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1.
An anionic poly(urethane–urea) dispersion (PUD) was cross-linked with different amount of partially methylated melamine formaldehyde
(PMMF). The isothermal curing behavior was observed by a rigid-body pendulum rheometer. The test results showed that cure
response of PUD cross-linked with PMMF was a function of the concentration of PMMF. Also, PMMF self-condensation could take
place during the curing process. In this experiment, the anionic poly(urethane–urea) dispersion has a large number of >N–H
cross-linking or branching sites in urethane and urea groups per molecule that allow a large number of PMMF to couple into
elastic PUD backbone to form branched structure with partial cross-linking. The dynamic mechanical properties of PUD cross-linked
with PMMF were affected by the concentration of PMMF. It was further shown that the tensile properties were strongly influenced
by the concentration of PMMF and curing temperature. 相似文献
2.
Wenshou Wang Peng Ping Haijun Yu Xuesi Chen Xiabin Jing 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5505-5512
A series of biodegradable, thermoplastic polyurethane elastomers poly(?‐caprolactone‐co‐lactide(polyurethane [PCLA–PU] were synthesized from a random copolymer of L ‐lactide (LA) and ?‐caprolactone (CL), hexamethylene diisocyanate, and 1,4‐butanediol. The effects of the LA/CL monomer ratio and hard‐segment content on the thermal and mechanical properties of PCLA–PUs were investigated. Gel permeation chromatography, IR, 13C NMR, and X‐ray diffraction were used to confirm the formation and structure of PCLA–PUs. Through differential scanning calorimetry, tensile testing, and tensile‐recovery testing, their thermal and mechanical properties were characterized. Their glass‐transition temperatures were below ?8 °C, and their soft domains became amorphous as the LA content increased. They displayed excellent mechanical properties, such as a tensile strength as high as 38 MPa, a tensile modulus as low as 10 MPa, and an elongation at break of 1300%. Therefore, they could find applications in biomedical fields, such as soft‐tissue engineering and artificial skin. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5505–5512, 2006 相似文献
3.
Three high molecular weight aliphatic polyesters derived from adipic acid and the appropriate diol - poly(ethylene adipate) (PEAd), poly(propylene adipate) (PPAd) and poly(butylene adipate) (PBAd) - were prepared by two-stage melt polycondensation method (esterification and polycondensation) in a glass batch reactor. Intrinsic viscosities, GPC, DSC, NMR and carboxylic end-group measurements were used for their characterization. Mechanical properties of the prepared polyesters showed that PPAd has similar tensile strength to low-density polyethylene while PEAd and PBAd are much higher. From TGA analysis it was found that PEAd and PPAd have lower thermal stability than poly(butylene adipate) (PBAd). The decomposition kinetic parameters of all polyesters were calculated while the activation energies were estimated using the Ozawa, Flynn and Wall (OFW) and Friedman methods. Thermal degradation of PEAd was found to be satisfactorily described by one mechanism, with activation energy 153 kJ/mol, while that of PPAd and PBAd by two mechanisms having different activation energies: the first corresponding to a small mass loss with activation energies 121 and 185 kJ/mol for PPAd and PBAd, respectively, while the second is attributed to the main decomposition mechanism, where substantial mass loss takes place, with activation energies 157 and 217 kJ/mol, respectively. 相似文献
4.
Thermal degradation at processing temperature and the effect on the rheological properties for poly(3-hydroxybutyrate) have been studied by means of oscillatory shear modulus and capillary extrusion properties, with the aid of molecular weight measurements. Thermal history at processing temperature depresses the viscosity because of random chain scission. As a result, gross melt fracture hardly takes place with increasing the residence time in a capillary rheometer. Moreover, it was also found that the molecular weight distribution is independent of the residence time, whereas the inverse of the average molecular weight is proportional to the residence time. Prediction of average molecular weight with a constant molecular weight distribution makes it possible to calculate the flow curve following generalized Newtonian fluid equation proposed by Carreau as a function of temperature as well as the residence time. 相似文献
5.
《先进技术聚合物》2018,29(6):1706-1717
Biodegradable poly(lactic acid) (PLA)/poly(butylene adipate‐co‐terephthalate) (PBAT) blends and films were prepared using melt blending and blowing films technique in the presence of chain extender‐Joncryl ADR 4370F. The ADR contains epoxy functional groups and used as a compatibilizer. The morphological, mechanical, rheological, thermal, and crystalline properties of the PLA/PBAT/ADR blown films were studied. Scanning electron microscopy micrographs of the films revealed more ductile deformation with increasing PBAT content. The addition of PBAT enhanced the toughness of the PLA film. Tensile tests indicated that the elongation at break increased from 20.5% to 334.6% in the machine direction and from 7.1% to 715.9% in the transverse direction. The Young modulus increased from 2690.5 to 395.6 MPa in the machine direction and from 2623.5 to 154.0 MPa in the transverse direction. The sealing strength of 40/60/0.15 PLA/PBAT/ADR film was the highest among all the samples up to 9.4 N 15 mm−1. These findings gave important implications for designing and manufacturing polymer packaging materials. 相似文献
6.
Mehdi Barikani Shahram MehdipourAtaei 《Journal of polymer science. Part A, Polymer chemistry》2000,38(9):1487-1492
A new aromatic sulfone ether diamine was synthesized by nucleophilic aromatic substitution reaction of 5‐amino‐1‐naphthol with bis(4‐chlorophenyl) sulfone in the presence of potassium carbonate in a polar aprotic solvent. Polycondensation reactions of the obtained diamine with pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic anhydride (6FDA) resulted in preparation of thermally stable poly(sulfone ether imide)s. Poly(sulfone ether amide)s also were prepared by reaction of the diamine with terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC). The prepared monomer and polymers were characterized by conventional methods. Physical and mechanical properties of polymers, including thermal stability, thermal behavior, solution viscosity, solubility behavior, and modulus, also were studied. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1487–1492, 2000 相似文献
7.
Poly(imido-ester-amides) (PIEAs) derived from three new asymmetric dicarboxylic acids containing an imide and ester groups and an aminoacidic moiety (glycine, L-alanine or L-valine) and a wholly aromatic silicon-containing diamine were synthesized according to the Yamazaki method. PIEAs were characterized by spectroscopic methods including 29Si NMR and elemental analysis, and the results were in agreement with the proposed structures. The thermal properties, glass transition temperature (Tg) and thermal decomposition temperature (TDT), were determined and the results showed that both parameters decreased when the aliphatic side chain provides by the amino acids increased, due to the higher free volume between the chains, which minimizes the interactions between them. Two of the PIEAs showed transparency according to the UV-vis spectra, due to that the side chains act as chain spacers, in front of PIEA-a including glycine as aminoacidic moiety, without side aliphatic group, which did not show transparence. 相似文献
8.
Synthesis,rheological, and thermal properties of waterborne hyperbranched polyurethane acrylate dispersions for UV curable coatings 总被引:1,自引:0,他引:1
A series of waterborne hyperbranched polyurethane acrylate (WHUAs) ionomers used for ultraviolet curable waterborne coatings
were synthesized. The average particle size of aqueous dispersion ranged between 48.2 and 75.3 nm at 0.05% concentration determined
by laser light scattering. The effects of end group of WHUAs on rheological properties were investigated. WHUAs have much
lower viscosity than EB2002, commercial linear waterborne polyurethane acrylate. Moreover, the glass transition temperature
(Tg) evaluated by differential scanning calorimetry of samples showed that the influence of end capping by hard segment consisting
of toluene diisocyanate–hydroxyethyl acrylate is significant due to the increase of crosslink density. All cured WHUA have
higher glass transition temperatures than those of cured EB2002. The results of thermogravimetric analysis for cured WHUA
films indicated good thermal stability with no appreciable weight loss until 200°C, and that an increase in the hard segment
content provoked the increases in thermal degradation temperature. The activation energies were calculated by Flynn–Wall method
to be 91.3, 114.3, and 139.7 kJ mol−1 for cured WHUA62, WHUA44, and WHUA26, with the individual ratios of 6:2, 4:4, and 2:6 for salt-like group to double bond
at the terminals, compared with 81.1 kJ mol−1 of EB2002 in N2 atmosphere, respectively. 相似文献
9.
In this work, based on castor oil (CO), flame retardant polyurethane sealants (FRPUS) with ammonium polyphosphate (APP) and aluminum hypophosphite (AHP) were prepared. The synergistic flame retardant effects between APP and AHP on flame retardancy, thermal stability, and flame retardant mechanisms of FRPUS were investigated. It was found that when the mass ratio of APP and AHP was 5:1, the limiting oxygen index (LOI) value of FRPUS increased to 35.1%, In addition, at this ratio, the parameters from cone calorimeter testing (CCT) were reduced; these parameters include peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR) and total smoke production (TSP). The thermal decomposition behavior of the FRPUS was investigated by thermogravimetric analysis (TGA). The results showed that AHP improved the thermal stability of the PUS/APP system and increased char residue at high temperatures. Moreover, the residual carbon was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM), gas phase pyrolysis products were investigated by thermogravimetric analysis/infrared spectrometry (TG-IR) and thermogravimetric analysis/mass spectrometry (TG-MS). It was observed that the flame retardant mechanisms of the APP/AHP system was the combination of gas and condensed phase flame retardant mechanisms. 相似文献
10.
El-Wahed MG Refat MS El-Megharbel SM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(4):916-922
Compounds having general formula: [M(FO)(Cl)(x)(H(2)O)(y)].zH(2)O, where (M=Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), FO=folate anion, x=2 or 4, y=2 or 4 and z=0, 1, 2, 3, 5 or 15) were prepared. The obtained compounds were characterized by elemental analysis, infrared as well as electronic spectra, thermogravimetric analysis and the conductivity measurements. The results suggested that all folate complexes were formed by 2:1 molar ratio (metal:folic acid) as a bidentate through both of the two carboxylic groups. The molar conductance measurements proved that the folate complexes are electrolytes. The kinetic thermodynamic parameters such as: E*, DeltaH*, DeltaS* and DeltaG* were estimated from the DTG curves. The antibacterial evaluation of the folic acid and their complexes was also done against some Gram positive/negative bacteria as well as fungi. 相似文献
11.
Terpolymer (8-HQGF) has been synthesized using the monomers 8-hydroxyquinoline, guanidine, formaldehyde in 1:1:2 molar proportions. The structure of 8-HQGF terpolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e. UV-Visible, FTIR-ATR and 1H NMR spectroscopy. Detailed thermal degradation study of the new terpolymer has been carried out to ascertain its thermal stability. Thermal degradation curve is discussed which shows two decomposition steps (265-475 °C and 540-715 °C). Sharp-Wentworth and Freeman-Carroll methods have been used to calculate activation energies and thermal stability. The activation energy (Ea) calculated by using the Sharp-Wentworth (21.98 kJ/mol) has been found to be in good agreement with that calculated by Freeman-Carroll (23.57 kJ/mol) method. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S∗) and frequency factor (Z) have also been evaluated on the basis of the data of Freeman-Carroll method. The order of reaction (n) is found out to be 0.9979. 相似文献
12.
S. Papadimitriou D. N. Bikiaris K. Chrissafis K. M. Paraskevopoulos S. Mourtas 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5076-5090
Poly(propylene succinate)/poly(ε‐caprolactone) (PPSu/PCL) 25/75, 50/50, and 75/25 w/w copolymers were prepared using a combination of polycondensation and ring opening polymerization. The randomness of copolymers was characterized using 1H NMR and 13C NMR spectroscopy. From molecular weights and DSC measurements it was observed that the molecular weight decreased with increasing the wt % content of PPSu, while the copolymers containing 50 and 75 wt % PPSu were completely amorphous. Enzymatic hydrolysis revealed that biodegradation rate was much enhanced compared with that of neat PCL and increased by increasing the PPSu content. From TGA analysis it was also found that the PPSu/PCL copolymers had similar thermal decomposition behaviour with the pure polyesters and exhibited their maximum decomposition rates at temperatures 400–420 °C. Two different mechanisms, which follow each other, were used to adequately describe their decomposition kinetics. The first one corresponded to the first stage taking place at 280–365 °C, where small mass loss was recorded and activation energies ranged between 94 and 156 kJ/mol. The second one took place at 370–460 °C and corresponded to the stage where the main polyester mass was decomposed. The activation energies for this stage ranged between 200 and 240 kJ/mol. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5076–5090, 2007 相似文献
13.
Mahalingam Vanjinathan A. Raghavan A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2959-2977
3,5‐bis(4‐aminophenoxy)phenyl phenylcarbamate—a novel AB2‐type blocked isocyanate monomer and 3,5‐bis{ethyleneoxy(4‐aminophenoxy)}phenyl carbonyl azide—a novel AB2‐type azide monomer were synthesized in high yield. Step‐growth polymerization of these monomers were found to give a first example of hyperbranched poly (aryl‐ether‐urea) and poly(aryl‐alkyl‐ether‐urea). Molecular weights (Mw) of the polymer were found to vary from 1,858 to 52,432 depending upon the monomer and experimental conditions used. The polydispersity indexes were relatively narrow due to the controlled regeneration of isocyanate functional groups for the polymerization reaction. The degree of branching (DB) was determined using 1H‐NMR spectroscopy and the values ranged from 87 to 54%. All the polymers underwent two‐stage decomposition and were stable up to 300 °C. Functionalized end‐capping of poly(aryl‐ether‐urea) using phenylchloroformate and di‐t‐butyl dicarbonate (Boc)2O changed the thermal properties and solubility of the polymers. Copolymerization of AB2‐type blocked isocyante monomer with functionally similar AB monomer were also carried out. The molecular weights of copolymers were found to be in the order of 6 × 105 with narrow dispersity. It was found that the Tg's of poly(aryl‐alkyl‐ether‐urea)s were significantly less (46–49 °C) compared to poly(aryl‐ether‐urea)s. Moreover the former showed melting transition at 154 °C, which was not observed in the latter case. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2959–2977, 2007 相似文献
14.
Several calcium silicate hydrate (C–S–H)-polymer nanocomposite
(C–S–HPN) materials have been prepared by incorporating poly(acrylic
acid) (PAA) into the inorganic layers of C–S–H during precipitation
of quasicrystalline C-S-H from aqueous solution. The synthetic C–S–HPN
materials were characterized by X-ray fluorescence (XRF), X-ray diffraction
(XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy/energy
dispersive spectroscopy (SEM-EDS), thermogravimetry (TG), differential thermogravimetry
(DTG) and differential scanning calorimetry (DSC). The XRD peaks of C–S–HPN
materials suggest the intermediate organizations presenting both intercalation
of PAA and exfoliation of C–S–H. The SEM images of C–S–H
and C–S–HPN materials with different PAA contents exhibit the
significant differences in their morphologies. Effects of the material compositions
on the thermal stability of series of C–S–HPN materials along
with PAA and C–S–H has been studied by TG, DTG and DSC. Three
significant decomposition temperature ranges were observed on the TG curves
of all C–S–HPN materials. 相似文献
15.
《先进技术聚合物》2018,29(9):2467-2476
Poly (caprolactone) membranes with addition of different poly (ethylene glycol) concentrations were prepared for separation of water/isopropanol azeotropic mixture by pervaporation process. Different characterization tests including Fourier transform infrared, scanning electron microscopy, water contact angle, and thermogravimetric analysis were carried out on the prepared membranes. In addition, the effect of poly (ethylene glycol) PEG content on the swelling degree and the performance of the prepared membranes in pervaporation process were investigated. According to the obtained results, all the membranes were water selective and the blend membrane containing 3 wt% PEG exhibited the best pervaporation performance with a water flux of 0.517 kg/m2 hour and separation factor of 1642 at the ambient temperature. Hydrophilicity improvement of the blend membranes was confirmed by constant decrease in water contact angle of the membranes as PEG content increased in the casting solution. Scanning electron microscopy cross‐sectional images indicated that the blend membranes containing PEG had a closed cellular structure. Furthermore, mechanical and thermal properties of the membranes decreased by adding PEG. 相似文献
16.
S. Kiran 《International Journal of Polymer Analysis and Characterization》2017,22(2):125-138
Synthesis and characterization of X-ray shielding thermoplastic polyurethane elastomers which are capable of blocking harmful radiation emitted by various sources are reported. X-ray shielding capability was generated in the polymer by covalently binding iodine atoms in a monomer and polymerizing it with other monomers such that the resultant polymer has the capability of shielding X-radiation. For rendering X-ray shielding capability to the polyurethane, Bisphenol-A (BPA) was iodinated to 4,4′-isopropylidinedi-(2,6-diiodophenol) (IBPA) and it was used as a chain extender during the synthesis of polyurethane. Polyurethanes were synthesized by reacting 1,6-diisocyanatohexane and IBPA with two different polyols, namely, poly(tetramethylene glycol) and poly(hexamethylene carbonate) diol. X-ray shielding polyurethanes (XPU) were characterized by infrared spectroscopy, thermogravimetry, dynamic mechanical analysis, energy-dispersive X-ray analysis, gel permeation chromatography, and X-radiography. Studies showed that by effectively changing polyol from polyether to polycarbonate, XPUs having different physicomechanical properties could be manufactured. Furthermore, these polyurethanes were also found to be noncytotoxic to L929 fibroblast cell lines. X-ray images revealed that the incorporation of IBPA has rendered X-ray opacity to the polyurethanes which are several times higher than the aluminum wedge of equivalent thickness. The materials are sufficiently flexible and rubbery, so can be used as coatings, films, or sheets for applications in energy sector, power-generating nuclear power plants, defense sector (bunkers for army personnel), medical applications (X-ray diagnostic and CT scanner rooms, gamma radiation therapy of cancer), etc. 相似文献
17.
S. Rajalekshmi M. Saminathan C. K. S. Pillai C. P. Prabhakaran 《Journal of polymer science. Part A, Polymer chemistry》1996,34(14):2851-2856
Poly(1,3-phenyl octanoate) (polyHPOA) was prepared by melt and solution polycondensation methods from 8-(3-hydroxyphenyl)octanoic acid (HPOA), a novel monomer useful as a chain disruptor in liquid crystalline copolyesters. The melt polycondensation technique gave a polyester of higher inherent viscosity (0.80 dL/g in p-chlorophenol) than that (0.75 and 0.56 dL/g, respectively, for the Ogata method and thionyl chloride/pyridine method in the same solvent) of solution techniques. The solubility of the polyesters was limited to strongly acidic and polar solvents. The polyester was characterized by elemental analysis, IR spectroscopy, WAXD, TGA, isothermal TGA and DTA. x-ray diffraction pattern of the polyesters indicated that it is amorphous in nature. TGA of the polyesters gave a thermal stability of 470°C in nitrogen atmosphere at 50% decomposition. The available thermal data suggest that the polyester undergoes thermal decomposition by a pyrolytic cleavage involving the ester linkage with the formation of ketene and phenol ended groups as intermediates. © 1996 John Wiley & Sons, Inc. 相似文献
18.
In this study, we proposed to synthesize soluble polyphenol derivatives containing azomethine bond. For this reason, o-dianisidine was chosen to synthesize Schiff base monomers due to containing dimethoxy groups. Four phenolic Schiff bases were synthesized by condensation reaction of o-dianisidine with salicylaldehyde (2-HBADIAN), 4-hydroxybenzaldehyde (4-HBADIAN), vanillin (MHBADIAN) and 3-ethoxy-4-hydroxybenzaldehyde (EHBADIAN). These monomers were converted to their polyphenol derivatives via oxidative polycondensation reaction (OP). The structures of the obtained compounds were confirmed by FT-IR, UV-vis, 1H NMR and 13C NMR techniques. Progressing of OP was also followed by a time-controlled spectrum mode of a UV-vis spectrophotometer. The molecular weight distribution parameters of the synthesized polyphenols were determined by the size exclusion chromatography (SEC). The synthesized compounds were also characterized by solubility tests, TG-DTA and DSC. Cyclic voltammetry (CV) measurements were carried out and HOMO-LUMO energy levels and electrochemical band gaps () were calculated. Additionally, optical band gaps (Eg) were determined by using UV-vis spectra of the materials. Electrical conductivities of both doped and undoped states of the synthesized materials were measured by four-point probe technique using a Keithley 2400 electrometer showing that P-2-HBADIAN has approximately 130 times higher electrical conductivity than the others. Also, it was stressed that the synthesized polyphenols are semiconductors which have a potential for electronic and optoelectronic applications, with fairly low band gaps. 相似文献
19.
Wenwei Zhao Yukio Yamamoto Seiichi Tagawa 《Journal of polymer science. Part A, Polymer chemistry》1998,36(17):3089-3095
Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998 相似文献
20.
Spacer length controlled highly thermo reversible polyurethane–urea based on polystyrene: synthesis and crystallization studies
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Poly(urethane–urea) (PUU) is prepared using dihydroxy functionalized polystyrene having Mw 2000 g/mol, 1,6 hexamethylene diisocyanate and three different diamines (1,2‐ethylenediamine, 1,4‐butanediamine and 1,6‐hexamethylene diamine) by melt polymerization method. The synthesized copolymer is characterized by viscosity measurements, Fourier transform infrared (FT‐IR) spectroscopy, wide angle 2D‐X‐ray scattering (WAXS) and differential scanning colorimetry (DSC). The inherent viscosity of the polymers is found to be in the range of 0.4–0.5 dl/g, suggesting that the polymers are of high molecular weight. FT‐IR results conclude that the urea groups form both monodendate and bidendate assemblies. Temperature‐dependent FT‐IR and WAXS data confirm that the crystallinity of the copolymer is highly reversible and depends on the spacer length. DSC data also confirm that the crystallization pattern depends on the spacer length. The swelling behavior in water and the solubility of the polymer in chloroform are depending on the type of chain extender used in the PUU synthesis. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献