Numerical investigation of film forming characteristics and mass transfer enhancement in horizontal polycondensation kettle

The process of producing high viscosity polyester by transesterification polycondensation needs to adjust the operating conditions and equipment structure of pre-polycondensation kettle and final polycondensation kettle to realize process intensification.In view of this,the fluid volume function method of computational fluid dynamics numerical simulation was used to investigate the film formation and surface renewal characteristics of horizontal polycondensation kettle under different operating conditions,including viscosity,rotating speed and liquid height.The results show that the viscosity and rotating speed were positively correlated with the film area and surface renewal in the pre-polycondensation stage.However,increasing the viscosity by several orders of magnitude in the final polycondensation kettle,the larger the film area and film thickness,but the overall surface renewal of the disk decreased.Therefore,a hexagonal hole disk is designed.By comparison,it is found that the film is more uniform,the surface update frequency is higher,and the power consumption can be reduced by more than 20%.

Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.

Polycondensation reaction and its mechanism during lignocellulosic liquefaction by an acid catalyst: a review

The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of the residue formed from liquefaction and the mechanism of polycondensation were reported mainly by Lin,Yamada and Kobayashi.The major products of cellulosic liquefaction are levulinic acid and hydroxymethylfurfural（HMF） derivatives under polyhydric alcohols and phenolated compounds under phenols.The cleavage of the β-O-4 bonds is the major reaction pathway of lignin liquefaction under various liquefying reagents regardless of whether they contain acid catalysts or not.The break up compounds by decomposition are polymerized to substances with high molecular weight by polycondensation in lignocellulosic liquefaction.The molecular weight of condensed residues increases almost linearly as a function of liquefaction time at the later stage of lignocellulosic liquefaction.The longer the time required,the greater the content of new residue generated by polycondensation during the entire process of liquefaction.We conclude that the condensed residues may stem from the interaction of degraded lignin and cellulose components in wood or from the products of two major components reacting with liquefying reagents.

High-efficiency acetaldehyde removal during solid-state polycondensation of poly(ethylene terephthalate) assisted by supercritical carbon dioxide

The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxide(sc CO2) during the solid-state polycondensation of PET.The influence factors of AA removal including the temperature,pressure,reaction time and the size of pre-polymer particles are systematically studied in this work.The results indicate that it is a highly efficient way to obtain high molecular weight PET with relative low concentration of AA.Correspondingly,the polymerization degree of PET could increase from 27.9 to 85.6 while the concentration of AA reduces from 0.229 × 10^(-6) to 0.055 × 10^(-6) under the optimal operation conditions of 230 °C,8 MPa and size of 0.30–0.45 mm.Thermodynamic performance tests show the increasing extent of PET crystallinity due to the fact that the plasticization of sc CO_2 is not obvious with extended reaction time,therefore the increasing crystallinity has no significant influence on AA removal.SEM observations reveal that the effects of sc CO_(2-) induced plasticization and swelling on PET increase significantly with the decrease of prepolymer size,and the surface of PET becomes more loose and porous in favor of the AA removal.

SYNTHESIS OF POLY(SILPHENYLENE-SILOXANE) THROUGH DEHYDROCARBON POLYCONDENSATION OF 1,4-BIS(DIMETHYLSILYL)BENZENE AND DIALKOXYSILANE

Poly(silphenylene-siloxane)s had been synthesized through dehydrocarbon polycondensation of 1,4- bis(dimethylsilyl)benzene(BDSB)and dialkoxysilane.The polymer composition and structure was characterized by ^(29)Si-NMR.The influence of temperature,B(C_6F_5)_3 concentration and monomer structure on the composition and the microstructure of the copolymers were investigated.It shows that elevating reaction temperature or using substrate (R O)_2R_2R_1Si with bulk organic group of R_1 or R_2 augments the run numb...

Preparation and characterization of biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids via in situ melt polycondensation

In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.

Sol-Gel Distribution of Polycondensation Reaction

A theoretical approach to polycondensation reaction of Aa-Bb type Involving intramolecular cycllzatlon has been proposed by Tang Au-chin et al.. In this paper, the theoretical sol-gel distribution is tested by polycondensation of adipic acid with trimethylol propane in a sto-ichiometric ratio of 0. 8, and the effect of intramolecular cyclization is discussed in detail.

Preparation of Microcapsules Containing Phase Change Material and Silicon Carbide Powder with Interfacial Polycondensation Reaction Method

The fundamental experiments were performed to establish the operational conditions required to prepare the microcapsules containing paraffin wax as a phase change material (PCM) and SiC powder with the interfacial polycondensation reaction. It was investigated how SiC powder affected a few characteristics of microcapsules such as the diameters of microcapsules, latent heat storage density, thermal responsibility and supercooling. In the experiment, the concentration of oil soluble surfactant, the revolution speed of impeller for preparing the (O/W) emulsion and the added weight of SiC powder were changed stepwise. The microcapsules containing PCM in which SiC powder was dispersed could be prepared well and characterized. The diameters of microcapsules increased by containing SiC powder and the content of SiC powder could be increased by performing surface modification of SiC powder. Latent heat storage density decreased with the content of SiC powder. Supercooling of PCM and thermal responsibility could be improved to some degree by containing SiC powder.

STUDY ON SOLID STATE POLYCONDENSATION OF POLYETHYLENE TEREPHTHALATE COPOLYMERS

The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polyconden-sation, and increases with the comonomers content. But the reaction rate of copolycondensationin melt state of this kind of copolymers is lower than that of PET. It is considered that the chemi-cal reactivity of comonomer is the main factor which affect the polycondensation in melt state,whereas the aggregative structure of the polymer is the main factor in solid state. The crystallinity and crystallite size of the copolymers have been measured by X-ray method.

PREPARATION OF LIQUID CRYSTALLINE COPOLYESTERS WITH SPACERS BASED ON BISPHENOL-A,BISPHENOL-S OR POLYSULFONE BY DIRECT POLYCONDENSATION

Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.

Novel Method of Hyperbranched Polymer Modified Nano-SiO_2-Grafting Hyperbranched Poly(amide-ester) from Nano-SiO_2 by One-Step Polycondensation

A new method of surface chemical modification of nano-SiO2 is proposed in this paper. In the presence of catalyst, the active hydroxyl groups on the surface of nano-SiO2 reacted with AB2-type monomer （N, N-dihydroxyethyl-3-amino methyl propionate） by one-step polycondensation. And the product＇s Fourer transform infrared （FTIR） graphs and transmission electron microscopy（TEM） images proved that hyperbranched poly （amine-ester） was grafted on nano-SiO2 surface successfully. Results show that the modified nano-SiO2 exhibits excellent dispersion and stability in some solvents such as alcohol and chloroform.

Polymer Radii and Moments in the Polycondensation Reaction of A_a Type

For the polycondensation reaction of A. type, the kth radius for k>2 can be expressed in terms of polymer moments.

Microwave-assisted Polycondensation of L-2-Hydroxy-3-phenylpropanoic Acid

Amorphous poly (L-2-hydroxy-3-phenylpropanoic acid) (PLHPPA) was synthesized by the microwave-assisted polycondensation of L-2-hydroxy-3-phenylpropanoic acid (LHPPA). The weight average molar mass (Mw) of PLHPPA ranged from 3600 to 5300 and polydispersity index (Mw/Mn) from 1.0 to 1.4 when the reaction mixture was irradiated by microwave at 255, 340 and 510 w for 1 to 10 h, respectively.

Synthesis of Soluble Polythiophene Partially Containing 3,4-Ethylenedioxythiophene and 3-Hexylthiophene by Polycondensation

A novel poly(quinquethiophene) partially containing 3,4-ethylenedioxythiophene (EDOT) and 3-hexylthiophene, poly(3,3 ''''-dihexyl-3',4',3''',4'''-diethylenedioxy-2,2':5',2'':5'',2''':5''',2''''-quinquethiophene), was synthesized by three types of polycondensations. Among them, direct C-H coupling reaction gave the polymer with the highest molecular weight. The resulting polymer was soluble in common organic solvents. Absorption and fluorescence spectra of the polymer showed a remarkable red-shift compared with the corresponding monomer due to the expansion of effective π-conjugation length.

Catalytic Cs₂CO₃Promotes “Silyl Method”-Type Polycondensation

Catalytic amounts of cesium carbonate are sufficient to initiate the “silyl method”-type step-growth polymerization of phenylene-bis-TMS-ethers and -thioethers with activated aryl fluoride monomers, and can thus be used instead of ce-sium fluoride or potassium carbonate. Cesium fluoride is very hygroscopic and potassium carbonate is generally used in equimolar amounts. The efficiency of catalytic amounts of cesium carbonate is demonstrated by the synthesis of poly(phenylene ether ether ketone) and poly(phenylene sulfide sulfone) examples.

New Synthetic Route to Copoly(Ester-Thioester)s by Direct Polycondensation of Thio-Acids with Diols of Cycloketones Derivatives

A new series of copoly(ester-thioester)s had been synthesized using direct polycondensation technique. These copolythioesters were synthesized by direct polycondensation of 4,4'-(tereph-thaloyIdithio) diacetic acid I, 3,3'(isophthaloyl-dithio) diacetic acid II, or 1,8 (sebacoyldithio) diacetic acid III, with 2,6-bis(p-hydroxybenzylidene) tert. butyl cyclohexanone IV and 2,6-divanyli-dene tert. butyl cyclohexanone V, using a condensing agent consisting of pyridine-thionyl clhloride complex. The resulting copolymers were characterized by elemental and spectral analyses, solubility, viscometery, electronic spectra and thermogravimietric analyses. The crystallinity of some copolymers was examined by X-ray diffraction analyses. Furthermore, the morphology of selec ted examples of the copolymers was examined by scanning electron microscopy.

PREPARATION OF POLY (LACTIC ACID)THROUGH THIONYL CHLORIDE ACTIVATED POLYCONDENSATION

A two-step process was used to synthesize the high molecular weight poly (lactic acid) using thionyl chloride as an activator for the polycondensation of prepolymer of lactic acid. The products were characterized by GPC, DSC, and 1H-NMR. Poly (L-lactic acid) (PLLA) with molecular weight Mw: 32875 was obtained when thionyl chloride was used, while low molecular weight PLLA Mw: 7350 was yielded without thionyl chloride. Effects of the concentration of thionyl chloride, polymerization time and bases on the molecular weight of poly (lactic acid) were investigated. In DSC scans the glass transition temperatures (Tg) of the resulting polymers varied from 25.3 to 57.6℃, and the Tg of poly(L-lactic acid) was higher than that of poly (D,L-lactic acid) (PDLLA). The melting points of poly (L-lactic acid) and poly (D, L-lactic acid) could not be found unless the polymers were obtained by thionyl chloride activator.

Highly elastic and degradable vitrimeric elastomers using polycondensation

Introducing covalently crosslinked network to polymer matrix can merge the advantages in reprocessing and durability of polymers.In this contribution,a series of high-performance vitrimeric elastomers were achieved via polycondensation.The topological structures of polymers were tuned by varying the feeding ratios of bisacetoacetate,hex–substituted bisacetoacetate,bisamine and tris(2-aminoethyl)amine.With these structural manipulations,the vitrimeric elastomers presented great elastic recovery properties(strain recovery value up to 80%)benefiting from the introduction of long chain branch.Furthermore,the elastomers exhibited excellent reprocessing property,water vapor/oxygen barrier and adhesive properties.Specially,the elastomers could be degraded into monomer under acid conditions which enabled the elastomer synthesis again in closed loop recycling system.The ease of the polycondensation in this work to prepare highly elastic and recyclable vitrimeric elastomers demonstrated exciting opportunities for the synthesis of sustainable polymers.

Influence of tectonic stress on coalification:Stress degradation mechanism and stress polycondensation mechanism

The function of pressure for coalification is a long-term controversial issue, and the main cause is that the strata pressure and the tectonic stress were confused, which are two different actions of "pres-sure" . The former benefits the physical coalification but retards the chemical coalification, whereas the latter may not only affect the physical structure of coal but also promote its chemical composition changes. In accordance with the organic molecule evolution of coal, there are two kinds of basic mechanisms of the influence of the tectonic stress on the chemical coalification: the tectonic stress degradation and the tectonic stress polycondensation. The stress degradation mechanism is a process of that, when the tectonic stress acted on the large molecule of coal in the form of mechanical force or kinetic energy, some chemical bonds of low decomposed energy, such as aliphatic side-chain and oxygenic functional groups, were broken up and then were degraded into free radicals of less mo-lecular weight, and finally escaped from coal in the form of liquid organic matter (hydrocarbon). The stress polycondensation is considered that, under the control of the anisotropic tectonic stress, the condensed aromatic nucleus trend to be parallel arranged and to be enhanced through rotating or displacing of aromatic rings, the basic structural unit of coal (BSU) increases by directional develop-ment and preferential stack. X-ray diffraction (XRD), Fourier transformation infrared microspectroscopy (FTIR), and rock pyrolysis analysis (Rock-eval) were employed to study the deformed coal series and the non-deformed coal series. The results showed that, compared with the non-deformed coal, the de-formed coal exhibits particular characteristics: weaker aliphatic absorbance peak and stronger aro-matic absorbance peak, lower pyrolysed hydrocarbon yield, and more increscent BSU. The concepts of stress degradation mechanism and stress polycondensation mechanism presented here would not deny the dominant function of the temperature in coalification, but emphasize the "catalysis" of the tectonic stress in coalification.

Non-aqueous Suspension Polycondensation in NMP-Ca Cl_2/Paraffin System―A New Approach for the Preparation of Poly(p-phenylene terephthalamide)

A non-aqueous suspension polycondensation method was proposed to proceed the reaction ofp-phenylenediamine and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide） （PPTA）. The system was operated with NMP-CaCI2 solution as the dispersed phase and inert liquid paraffin as the continuous phase. Each of NMP-CaCl2 solution microdroplet suspended in paraffin served as a microreactor where the polycondensation took place. According to the results of TGA, XRD, IR, SEM and EA, PPTA with good quality was obtained through this novel method, and a number of main factors influencing this process were investigated to determine the optimum condition for the preparation of PPTA. Besides, this two-phase polycondensation system brings many unique advantages compared to the conventional solution polycondensation method, including a sealed reaction environment keeping the reactants away from oxygen and water, easy removal of HCI to promote the reaction, well-controlled temperature and low viscosity which means less energy cost.