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1.
The average relaxation time τ0, relaxation times corresponding to segmental motion τ1 and group rotations τ2, of a series of binary mixtures of poly(ethylene glycols) (PEG 200+PEG 300, PEG 400+PEG 600, PEG 1500+PEG 4000, PEG 6000+PEG 9000, PEG 200+PEG 1500, PEG 300+PEG 4000, PEG 400+PEG 6000 and PEG 600+PEG 9000) have been carried out in dilute solutions of benzene and carbon tetrachloride at 9·83GHz. The effect on chain flexibility due to inter- and intra-molecular association in these binary mixtures is discussed by comparing relaxation times of these mixtures with their individual relaxation times in solution. It is inferred that the extent of hydrogen bonding in different binary mixtures is not similar and is influenced by solvent environment, but there is correlation between τ0 and τ1 values in all these binary mixtures, which may be because of hydrogen bonding. The observed τ2 values in all these mixtures suggests that the chain-ends remain excluded from the intermolecular association and τ2 is independent of the polymer constituents of the mixture and solvent. It is also equal to the τ2 values of the individual polymers. © 1998 SCI.  相似文献   

2.
Dielectric relaxation study of binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw = 40 000 g mol?1) and poly(ethylene glycol)s (PEGs) (Mn = 200, 400 and 600 g mol?1) with concentration variation was carried out in dilute solutions of benzene at 10.1 GHz and 35 °C. The average relaxation time τo, corresponding to segmental motion τ1 and group rotations τ2 was determined for PVP–PEGs mixtures. A comparison of these mixtures relaxation times was made with the relaxation times of PEGs in benzene solvent. The evaluated τo values of PVP–PEGs mixtures in benzene solution are assigned to the reorientation of PEG molecules. It has been observed that the τo value of PVP–PEG200 mixtures increases with increasing concentration of PVP but their values are small in comparison with the τo value of PEG200 molecules. In the case of PVP–PEG400 and PVP–PEG600 mixtures, the evaluated values of τo are greater than the corresponding τo values of PEG400 and PEG600 molecules in benzene solvent. The variation in τo values in these systems has been discussed by considering the stretching effect in the PEGs molecular chains in PVP–PEGs mixtures in benzene solutions. The high value of distribution parameter α (≈0.4 to 0.7) suggests that in these mixtures there is a large contribution of segmental motion and group rotations to the relaxation processes. The nature of the formation of hydrogen‐bonded PVP–PEG complex heterogeneous network due to hydrogen bonding between carbonyl groups of PVP monomer units and terminal hydroxyl groups of PEGs is discussed. Furthermore, the elongation behaviour of PVP–PEG complex networks in benzene solvent and the molecular dynamics in the mixture due to breaking and reforming of hydrogen bonds has been explored by comparing the evaluated relaxation times and the Kirkwood correlation factor of pure PEG molecules for their possible use in drug control release systems. The relaxation times of these mixtures are independent of their viscosity, but the elongation of the mixture network is influenced by the PEG chain length and the number of hydroxyl groups in comparison with the number of carbonyl groups in the mixtures. Copyright © 2003 Society of Chemical Industry  相似文献   

3.
Dielectric relaxation studies of poly(propylene glycol), average molecular weight 2000 g mol−1, in dilute solution of cyclohexane, decaline, benzene and carbon tetrachloride have been carried out at 10.10 GHz and 35 °C. Average relaxation time τ0, and relaxation times corresponding to segmental motion τ1, group rotations τ2 and dipole moment µ have been determined. It is found that τ0, τ1 and µ are influenced by the solvent environment while the τ2 value is solvent‐independent. A comparison has been made with the dielectric behaviour of poly(ethylene glycol), average molecular weight 1500 g mol−1, in dilute solutions of benzene and carbon tetrachloride because both systems have an equal number of monomer units. The effect of methyl side‐groups on dielectric relaxation in poly(propylene glycol) molecules is discussed. The Kirkwood correlation factor is also evaluated in dilute solutions with concentration variation and it is found that these molecules exist in cluster form due to intermolecular hydrogen bonding. © 2000 Society of Chemical Industry  相似文献   

4.
Dielectric behaviour of poly(propylene glycol) (PPG) of number‐average molecular weight 2000 g mol?1 and binary mixtures of PPG with water (PPG–W) of various concentrations were carried out in the frequency range 10 MHz to 4 GHz at 25 °C. The dielectric dispersion and absorption curves related to the orientational motion of these molecules in the binary mixtures are described by a single relaxation time using Debye's model. The values of static dielectric constant εo, high frequency limiting dielectric constant ε, and dielectric relaxation time τo were determined for PPG and PPG–W mixtures. The values of the dielectric parameters were used to explore the nature of homogeneous and heterogeneous dynamic networks formed through hydrogen bonding in the binary mixtures of PPG and water molecules with concentration variation. The dielectric studies of PPG molecules were also carried out in the same frequency range at four temperatures, namely 25, 35, 45 and 55 °C. The temperature‐dependent relaxation times were used to evaluate the thermodynamical parameters for the dielectric relaxation processes. The dielectric relaxation free energy of activation ΔFτ for PPG molecules was found in the range ~4.5 to 4.7 kcal mol?1, which corresponds to the activation energy needed for the breakage of hydrogen bonds. Furthermore, the large negative value of the entropy ΔSτ of PPG molecules confirms that the configuration involved in dipolar orientation has an activated state, which is more ordered than in the normal state. Copyright © 2004 Society of Chemical Industry  相似文献   

5.
This paper reports the measured values of dielectric permittivity ε′ and dielectric loss ε″ of ethylene glycol, diethylene glycol and poly(ethylene glycol)s of average molecular weight 200, 300, 400 and 600 g mol−1 in the pure liquid state. The measurements have been carried out in the frequency range 200 MHz to 20 GHz at four different temperatures of 25, 35, 45 and 55 °C. The complex plane plots (ε″ versus ε′) of these molecules are Cole–Cole arcs. The static dielectric constant ε0, high‐frequency limiting dielectric constant ε, average relaxation time τ0 and distribution parameter α have been determined from these plots. The value of the Kirkwood correlation factor g and the dielectric rate free energy of activation ΔF have also been evaluated. The dependence of relaxation time on molecular size and viscosity has been discussed. A comparison has also been made with the dielectric behaviour of these molecules in dilute solutions of non‐polar solvents, which were carried out earlier in this laboratory. The influences of intermolecular hydrogen bonding and molecular chain coiling on the dielectric relaxation of these molecules have been recognized. © 2000 Society of Chemical Industry  相似文献   

6.
Dielectric complex permittivity of propylene glycol (PG), poly(propylene glycol) (PPG-2000) and their mixtures with concentration of 25, 50 and 75 vol% of PG were measured in the frequency range 10 MHz-4 GHz at 25°C using time domain reflectometry (TDR). For these molecules and their mixtures, only one frequency independent dielectric loss peak was observed. The relaxation for these systems is described by a single relaxation time using Debye model. The large value of observed relaxation time for PG molecules shows the formation of molecular clusters. It is found that the relaxation time for PG-PPG mixtures is smaller in comparison to the relaxation times of PG and PPG molecules, and it linearly increases with the concentration of the PG in the mixtures. The values of relaxation times of PG-PPG mixtures are discussed particularly with respect to the solvent (PG) behaviour, which can be assigned to unaffected, loosely affected and tightly bound solvent and also with respect to the PPG chain coiling. As a peculiar feature the observed relaxation time is direct evidence of the interchange of solvent-solvent to solvent-polymer interaction.  相似文献   

7.
This paper reports the results of a systematic study of microwave dielectric relaxation times of poly(ethylene glycols), average molecular weight 200–9000, in dilute solutions of benzene at 9·83GHz. These results are compared with the values of relaxation times obtained earlier in carbon tetrachloride solutions. This shows that the average relaxation times τ0 and the relaxation time corresponding to segmental reorientation τ1 are influenced by the solvent environment. The variation in chain flexibility in these polymers with the increase in degree of polymerization and formation of intra- and inter-molecular hydrogen bonding in benzene and carbon tetrachloride solutions is discussed with the help of relaxation data. The relaxation time τ2 corresponding to group rotations has been determined. It is found that the τ2 value is independent of solvent environment and degree of polymerization, and may be attributed to the rotation of chain −OH end-groups around the C−O bonds in dynamic equilibrium, with the formation of a five-membered ring due to intra-molecular hydrogen bonding at the end of the chain. © 1998 SCI.  相似文献   

8.
E. Piorkowska  R. Masirek 《Polymer》2006,47(20):7178-7188
Plasticization of semicrystalline poly(l-lactide) (PLA) with a new plasticizer - poly(propylene glycol) (PPG) is described. PLA was plasticized with PPG with nominal Mw of 425 g/mol (PPG4) and 1000 g/mol (PPG1) and crystallized. The plasticization decreased Tg, which was reflected in a lower yield stress and improved elongation at break. The crystallization in the blends was accompanied by a phase separation facilitated by an increase of plasticizer concentration in the amorphous phase and by annealing of blends at crystallization temperature. The ultimate properties of the blends with high plasticizer contents correlated with the acceleration of spherulite growth rate that reflected accumulation of plasticizer in front of growing spherulites causing weakness of interspherulitic boundaries. In PLA/PPG1 blends the phase separation was the most intense leading to the formation of PPG1 droplets, which facilitated plastic deformation of the blends that enabled to achieve the elongation at break of about 90-100% for 10 and 12.5 wt% PPG1 content in spite of relatively high Tg of PLA rich phase of the respective blends, 46.1-47.6 °C. Poly(ethylene glycol) (PEG), long known as a plasticizer for PLA, with nominal Mw of 600 g/mol, was also used to plasticize PLA for comparison.  相似文献   

9.
To improve the processability of micropolymer‐based devices used for biomedical applications, poly(lactic acid) (PLA) was melt‐blended with poly(ethylene glycol)s (PEGs) of different molecular weights (MWs; weight‐average MWs = 200, 800, 2000, and 4000; these PEGS are referred to as PEG200, PEG800, PEG2000, and PEG4000, respectively, in this article). The thermal properties, mechanical properties, and rheological properties of the PLA and the PLA–PEG blends were investigated. The tensile samples’ morphologies showed that the low‐MW PEGs filled molds well. The rheological properties confirmed that the low‐MW PEGs decreased the complex viscosity, and improved the processability. With decreasing PEG MW, the PLA glass‐transition temperature decreased. The nanoindenter data show that the addition of PEG decreased the modulus and hardness of PLA. The morphologies of the tensile samples showed that with increasing PEG MW, the thicknesses of the core layers increased gradually. The elongation at break was improved by approximately 247% with the addition of PEG200. Such methods can produce easily processed biological materials for producing biomedical products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45194.  相似文献   

10.
Recent advances in the catalyst technology associated with the production of poly(propylene glycol) (PPG) have allowed for the fabrication of ultralow monol content PPG macrodiols (Acclaim? polyols), which are highly bifunctional and can be produced in substantially higher molecular weights and with narrower molecular weight distributions than previously possible. These factors have enabled the preparation of higher value elastomers and may allow for the first manufacture of economically attractive PPG‐based poly(urethane‐urea) (PUU) fibers. In the past, many performance polyurethane and PUU elastomers used poly(tetramethylene ether glycol) (PTMEG) for the soft segments either alone or in combination with other macrodiols. The work presented here details the investigation of the morphological features of PUU systems with mixed soft segments of PPG, PTMEG, and a low molecular analog of PPG, tri(propylene glycol) (TPG) in an effort to ascertain the influence of structural features on the mechanical and thermal properties of the elastomers. Also of interest was whether the incorporation of PPG and TPG would either prohibit or greatly hinder the formation of strain‐induced PTMEG crystallites. It was found that, even when only 60 wt % of the soft segments consisted of PTMEG, those soft segments were still able to undergo recognizable strain‐induced crystallization as detected by wide‐angle X‐ray scattering. It was also seen that, as the ratio of PPG to PTMEG was varied, there were systematic changes in the soft segment glass transition and cold crystallization characteristics. Inclusion of PPG and TPG resulted in PTMEG's diminished ability to undergo cold and strain‐induced crystallization, as seen with differential scanning calorimetry and wide‐angle X‐ray scattering. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3520–3529, 2003  相似文献   

11.
Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997  相似文献   

12.
Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in Tg and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb2O3 as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry  相似文献   

13.
Pressure-volume-temperature properties were measured for polymer solutions of poly(propylene glycol) (PPG)+anisole, polymer blends of PPG+poly(ethylene glycol methyl ether) (PEGME), and the blends of PPG+PEGME and poly(ethylene glycol) (PEG)+PPG with anisole at temperatures from 298.15 to 348.15 K and pressures up to 50 MPa. The Tait equation represents accurately the pressure effect on the liquid densities over the entire pressure range. The excess volumes change from positive to negative as increasing the mole fraction of PPG in the binary systems of PPG+anisole and PPG+PEGME. The volumetric data of the related binary systems were correlated with the Flory-Orwoll-Vrij and the Schotte equations of state to determine the binary parameters. By using these determined binary parameters, both equations predicted the specific volumes of the polymer blends with anisole to average absolute deviations of better than 0.13%.  相似文献   

14.
Poly(vinyl alcohol) (PVA) hydrogels have shown potential applications in bionic articular cartilage due to their tissue-like viscoelasticity, good biocompatibility and low friction. However, their lack of adequate mechanical properties is a key obstacle for PVA hydrogels to replace natural cartilage. In this study, poly(ethylene glycol) (PEG) and glycerol were introduced into PVA, and a PVA/PEG–glycerol composite hydrogel was synthesized using a mixing physical crosslinking method. The mechanical properties, hydrophilicity and tribological behavior of the PVA/PEG–glycerol hydrogel were investigated by changing the concentration of glycerol in PEG. The results showed that the tensile strength of the hydrogel reached 26.6 MPa at 270% elongation at break with 20 wt% of glycerol plasticizer, which satisfied the demand of natural cartilage. In addition, the excellent hydrophilicity of glycerol provides good lubricating properties for the composite gel under dry friction. Meanwhile, self-healing and cellular immunity assays demonstrated that the composite gel could have good self-healing ability and excellent biocompatibility even in the absence of external stimuli. This study provides a new candidate material for the design of articular cartilage, which has the potential to facilitate advances in artificial joint cartilage repair. © 2022 Society of Industrial Chemistry.  相似文献   

15.
The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the Tg value by 13 °C, although a 62% increase in fracture toughness (KIC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in Tg values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol?1 reduced the modulus of elasticity by approximately 47% and increased toughness (KIC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry  相似文献   

16.
BACKGROUND: To obtain a biodegradable thermoplastic elastomer, a series of poly(ester‐ether)s based on poly(butylene succinate) (PBS) and poly(propylene glycol) (PPG), with various mass fractions and molecular weights of PPG, were synthesized through melt polycondensation. RESULTS: The copolyesters were characterized using 1H NMR, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, mechanical testing and enzymatic degradation. The results indicated that poly(ester‐ether)s with high molecular weights were successfully synthesized. The composition of the copolyesters agreed very well with the feed ratio. With increasing content of the soft PPG segment, the glass transition temperature decreased gradually while the melting temperature, the crystallization temperature and the relative degree of crystallinity decreased. Mechanical testing demonstrated that the toughness of PBS was improved significantly. The elongation at break of the copolyesters was 2–5 times that of the original PBS. Most of the poly(ester‐ether) specimens were so flexible that they were not broken in Izod impact experiments. At the same time, the enzymatic degradation rate of PBS was enhanced. Also, the difference in molecular weight of PPG led to properties being changed to some extent among the copolyesters. CONCLUSION: The synthesized poly(ester‐ether)s having excellent flexibility and biodegradability extend the application of PBS into the areas where biodegradable thermoplastic elastomers are needed. Copyright © 2009 Society of Chemical Industry  相似文献   

17.
This article reports on the modification of unsaturated polyesters by poly(ethylene glycol) end groups in order to influence the solution behavior in styrene and to modify mechanical properties of the cured resin. The synthesis was done by the reaction of a carboxyl-terminated unsaturated polyester with various poly(ethylene glycol) mono-methyl ethers of molecular weights from 350 to 2000 g/mol. The characterization and curing properties of the synthesized block copolymers are presented. The glass transition temperatures decrease with increasing length of the poly(ethylene glycol) end groups. The introduction of long poly(ethylene glycol) end groups (2000 g/mol) leads to a phase separated and partly crystalline block copolymer with a melting point of 48°C. The block copolymers can be easily diluted in styrene to create the curable resins. The mixtures containing the block copolymers with the short poly(ethylene glycol) end groups (350 and 550 g/mol) could be cured in a reasonably short time. Compared to commercial unsaturated polyesters the mechanical testing revealed that the tensile strength is decreasing while the elongation is increasing. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 527–537, 1997  相似文献   

18.
Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (Tm), cold crystallization and glass transition (Tg) decreased with the copolymerization. Tm depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. Tg was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.  相似文献   

19.
Poly(1,4-butanediol succinate) copolymers were prepared by melt polycondensation of succinic acid and 1,4-butanediol with 10–50mol% (in feed) of poly(ethylene glycol) (PEG), where molecular weight (MW) of PEG is 200–2000. The reduced specific viscosity of the copolymers increased with incorporation of the PEG component, but a higher PEG content in the copolymers reduced it. The temperature of melting (Tm) and crystallinity decreased with increasing PEG content. Tm depression of the copolymers followed approximately Flory’s equation, suggesting that these are random type copolymers. Tensile strength and elongation decreased with increasing MW and content of PEG. The weight loss of copolymer films in a buffer solution with or without lipase at 37°C, as well as water absorption, increased with increasing PEG content, implying that higher water absorption contributes to hydrolytic degradation of the films. However, the weight loss of copolymers with PEG of lower MW increased greatly in spite of lower water absorption, demonstrating that hydrolytic degradation is influenced by the concentration of degradable ester linkages between succinic acid and PEG segments rather than water absorption. © of SCI.  相似文献   

20.
A series of carboxyl‐terminated poly(ethylene glycol) adipate (CTPEGA) was synthesized by polycondensation of poly(ethylene glycol) (PEG) of various molecular weights (“2000,” “4000,” “6000,” “8000,” “10,000” g/mol) and adipic acid. CTPEGA was incorporated into the epoxy by a prereaction method. The CTPEGA and modified epoxy samples were thoroughly characterized by Fourier transform infrared spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. The effects of molecular weight of CTPEGA on thermomechanical and viscoelastic properties of the modified epoxy networks were investigated. Maximum improvement in impact strength was found for the epoxy network modified with CTPEGA containing PEG of molecular weight 2000 g/mol. With further increase in molecular weight of CTPEGA, the impact strength of the modified network decreases. However, in case of higher molecular weight CTPEGA, the improvement in toughness was achieved without any reduction in Tg due to the complete phase separation. The results were explained in terms of morphology studied by scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1723–1730, 2007  相似文献   

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