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1.
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  相似文献   

2.
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 (KIC) 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.  相似文献   

3.
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 (KIC) 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  相似文献   

4.
Poly(ester imide)s containing trimellitimide moieties have been used to reduce the brittleness of the bismaleimide resin composed of 4,4′‐bismaleimidediphenyl methane and o,o′‐diallyl bisphenol A. The poly(ester imide)s include poly[ethylene phthalate‐co‐ethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s containing 20–40 mol% trimellitimide (TI) unit, and poly[trimethylene phthalate‐co‐trimethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s (PESIP) containing 20 mol% TI unit. The poly(ester imide)s are effective modifiers for reducing the brittleness of the bismaleimide resin. For example, when using 30 wt% of PESIP (20 mol% TI unit, Mw 13 500 g mol?1), the fracture toughness (KIC) for the modified resin is increased by 80% with retention in flexural properties and a slight loss of the glass transition temperature, compared with the values of the unmodified cured bismaleimide resin. Microstructures of the modified resins have been examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified bismaleimide resin system. © 2004 Society of Chemical Industry  相似文献   

5.
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 (KIC) 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  相似文献   

6.
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 (Tc) 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 Go, and nucleation constant Kg than those of PBET copolymers. © 2001 Society of Chemical Industry  相似文献   

7.
A series of poly(ethylene terephthalate‐co‐isophthalate) copolyesters containing upto 50%‐mole of isophthalic units were prepared by polycondensation from ethylene terephthalate and ethylene isophthalate fractions of linear oligomers containing from 5 to 6 repeating units in average. The polyesters were obtained in good yields and with high‐molecular‐weights. The microstructure of the copolyesters was studied as a function of reaction time by 13C‐NMR showing that a random distribution of the comonomers was achieved since the earlier stages of polycondensation. The melting temperature and enthalpy of the copolyesters decreased with the content of isophthalic units so that copolyesters containing more than 25% of these units were amorphous. Isothermal crystallization studies made on crystalline copolyesters revealed that the crystallization rate of copolyesters decreased with the content in isophthalic units. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

8.
Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol−1) led to an 80% increase in the fracture toughness (KIC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry  相似文献   

9.
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 (KIC) 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 KIC 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  相似文献   

10.
Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET60I40), abbreviated PET/PET60I40 (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. 13C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET60I40 (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003  相似文献   

11.
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 (KIC) 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  相似文献   

12.
Thermal properties and crystalline structure of liquid crystalline (LC) poly(ethylene terephthalate‐co‐2(3)‐chloro‐1,4‐phenylene terephthalate) [copoly(ET/CPT)] were investigated using differential scanning calorimetry (DSC), thermogravimetry (TGA), limiting oxygen index (LOI) measurement, electron dispersive X‐ray analysis (EDX), X‐ray diffractometry, and infrared spectrometry (IR). The thermal transition temperatures of copoly(ET/CPT) were changed with the composition. Copoly(ET/CPT) showed two thermal decomposition steps and the residues at 700°C and LOI values of copoly(ET/CPT) were almost proportional to its chlorine content. The activation energy of thermal decomposition of LC units was very low compared to that of poly(ethylene terephthalate)(PET) units. Crystal structure of copoly(ET/CPT) (20/80) was of triclinic system with the lattice constants of a = 9.98 A?, b = 8.78 A?, c = 12.93 A?, α = 97.4°, β = 96.1°, and γ = 90.8°, which is very close to that of poly(chloro‐p‐phenylene terephthlate) (PCPT) with the lattice constants of a = 9.51 A?, b = 8.61 A?, c = 12.73 A?, α = 96.8°, β = 95.4°, and γ = 90.8°. When copoly(ET/CPT)(50/50) was annealed at 220°C in vacuum, crystallization induced sequential reordering (CISR) was not observed but the heat of fusion was slightly increased due to the increase of the trans isomer content in PET units. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1286–1294, 2002; DOI 10.1002/app.10451  相似文献   

13.
Poly(trimethylene terephthalate‐co‐2‐methyl‐ ethylene terephthalate) random copolymers of various compositions were synthesized via traditional two‐step polycondensation by incorporating of 1,2‐propanediol. The molar composition of trimethylene terephthalate and 2‐methyl‐ethylene terephthalate units and chemical structure were confirmed by means of 1H‐NMR and Fourier transform infrared. The thermal properties of the copolyesters were evaluated by DSC and TGA. As far as the thermal properties is concerned, the main effect of incorporation of 1,2‐propanediol was a lowering in the melting temperature, and an increment of glass transition temperature compared to homopolymer PTT. Due to the effect of the lateral methyl groups in the polymeric chain, the thermal stability is slightly decreased as the amount of the MET units is increased. Furthermore, the crystals of PTT/MET copolyesters were observed by hot‐stage optical polarizing microscopy at the indicated crystallization temperatures. As expected, the incorporation of MET units in the polymer chain of PTT was found to decrease the dimension of the crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

14.
Various problems, including high crystallinity, high melting temperature, poor thermal stability, hydrophobicity and brittleness, have impeded many practical applications of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV) as an environmentally friendly material and biomedical material. In the work reported here, multi‐block copolymers containing PHBV and poly(ethylene glycol) (PHBV‐b‐PEG) were synthesized with telechelic hydroxylated PHBV as a hard and hydrophobic segment, PEG as a soft and hydrophilic segment and 1,6‐hexamethylene diisocyanate as a coupling reagent to solve the problems mentioned above. PHBV and PEG blocks in PHBV‐b‐PEG formed separate crystalline phases with lower crystallinity levels and lower melting temperatures than those of phases formed in the precursors. The crystallite dimensions of the two blocks in PHBV‐b‐PEG were smaller than those of the corresponding precursors. Compared to values for the original PHBV, the maximum decomposition temperature of the PHBV block in PHBV‐b‐PEG was 16.0 °C higher and the water contact angle was 9° lower. In addition, the elongation at break was 2.8% for a pure PHBV fiber but 20.9% for a PHBV/PHBV‐b‐PEG fiber with a PHBV‐b‐PEG content of 30%. PHBV‐b‐PEGs can overcome some of the disadvantages of pure PHBV; it is possible that PHBV might be a good candidate for the formulation of environmentally friendly materials and biomedical materials. Copyright © 2010 Society of Chemical Industry  相似文献   

15.
Poly(butylene terephthalate‐co‐triethylene terephthalate) random copolymers of various compositions and molecular weights were synthesized in bulk and characterized in terms of their chemical structure and thermal and rheological properties. At room temperature all the copolymers were partially crystalline and showed good thermal stability. The main effect of copolymerization was a decrease in the melting and glass‐transition temperatures with respect to the poly(butylene tere‐ phthalate) homopolymer. The fusion temperatures were well correlated with the composition by the Baur equation and the equilibrium melting temperature and the heat of fusion extrapolated values for poly(butylene terephthalate) were in good agreement with those reported elsewhere. Triethylene terephthalate units were found to influence the rheological behavior in the melt, the viscosity being significantly higher than that of the poly(butylene terephthalate‐co‐diethylene terephthalate) copolymers investigated previously. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 981–990, 2001  相似文献   

16.
A series of random copolymers were synthesized by the bulk polycondensation of dimethyl terephthalate with ethylene glycol (EG) and propane‐1,3‐diol (PDO) in various compositions. Their composition and thermal properties were investigated. The copolymers with 57.7 mol % or more PDO or 14.4 mol % or less PDO were crystallizable, but those with 36–46.2 mol % PDO were amorphous. The nonisothermal crystallization behavior was investigated with varying cooling rates by DSC. Poly(ethylene terephthalate) (PET) and poly(trimethylene terephthalate) (PTT) homopolymers have relatively lower activation energy than their copolymers. PET‐rich copolymers (EG > 85.9%) exhibited PET crystal structure, and exhibited no PTT crystal structure; and PTT‐rich copolymers (PDO > 41.7%) exhibited PTT crystal structure, and exhibited no PET crystal structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

17.
Aromatic polyesters, prepared by the reaction of aromatic dicarboxylic acids and 1,4-butanediol, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulfone. These polyesters contained poly(butylene phthalate)s (PBP), poly(butylene phthalate-co-butylene isophthalate)s, poly(butylene phthalate-co-butylene terephthalate)s, and poly(butylene phthalate-co-butylene 2,6-naphthalene dicarboxylate)s. All aromatic polyesters used in this study were soluble in the epoxy resin without solvents and were found to be effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PBP (MW 16,300) led to a 120% increase in the fracture toughness (KIC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 1996 John Wiley & Sons, Inc.  相似文献   

18.
Poly(ether ketone ketone)s were prepared and used to improve the brittleness of the bismaleimide resin. The bismaleimide resin was composed of 4,4′-bismaleimidediphenyl methane (BMI) and o,o′-diallyl bisphenol A (DBA). 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). PPIDE (50 mol % isophthaloyl unit) was more effective as a modifier for the bismaleimide resin than were PPDE and PPTDE (50 mol % terephthaloyl unit). Morphologies of the modified resins changed from particulate to cocontinuous and to phase-inverted structures, depending on the modifier structure and content. The most effective modification for the cured resins could be attained because of the cocontinuous phase or phase-inverted structure of the modified resins. For example, when using 10 wt % of PPIDE (50 mol % IP unit, MW 349,000), the modified resin had a phase-inverted morphology and the fracture toughness (KIC) for the modified resins increased 75% with retention in flexural properties and the glass transition temperature, compared to those of the unmodified cured bismaleimide resin. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:769–780, 1998  相似文献   

19.
The synthesis of two low molecular weight linear unsaturated oligoester precursors, poly(propylene fumarate‐co‐sebacate) (PPFS) and poly(ethylene fumarate‐co‐sebacate) (PEFS), are described. PPFS, PEFS, and poly(ethylene glycol) are then used to prepare poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PPFS‐co‐PEG) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PEFS‐co‐PEG) block copolymers. The products thus obtained are investigated in terms of the molecular weight, composition, structure, thermal properties, and solubility behavior. A number of design parameters including the molecular weights of PPFS, PEFS, and PEG, the reaction time in the polymer synthesis, and the weight ratio of PEG to PPFS or to PEFS are varied to assess their effects on the product yield and properties. The hydrolytic degradation of PPFS‐co‐PEG and PEFS‐co‐PEG in an isotonic buffer (pH 7.4, 37°C) is investigated, and it is found that the fumarate ester bond cleaves faster than does the sebacate ester bond. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 295–300, 2004  相似文献   

20.
Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999  相似文献   

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