sulfonyl bis(1,4‐phenylene) (p‐BEPSBP) and sulfonyl bis(4,1‐phenylene) bis[4‐(2,3‐epoxypropyloxy)benzoate] (p‐SBPEPB), were synthesized. Their liquid crystalline behavior and structure were characterized by Fourier transmittance infrared ray (FTIR), differential scanning calorimetry (DSC), ¹HNMR, polarized optical microscopy (POM) and X‐ray diffraction (XRD). The results show that p‐BEPSBP is a kind of thermotropic liquid crystal and has a smectic mesophase with a melting point (T_m) at 165°C; the p‐SBPEPB is a kind of nematic mesophase with the temperature range of 155–302°C from the T_m to the clearing point T_i. The curing behaviors and texture of the liquid crystalline epoxy resins with 4,4′‐diaminodiphenyl ether (DDE) were also studied by DSC and some kinetic parameters were evaluated according to the Ozawa's method. The dynamic mechanical properties of curing products were also investigated by torsional braid analysis (TBA), and the results suggest that the dynamic mechanical loss peak temperature (T_p) of p‐BEPSBP/DDE and p‐SBPEPB/DDE is 120 and 130°C, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008