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1.
A series of liquid polyester polyols (PEs) from adipic acid (AA), phthalic anhydride (PA) and trihydroxymethylpropane (TMP), and such glycols as ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), butanediol (BD) and hexanediol (HD), were prepared. Polyurethanes (PUs) were obtained from the PEs and polyaryl polymethylene isocyanate (PAPI) at room temperature. The effects of the structures of the glycols on viscosity, glass transition temperature and crystallinity of the PEs, and the mechanical, thermal and boiling‐water‐resistant properties of PUs were studied. The experiments showed that the viscosities and glass transition temperatures of the PEs decreased as the length of the glycol chains increased. The polyester based on HD lost flowability because of crystallization. The tensile strength and hardness of the PUs obtained decreased with increasing the length of the glycol chains, while the resistance to thermal deformation and boiling water increased. Thermogravimetric analysis demonstrated that thermal degradation of the polyurethane based on DEG proceeded in one step and for the others in two steps. The initial degradation temperature of the polyurethane based on EG was the lowest and that of the polyurethane based on BD was the highest. The residue of the former at 450 °C was the greatest, while that of the latter was the lowest. Copyright © 2004 Society of Chemical Industry  相似文献   

2.
The basic thermal properties, isothermal melt crystallization kinetics, spherulitic morphology, mechanical properties, and hydrolytic degradation behavior of a novel eco‐friendly polyester poly(butylene diglycolate) (PBDG) containing ether linkages were systematically studied with several techniques in this research. PBDG is an aliphatic polyester with high thermal stability. It had a glass transition temperature (Tg) of ?25.7 °C, a melting point temperature of 65.1 °C, and an equilibrium melting point of 73.2 °C. During the isothermal melt crystallization, PBDG crystallized slowly with increasing crystallization temperature, but the crystallization mechanism did not change. Negative spherulites were observed for PBDG. The mechanical properties of PBDG were investigated from the tensile testing. As a ductile polyester, PBDG possessed good mechanical properties. PBDG also showed a fast hydrolytic degradation rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44186.  相似文献   

3.
A series of novel fluorinated aromatic polyesters containing trifluoromethylphenoxy pendant groups was synthesized by interfacial polycondensation of 2‐(4‐trifluoromethylphenoxy)terephthalyl chloride with various bisphenols in dichloromethane. The polyesters obtained in good yields had weight‐average molecular weights of 70,600–29,800 g/mol, polydispersities of 1.81–2.08, and were all amorphous. All polyesters were easily soluble in organic solvents such as N,N‐dimethylformamide, tetrahydrofuran, o‐chlorophenol, pyridine, and dichloromethane. These fluorinated polyesters showed glass transition temperature of 133–210°C, and good thermal stability with almost no weight loss up to 378°C, the 10% weight loss temperature of 472–523°C as well as char yield of 32–63% at 600°C in nitrogen. These polyester films cast from chloroform solutions exhibited tensile strengths ranging from 102 to 126 MPa, elongation at break from 6.3% to 11.7%, and tensile moduli from 2.1 to 3.3 GPa. The resulting polyester films also displayed low dielectric constants between 2.18 and 2.49 (1 MHz), high transparency with an ultraviolet‐visible absorption cut‐off wavelengths in the 332–355 nm range, and excellent electric strengths (50.4–65.6 kV/mm) and volume resistivity (2.51–6.03 × 1016 Ω cm). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
Two new aromatic diester‐dicarboxylic acids containing furan rings, namely, benzofuro[2,3‐b]benzofuran‐2,9‐dicarboxyl‐bis‐pyridyl ester‐4,4′‐dicarboxylic acid and benzofuro[2,3‐b]benzofuran‐2,9‐dicarboxyl‐bis‐phenyl ester‐4,4′‐dicarboxylic acid were synthesized by the reaction of benzofuro[2,3‐b]benzofuran‐2,9‐dicarbonyl chloride with 6‐hydroxynicotinic acid and 4‐hydroxybenzoic acid, respectively. These monomers were converted to aromatic copoly(ester–amide)s by reaction with various aromatic diamines via direct polycondensation. Polymers were characterized by FTIR and 1H NMR spectroscopy, thermogravimetry, viscosity and solubility tests. The inherent viscosity of the polymers was in the range 0.23–0.46 dl g?1 in dimethyl sulfoxide at 30 °C. They dissolved readily in polar solvents at room temperature. They possess a glass‐transition temperature in the range 210–260 °C and exhibit excellent thermal stability. Copyright © 2004 Society of Chemical Industry  相似文献   

5.
A new monomer, 2,5‐bis(4‐carboxy methylene phenyl)‐3,4‐diphenyl thiophene (V) has been synthesized and characterized by physical and spectroscopic methods. A series of eight aromatic–aliphatic polyamides was prepared from the (V) and different aromatic diamines using Yamazaki's direct phosphorylation reaction. The polyamides were characterized by IR spectroscopy, viscosity measurements, and thermal analysis. An excellent yield of these polyamides was obtained, with inherent viscosities in the range of 0.28 to 0.67 dL/g, and the polyamide were readily soluble in aprotic polar solvents such as N‐methyl‐2‐pyrrolidone, N‐N‐dimethyl acetamide, dimethyl sulphoxide, and so forth. Polyamides could be cast into transparent and flexible films. They had glass‐transition temperatures of 225–273°C. When evaluated by thermogravimetry, thermal analysis of the polyamides showed no weight loss below 311°C, and the char yield in air at 900°C was 55%–67%. The structure–property correlation among these polyamides is also discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 566–571, 2001  相似文献   

6.
An aliphatic/aromatic polyester blend has been dealt with in this study. As an aliphatic polyester, poly(butylene succinate) (PBS) was used, which is thought to possess biodegradability, but it is relatively expensive. It has been blended with poly(butylene terephthalate) (PBT) in order to obtain a biodegradable blend with better mechanical properties and lower cost. The miscibilities of PBS–PBT blends were examined not only from the changes of Tg but also from log G′–log G" plots. Dynamic mechanical thermal analyzer (DMTA) was an appropriate, sensitive method to obtain the glass transitions properly. Thermal stabilities of PBS and PBT were also verified at the temperature of 240°C. A transesterification reaction between two polyesters at 240°C was hardly detectable so that it did not affect the miscibilities and properties of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 945–951, 1999  相似文献   

7.
Melting gels are hybrid gels that have the ability to soften and flow at around 100°C for some combinations of mono‐ and di‐substituted alkoxysiloxanes, where substitutions are either all aromatic or all aliphatic. In this study, melting gels were prepared using phenyltriethoxysilane (PhTES) and dimethyldiethoxysilane (DMDES), meaning both an aromatic and aliphatic substitution. Differential scanning calorimetry was performed to identify glass‐transition temperatures, and thermal gravimetric analysis coupled with differential thermal analysis (TGA‐DTA) was performed to measure weight loss. The glass‐transition temperatures (Tg) ranged from ?61°C to +5.6°C, which are between the values in the methyl only system, where all Tg values are less than 0°C, and those values in the phenyl only system, where Tg values are greater than 0°C. The Tg decreased with an increase in the DMDES fraction. Below 450°C, the gels lost little weight, but around 600°C there was a drop in weight. This temperature is lower than the temperature for gels prepared with only aromatic substitutions, but higher than that for gels prepared with only aliphatic substitutions. Final heat treatment was carried out at 150°C for the gel with 80%PhTES‐20%DMDES (in mol%), and the consolidation temperature increased with increasing DMDES content to 205°C for the gel with 50%PhTES‐50%DMDES. After this heat treatment, the melting gels no longer soften.  相似文献   

8.
This article describes a new, nonphosgene method for the synthesis of poly(bisphenol A carbonate) (PC). The method involves three steps: the reaction of an aliphatic diol with phenyl chloroformate to form an alkylene diphenyl dicarbonate, the reaction of the alkylene diphenyl dicarbonate with bisphenol A to produce an aromatic–aliphatic polycarbonate, and the thermal treatment of the polycarbonate at 180–210°C under a stream of nitrogen with Ti(OBu)4 to give PC and a cyclic alkylene carbonate. The method furnished low to moderate molecular masses of PC upon the complete elimination of the aliphatic moieties. The approach may be considered a new method, based on polycarbonate thermochemical degradation, for the synthesis of cyclic aliphatic carbonates. The obtained polymers were characterized by intrinsic viscosity and IR, 1H‐NMR, and 13C‐NMR spectroscopy. The thermal treatment step was conducted in a glass reaction tube at 180–210°C under a stream of nitrogen, and the reaction was completed by heating to 250°C. In the thermal treatment step, semisolid effluents composed of cyclic alkylene carbonates were formed and subsequently eliminated from the reaction mixture. Heating to 250°C under nitrogen or under a dynamic vacuum furnished the pure aromatic PC residue. This intrachange reaction provides a flexible method for the synthesis of polycarbonates with alkylene diols containing two or three methylene groups, from which the pure PC homopolymer can be prepared. The potential of this approach was demonstrated by the successful synthesis of PC homopolymer from five different polycarbonates with a bisphenol A unit linked to 1,2‐propylene, 1,3‐propylene, 2‐methyl‐1,3‐propylene, 2,2‐dimethyl‐1,3‐propylene, and 1,3‐butylene as the alkane chains. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

9.
The use of bio‐based polymeric plasticizers could expand the application range of plasticized poly(vinyl chloride) (PVC) materials. In this study, a novel bio‐based polyester plasticizer, poly(glutaric acid‐glyceryl monooleate) (PGAGMO), was synthesized from glutaric acid and glyceryl monooleate via a direct esterification and polycondensation route. The polyester plasticizer was characterized by gel permeation chromatography, 1H‐nuclear magnetic resonance, and Fourier‐transform infrared spectroscopy. The plasticizing effect of PGAGMO on PVC was investigated. The melting behavior, thermal properties, and mechanical properties of PVC blends were studied. The results showed that the PGAGMO could improve the thermal stability and reduce the glass transition temperature of PVC blends; when phthalates were substituted by PGAGMO in PVC blends, the thermal degradation temperature of PVC blends increased from 251.1°C to 262.7°C, the glass transaction temperature decreased from 49.1°C to 40.2°C, the plasticized PVC blends demonstrated good compatibility, and the decrement of the torque and the melt viscosity of PVC blends were conducive to processing. All results demonstrated that the PGAGMO could partially substitute for phthalates as a potential plasticizer of PVC. J. VINYL ADDIT. TECHNOL., 22:514–519, 2016. © 2015 Society of Plastics Engineers  相似文献   

10.
A detailed thermal study is presented of the melt polycondensation between the renewable monomers citric acid and d ‐glucono‐δ‐lactone. It was found that the polyester networks formed have glass transition temperature ranges that increase with increasing reaction temperature and time, corresponding to an increase in molecular weight. The minimum reaction temperature was investigated and found to be 130 °C for a 1/1 system. Moreover, the monomers show eutectic melt behaviour, with a eutectic melting temperature of 125 °C. A range of additional co‐monomers were evaluated, revealing that aliphatic and aromatic bifunctional co‐monomers result in lower glass transition temperatures. When polyfunctional co‐monomers were employed it was found that the chain flexibility influenced the resulting thermal properties. Moreover, it is shown that the ring structure of d ‐glucono‐δ‐lactone plays a key role in the thermal properties of the resulting polyesters. © 2016 Society of Chemical Industry  相似文献   

11.
Hydroxyl-terminated polyesters are the most common polyols that are crosslinked through an isocyanate group. In this study, the polyester polyol resins were synthesized by using 1,4-cyclohexanedimethanol (1,4-CHDM) with the mixture of different diacids as 1,3-cyclohexanedicarboxylicacid (1,3-CHDA), 1,4-cyclohexanedicarboxylicacid (1,4-CHDA), isophthalic acid (IPA), adipic acid (AA), and azelaic acid (AZA). The solubility and viscosity of these polyester polyol resins were determined by using suitable solvent. All the polyester polyols were crosslinked with HDI isocyanurate and IPDI trimer to form polyurethane coating films. These films were evaluated for their mechanical, thermal, and chemical resistance properties. The studies on film characteristics reveal that the cycloaliphatic diacids afforded polyurethane with greater performance properties than that of aromatic and linear aliphatic diacids.  相似文献   

12.
The thermal properties of a set of experimental aliphatic–aromatic polyamides containing ether linkages were examined as a function of their chemical structure. Variations of the glass transition temperature (Tg) and melting temperature (Tm) could be correlated with the length of the aliphatic spacers and with the orientation of the phenylene rings. Polymers with a high concentration of p-oriented phenylene units showed a higher Tg than those containing mainly m-oriented ones; Tg values ranged from 110 to 155°C. Surprisingly, a negligible dependence of Tgs on the nature of flexible spacers was observed. For all of the polymers, the thermal stability was virtually the same, about 440°C, when tested by dynamic thermogravimetric analysis (TGA). However, quite different levels of thermal stability were found by isothermal TGA analysis for polyamides with different flexible spacers. Moreover, the poly(ether-amide)s described here compare fairly well with wholly aromatic polyamides when measured by dynamic TGA; but isothermal TGA measurements clearly demonstrated that they decompose faster than aromatic polyamides. Treatment of the TGA curves by the method of McCallum provided kinetic data that confirmed a better long-term stability for poly(ether-amide)s with a higher proportion of para-oriented phenylene rings. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:975–981, 1998  相似文献   

13.
A series of copolyesters were prepared by a direct polycondensation of 3‐(4‐hydroxyphenyl) propionic acid and p‐hydroxybenzoic acid (HBA), vanilic acid (VA), or syringic acid (SGA) of different composition in pyridine using diphenyl chlorophosphate and lithium bromide as condensing agents. The effects of methoxy substitution in the benzene ring and copolymer composition on the synthesis and thermal properties as well as hydrolytic degradation were examined. The methoxy substitution increased a glass transition temperature and a solubility, while it decreased a crystallinity and a thermal stability. The HBA series copolyesters showed a homogenous nematic phase, while the VA and SGA series copolyestes neither revealed an anisotropic melt nor formed a mobile melt below around 350°C. The hydrolytic degradation of melt‐pressed films was performed in a 5% sodium hydroxide aqueous solution at 40°C to test a biodegradability of the copolyesters. HBA‐50 and HBA‐30 exhibited the much higher degradation rate than HBA‐70, showing that the aliphatic ester linkage was more degradable than aromatic one. The degradation rates of VA‐50 and SGA‐50 were remarkably slower than that of HBA‐50 due to the steric hindrance of the methoxy group in the ortho position. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2474–2481, 2000  相似文献   

14.
Because of high susceptibility to thermal degradation during conventional melt processing of poly(3‐hydroxybutyrate) (P3HB) homopolymer, incorporation of a second or third monomer unit in the polyester backbones is expected to reduce the melting temperature and crystallinity, resulting in a controlled thermal degradation with improved stability. In this work, random poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxyvalerate) (P3HB3HV4HV) terpolyesters biologically synthesized by Cupriavidus necator were investigated for the thermal stability and degradation over a broad temperature range (100–300°C) in comparison with P3HB homopolyester. The work revealed that below the complete melting point (around 150°C), the terpolyester exhibited a high thermal stability and became an amorphous semisolid suitable for conventional thermal processing. Size exclusion chromatography plus nuclear magnetic resonance analysis was used to examine the thermal degradation products and the vulnerability of different monomer units at high temperatures (240–290°C). We found that 3HV unit in P3HB3HV4HV copolymers was more vulnerable to thermal degradation than 3HB unit under air. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41715.  相似文献   

15.
Interfacial polymerization is used to prepare biobased furan polyamides from the carbohydrate‐derived monomer, 2,5‐furan dicarboxylic acid, aromatic diamines, and varying chain length aliphatic diamines. The molecular weights of the furan polyamides variations range 10,000–70,000 g/mol. These biobased polyamides have improved solubility relative to petroleum‐derived polyamides affording enhanced processability options. The glass transition temperatures (Tg) of the biobased furan polyamides are higher than that of aliphatic analogs, but lower than phenyl‐aromatic analogs. The Tg for these furan polyamides are as high as 280 °C. Also, the furan polyamide glass transition temperatures increase with decreasing aliphatic diamine chain length similar to results exemplified in petroleum‐based nylons. Group contribution parameters are determined for furans to enable simple prediction of the glass transition temperature and decomposition temperature of furan polyamides. The molar glass transition function for the furan is calculated to be 27.6 ± 1.5 K kg/mol. Thermal analysis measurements of the biobased furan polyamides have maximum thermal degradation temperatures at 350 °C or higher, similar to that of aliphatic polyamides when scaled with the number average molecular weight. The molar decomposition temperature functions are determined to be 37 K kg/mol for furans bonded to aliphatic units and 42 K kg/mol for furans bonded to phenyl units. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45514.  相似文献   

16.
A kind of semiaromatic polyamide, poly(dodecamethylene terephthalamide) (PA12T) was synthesized via a polycondensation reaction of terephthalic acid and 1,12‐dodecanediamine. The structure of prepared PA12T was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (1H‐NMR), and elemental analysis. The mechanical properties of PA12T were also studied. The thermal behavior of PA12T was determined by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. Pyrolysis products and thermal decomposition mechanism of PA12T were analyzed by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). Melting temperature (Tm), glass transition temperature (Tg), and decomposition temperature (Td) of PA12T are 310°C, 144°C, and 429°C, respectively. The Py‐GC/MS results showed that the pyrolysis products were mainly composed of 32 kinds of compounds, such as benzonitrile, 1,4‐benzenedicarbonitrile, N‐methylbenzamide, N‐hexylbenzamide, and aromatic compounds. The major pyrolysis mechanisms were β‐CH hydrogen transfer process, main‐chain random scission, and hydrolytic decomposition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.  相似文献   

17.
A series of eight poly(aminobismaleimide)s containing aromatic units have been synthesized from a one‐step nucleophilic addition reaction between diamine and bismaleimide, without exogeneous solvent, to provide encapsulant withstanding high temperature suitable for power electronics. To have a homogeneous medium at room temperature, the solid aromatic diamines are first mixed with different liquid aliphatic ones, and then mixed with bismaleimide. The syntheses were then carried out at 175 °C for 15 min. Thus, according to their composition, these obtained thermosetting resins are characterized by a relaxation temperature between 98 and 190 °C and a coefficient of thermal expansion between 20 and 150 ppm/K. All material surfaces are hydrophobic and their moisture uptake is lower than 2–3 wt %. Finally, as expected, the substitution of a part of the aliphatic diamine by an aromatic one improves the thermal stability under air atmosphere of the resulting materials (Td = 280–300 °C increased to Td = 315–340 °C). Their use as power module encapsulant can therefore be considered. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46105.  相似文献   

18.
Polyamide 6 (PA6) nanocomposites based on epoxy resin‐modified montmorillonite (EP‐MMT) were prepared by melt processing using a typical twin‐screw extruder. X‐ray diffraction combined with transmission electron microscopy was applied to elucidate the structure and morphology of PA6/EP‐MMT nanocomposites, suggesting a nearly exfoliated structure in the nanocomposite with 2 wt % EP‐MMT (PA6/2EP‐MMT) and a partial exfoliated‐partial intercalated structure in PA6/4 wt %EP‐MMT nanocomposite (PA6/4EP‐MMT). The thermogravimetric analysis under air atmosphere was conducted to characterize the thermal–oxidative degradation behavior of the material, and the result indicated that the presence of EP‐MMT could inhibit the thermal‐oxidative degradation of PA6 effectively. Accelerated heat aging in an air circulating oven at 150°C was applied to assess the thermal–oxidative stability of PA6 nanocomposites through investigation of reduced viscosity, tensile properties, and chemical structure at various time intervals. The results indicated that the incorporation of EP‐MMT effectively enhanced the thermal–oxidative stability of PA6, resulting in the high retention of reduced viscosity and tensile strength, and the low ratio of terminal carboxyl group to amino group. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40825.  相似文献   

19.
A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

20.
The long‐term thermal‐oxidative aging behavior of polyamide 6 (PA6) was studied by comparison with the stabilized sample in this work. The variation of mechanical properties of the pure and the stabilized samples of PA6 with aging time at 110°C, 130°C, and 150°C were investigated, respectively. The aging mechanism of PA6 under heat and oxygen was studied in terms of the reduced viscosity, crystallization behavior, dynamic mechanical behavior, and chemical composition through the methods of polarized light microscopy (PLM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray photoelectron energy spectrum (XPS), and so on. The results indicated that at the initial stage of aging, the molecular crosslinking reaction of PA6 dominated resulting in the increase of the mechanical strength, reduced viscosity, and the glass transition temperature of the sample. And the molecular degradation dominated in the subsequent aging process resulting in the decrease of the melting temperature, the increase of the crystallinity, and the formation of the oxides and peroxides products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

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