共查询到20条相似文献,搜索用时 492 毫秒
1.
Poly(ethylene terephthalate) (PET) formation in homogeneous, continuous-flow-stirred tank reactors (HCSTRs) operating at steady state has been simulated. The feed to the reactor is assumed to consist of the monomer bis-(hydroxyethyl) terephthalate and monofunctional compound (MF1) cetyl alcohol. The overall polymerization is assumed to consist of the polycondensation, reaction with monofunctional compounds, redistribution, and cyclization reactions. At a given time, the reaction mass consists of polyester molecules (Pn), polyester molecules with an ending of molecules of monofunctional compound (MFn), and cyclic polymers (Cn). A mass balance for each of these species in the reactor gives rise to a set of algebraic equations to be solved simultaneously. The MWD calculations show that the redistribution reaction plays a major role and cannot be ignored, This result is in contrast lo the observation for semi-batch reactors, for which redistribution becomes important when the cyclization reaction is included. For the same residence times of semi-batch and HCSTRs, the latter gives considerably lower-number average molecular weight, Nav, and polydispersity index, ρ. However, for the same conversions, the ρ for CSTR is higher. The concentration of the monofurctional compound, [MF1]0, in the feed and the reactor temperature both influence ρ, but the effect is small within the range studied. 相似文献
2.
The second stage of a batch polyethylene terephthalate (PET) reactor with a kinetic scheme consisting of side reactions like thermal degradation, redistribution, cyclization and reaction with monofunctional compounds (cetyl alcohol), in addition to the major polycondensation step, has been simulated. The cyclization equilibrium has been shown by Semlyen for various cyclic compounds to be chain-length-dependent1. Mass balance for various side products and the polymer, PET, have been carefully worked out and the resulting set of differential equations have been solved for the molecular weight distribution (MWD) of the polymer. It is found that the cyclization reaction has considerable effect on the polydispersity index of the polymer even though the total quantity of cyclic compound is no more than 5%. The effect of variation of temperature and initial concentration of monofunctional compound was found to have little influence on the polydispersity index of the polymer. Since the removal of the condensation product does not become diffusion-controlled till the average chain length of the polymer reaches the value of 30, the reaction mass can be assumed to attain a uniform ethylene glycol concentration for a given applied vacuum and can be determined by the vapour-liquid equilibrium relation. The fractional level of ethylene glycol concentration, , has been taken as a parameter and the MWD results were found to vary the redistribution rate constant with sensitivity increasing with decreasing [G]. It was shown that the importance of the redistribution reaction is increased when the cyclization reaction also occurs. 相似文献
3.
Anil Kumar 《应用聚合物科学杂志》1987,34(2):571-585
The differential equations governing the molecular weight distribution (MWD) in step-growth polymerization are coupled and nonlinear and a large number of them must be solved simultaneously to keep the truncation error low. In this work, these equations have been decoupled so that they can be solved sequentially. The solution of these is independent of the truncation error and there is considerable saving of computation time. To demonstrate the efficiency of the algorithm, the formation of polyethylene terephthalate (PET) in batch reactors with ethylene glycol evaporating has been analyzed. The feed to the reactor is taken as polymer with its oligomers present according to the Flory's distribution. The effect of pressure and temperature of the reactor on the progress of polymerization has been modelled and evaluated. The amount of ethylene glycol distilled, the concentrations of the first five oligomers Q1 to Q5, the number average chain length, and the polydispersity index of the polymer have been determined. It is shown that the reduced pressure and increased temperature reduce the concentration of the condensation product in the reaction mass, thus pushing the polymerization in the forward direction. Lastly the CPU time on Dec 1090 using this algorithm is only 0.40 s compared to about 10 min for similar computations using other existing methods. 相似文献
4.
A multicompartment model is proposed for a semibatch melt polycondensation of poly(ethylene terephthalate) in a rotating disk polymerization reactor and compared with laboratory experimental data. The reactor is a horizontal cylindrical vessel with a horizontal shaft on which multiple disks are mounted. The reactor is assumed to comprise N equal sized compartments and each compartment consists of a film phase on the rotating disk and a bulk phase in which disks are partially immersed. The effects of disk rotating speed, number of disks, reaction temperature, and pressure were investigated. It was observed that ethylene glycol is predominantly removed from thin polymer layers on the rotating disks and the enhanced interfacial area exerted by ethylene glycol bubbles accounts for about 30–50% of the total available interfacial mass transfer area. Although the rate of polymerization increases as more disks are used, the maximum number of disks in a reactor must be determined properly in order to prevent the formation of thick polymer films that result in a reduced specific interfacial area and reduced polymerization efficiency. At a fixed reaction pressure, the equilibrium conversion is reached but the rate of reaction can be further increased by increasing the reaction temperature. The results of the proposed multicompartment model are also compared with those predicted by a simple one-parameter model. © 1995 John Wiley & Sons, Inc. 相似文献
5.
Branched poly(ethylene terephthalate)s (PET) were synthesised with a variety of molar masses and with a large range of degree of branching by introduction of mono-, tri-(glycerol) and tetra-functional (pentaerythritol) comonomers to dimethyl terephthalate and ethylene glycol. The monofunctional alcohols, dodecanol and benzyl alcohol, were used as terminating agents to minimise gelation. The effect of various reaction parameters, such as percentage glycerol or pentaerythritol and polymerisation time, on limiting viscosity number [η] and weight average molar mass (Mw) were investigated. The thermal behaviour of branched PET was studied by differential scanning calorimetry; all samples showed a characteristic double endothermic melting peak and the glass transition temperature was not observed. Some branched PETs were subjected to solid-state polymerisation to increase the molar mass of previously prepared branched polymers. The solid-state polymerisation technique showed that the process not only promoted the molar mass but, more importantly, it increased the crystallinity of the polymer. Overall, the solid-state reaction rate was governed by initial molar mass, crystallinity, reaction temperature and time. © of SCI. 相似文献
6.
Anil Kumar Sushil K. Gupta Sanjiv Madan Nirmal G. Shah Santosh K. Gupta 《Polymer Engineering and Science》1984,24(3):194-204
The formation of polyethylene terephthalate (PET) has been modeled to have reactions with monofunctional compounds, redistribution, and cyclization reactions in addition to the usual polycondensation step. In the final stages, the overall polymerization is mass-transfer controlled and solution of the reactor performance equations have been determined through the orthogonal collocation technique. This technique is found to be considerably more efficient for PET reactors compared to the finite difference method; the use of ten collocation points gives results which are close to the exact solution. 相似文献
7.
Minoru Nagata Tsuyoshi Kiyotsukuri Susumu Minami Naoto Tsutsumi Wataru Sakai 《Polymer International》1996,39(2):83-89
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
8.
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
9.
Synthesis and characterization of poly(ethylene isophthalate‐co‐ethylene terephthalate) copolyesters
Poly(ethylene isophthalate‐co‐ethylene terephthalate) (PEIPET) copolymers of various compositions and molecular weights were synthesized by melt polycondensation and characterized in terms of chemical structure and thermal and rheological properties. At room temperature, all copolymers were amorphous and thermally stable up to about 400°C. The main effect of copolymerization was a monotonic increase of glass transition temperature (Tg) as the content of ethylene terephthalate units increased. The Fox equation accurately describes the Tg–composition data. The presence of ethylene terephthalate units was found to influence rheological behavior in the melt, with the Newtonian viscosity increasing as the content of ethylene terephthalate units increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 186–193, 2004 相似文献
10.
Influence of alkyl (C12–C14)-dimethyl-benzyl ammonium chloride in the solution of sodium hydroxide on the hydrolysis of poly(ethylene terephthalate) (PET), anionically modified poly(ethylene terephthalate) copolyster (CDP), and block polymer of poly(ethylene terephthalate)-poly(ethylene glycol) (EDP), has been studied under a variety of proportions, concentrations, time and temperature of reaction, M : L ratio, etc. Mechanical properties of treated polymeric materials are evaluated. Hydrolysis of two polymers in the same bath is compared with that in separate baths. 相似文献
11.
George P. Karayannidis Irini D. Sideridou Demetris N. Zamboulis Demetris N. Bikiaris Anastasios J. Sakalis 《应用聚合物科学杂志》2000,78(1):200-207
Poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI) homopolymers were synthesized by the two‐step melt polycondensation process of ethylene glycol (EG) with dimethyl terephthalate (DMT) and/or dimethyl isophthalate (DMI), respectively. Nine copolymers of the above three monomers were also synthesized by varying the mole percent of DMI with respect to DMT in the initial monomer feed. The thermal behavior was investigated over the entire range of copolymer composition by differential scanning calorimetry (DSC). The glass transition (Tg), cold crystallization (Tcc), melting (Tm), and crystallization (Tc) temperatures have been determined. Also, the gradually increasing proportion of ethyleno‐isophthalate units in the virgin PET drastically differentiated the tensile mechanical properties, which were determined, and the results are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 200–207, 2000 相似文献
12.
Genara S. Andrade David M. Collard David A. Schiraldi Yushan Hu Eric Baer Anne Hiltner 《应用聚合物科学杂志》2003,89(4):934-942
A series of poly[ethylene‐co‐bis(2‐ethoxy)hydroquinone terephthalate], PET‐co‐BEHQ copolymers were prepared by polymerization of various substituted bis(2‐hydroxyethyl)hydroquinones (BEHQs), dimethyl terephthalate (DMT), and ethylene glycol (EG). In addition to copolymers containing 6–16.5 mol % BEHQ, the homopolymer of BEHQ with dimethyl terephthalate, p(BEHQ‐T), was also prepared. The thermal and barrier properties of amorphous materials were studied. As the amount of comonomer was increased, the Tg and Tm of the materials decreased relative to those of PET. Oxygen permeability also decreased with increasing comonomer content. This improvement in barrier‐to‐oxygen permeability was primarily due to a decrease in solubility of oxygen in the polymer. All of the copolymers tested displayed similar oxygen diffusion coefficients. The decrease in solubility correlates with the decrease in Tg. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 934–942, 2003 相似文献
13.
Copoly(ethylene terephthalate–imide)s (PETI) were prepared by melt polycondensation of bis(2-hydroxyethyl)terephthalate (BHET) and imide containing oligomer, i.e., 4,4′-bis[(4-carbo-2-hydroxyethoxy)phthalimido]diphenylmethane(BHEI). The apparent rate of poly-condensation reaction was faster than that of homo poly(ethylene terephthalate) (PET) due to the presence of imide units. The PETI copolymers with up to 10 mol % of BHEI unit in the copolymer showed about the same molecular weight and carboxyl end group content as homo PET prepared under similar reaction conditions. The increase in Tg of copolymer was more dependent on molar substitution of BHEI than on substitution of BHEN, reaching 91°C with 8 mol % BHEI units in the copolymer from Tg = 78.9°C of homo PET. In the case of PETN copolymer, 32 mol % of bis(2-Hydroxyethyl)naphthalate (BHEN) units gave Tg of 90°C. The maximum decomposition temperature of PETI copolymer was about the same as that of homo PET by TGA analysis. The char yield at 800°C was higher than that of homo PET. © 1996 John Wiley & Sons, Inc. 相似文献
14.
A dynamic multicompartment model is proposed for a continuous flow rotating disk reactor for the finishing stage melt polycondensation of poly(ethylene terephthalate). In the multicompartment reactor model, ethylene glycol is removed from both the bulk melt phase and the film phase formed on the rotating disks. The specific interfacial area for the film phase is estimated using the empirical correlation for polymer film thickness, and the mass transfer coefficient is calculated using the penetration theory. The mass transfer enhancement factor is introduced to account for the increased interfacial area due to ethylene glycol bubbles. The effects of reactor design and operating parameters on molecular weight and ethylene glycol removal have been investigated through model simulations. In particular, a detailed analysis is presented on the ethylene glycol removal rate from the two phases. © 1996 John Wiley & Sons, Inc. 相似文献
15.
Rei‐Mei Chou Chi‐Chin Chang T Leon Yu Yu‐Hsien Tseng Mo‐Jyi Wu 《Polymer International》2001,50(2):213-221
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
16.
Taking advantage of a melt polycondensation process, a series of copolyesters composed of pure terephthalate acid (PTA), ethylene glycol (EG), and 1,3‐propanediol (1,3‐PDO) were synthesized. The component, molecular weight, molecular weight distribution, and thermal properties of the copolymers were characterized. The results show that the contents of trimethylene terephthalate (TT) units in the resulting copolyesters are higher than PDO compositions in original diol. Oligomer content in the copolyesters varies with the compositions and attains a minimum value when the TT ingredient is 49.52 mol %. The glass transition temperature (Tg) of the copolyesters varies from 78.5°C for PET (polyethylene terephthalate) to 43.5°C for PTT (polytrimethylene terephthalate) and decreases monotonically with the components. The copolyesters are amorphous copolymers when TT content is in the range of 32.4–40.8 mol %, as calculated from the melting enthalpy (ΔHm) measured via differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1511–1521 2006 相似文献
17.
Poly(ethylene terephthalate) waste materials were depolymerized by ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG) in the presence of a novel catalytic system: titanium (IV)‐phosphate. The new catalyst was synthesized through a reaction of TiCl4 with triethyl phosphate (C2H5O)3P(O). It was found that the depolymerization of poly(ethylene terephthalate) fiber proceeds faster in the presence of titanium (IV)‐phosphate compared with compounds traditionally used in this process like Zn(OOCCH3)2. The oligomer distribution in the glycolysis products was studied by size‐exclusion chromatography. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1148–1152, 2003 相似文献
18.
A mathematical model of a polycondensation reactor that can be used in the final stage for poly(ethylene terephthalate) (PET) is established and compared with experimental data obtained from a laboratory scale reactor with film renewal. Detailed side reactions are considered along with the diffusional removal of the small molecules through thin film. Among several kinetic constants, the polycondensation reaction rate constant k1(= k8) and diester group degradation reaction rate constant k7 have an influence over the degree of polymerization. The values of k1(= k8) and k7 for 0.05 wt% Sb2O3 were obtained as curve-fit values: (1) k1(= k8) = 3.4 × 106 exp(? 18.500/RT′) (L/mol-min); (2) k7 = 1.3 × 1011 exp(? 37,800/RT′) (min?1). Effects of the film exposure time, reduced pressure of vacuum, temperature, the initial terephthalic acid (TPA)/ethylene glycol (EG) mole ratio, the initial degree of polymerization, and catalysts were well explained by the model. 相似文献
19.
The effect caused by the presence of ethylene glycol on the gas‐liquid mass transfer velocity of CO2 in a aqueous phase has been studied. In this study two different gas‐liquid contactors have been used, a bubbling stirred reactor and a flat surface stirred vessel. The first contactor, gas phase, was introduced using a porous bubbling plate. The influence of operational variables, stirring rate, gas flow rate and ethylene glycol concentration were studied. The experiments were carried out at 298.15 K using a semicontinuous regime. The final aim was to obtain empirical equations that allow the calculation of the mass transfer velocity for this system a priori. 相似文献
20.
The behavior of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) on water aging has been studied above and below the glass transition temperature (Tg). The aging process is caused by: degradation of the matrix and an increase in crystallinity above Tg, and microcavitation at the amorphous/crystalline interface below Tg. Such behavior well explains the deviation of the sorption kinetics from the Fickian model. The apparent water diffusion coefficients and the transport activation energies of PET and PBT have been calculated at temperatures above and below Tg. The mechanical behavior of the two polymers on water aging has been measured by means of fracture mechanics and Izod impact tests at different stress concentration factors. An increase of toughness of PET at short aging times has been shown by mechanical tests and SEM analysis fracture surfaces of differently aged samples. Izod tests of PET and PBT composites reinforced by long glass fibers have shown the contribution of fibers to the total fracture energy. 相似文献