Synthesis of flexible polyarylate by interfacial polycondensation

Products with hydroxyl ends were synthesized from the esterification of bisphenol-A, terephthalic acid and ethylene glycol. These ester products were then used for synthesis of polyarylate by interfacial polycondensation. Not only the relative concentrations of reactants for esterification but also the conditions for interfacial polycondensation, such as the monomer ratio between two phases and the reaction time, play significant roles in affecting the properties of final products. Under proper synthesis conditions, the polyarylate formed could possess equivalent thermal characteristics and much higher impact strength in comparison with unmodified polyarylate due to the incorporation of flexible aliphatic segments from ethylene glycol. X-ray diffraction showed the existence of aliphatic segments would induce small degree of orderly alignment locally in structure.     

A model for microencapsulation in polyurea shell by means of interfacial polycondensation

A quasi-steady state model, based on two parallel modes of diffusion and a polycondensation reaction at the inside surface of a microcapsule, is formulated to compute the time of this microencapsulation process. The predicted times of encapsulation are in agreement with observed values reported in patents. It is also shown that, for small shell thickness, the process is reaction-controlled.     

固相缩聚PET的分子量分布

在研究聚酯（PET）固相缩聚反应动力学的基础上,进一步利用多组分模型,模拟分析了固相缩聚PET的分子量分布,模拟结果与凝胶渗透色谱测试结果相吻合。     

Synthesis of new polyesters with chelating subunits by solution and interfacial polycondensation

New polyesters have been prepared by solution and interfacial polycondensation of acid chlorides obtained from bis‐α,ω‐polymethylene‐[(2‐methoxy)phenoxy]acetic acids, acid‐ether siderophores AE _n (n being the number of methylene units), and diols including bisphenol A, ethylene glycol and propanediol. For interfacial polycondensation, average molecular weights range from 1000 to 4500 g mol^?1; at higher temperature the molecular weights increase but the yield is smaller. Differential scanning calorimetry shows T_g ranging from ?5 to + 110 °C. Polyesters are crystalline with n = 6 and amorphous with n = 2 and 4; in addition, increasing n in AE _n increases molecular weights and T_g values. In solution polycondensation, the average molecular weights are around 3000 g mol^?1 and T_g is low. © 2001 Society of Chemical Industry     

Main-chain sulphur containing water soluble poly(N-isopropylacrylamide-co-N,N′-dimethylacrylamide sulphide) copolymers via interfacial polycondensation

Here, we report the first synthesis of water soluble poly(N-isopropylacrylamide-co-N,N′-dimethylacrylamide sulfide) copolymers via conventional interfacial polycondensation method using phase transfer catalyst (PTC). The effect of various kinds of PTC having different aliphatic chain length and counter ion were employed to examine the kinetics of polysulfide polymer formation. The reactivity ratios, determined employing extended Kelene–Tüdös method using feed composition obtained from ¹H NMR analysis, suggest that N-isopropylacrylamide (NIPAM) is more reactive than N,N′-dimethylacrylamide (DMA) in both mono- and di-sulfide polymers. Thermal transition behavior investigated by differential scanning calorimetry (DSC) demonstrated that as the sulphur rank of the sulfide main chain linkages increased, the flexibility of the polymers increased reflected by lower glass transition temperature (T_g) values. The thermal degradation behavior and the major degradation products have been characterized by thermogravimetric analysis (TGA) and electron-impact mass spectroscopy (EI-MS), respectively. Both the studies reveal that the degradation takes place due to weak-link scission of the polymeric main chain. Solubility in water and in most of the common organic solvents even after the sulphur rank increased from 1 to 2 in the main chain, is expected to render potential applications in biological field as well as in industry for these interesting new class of polymers.     

界面缩聚法制备间位芳香族聚酰胺的研究

采用界面缩聚的方法制得了比浓对数粘度较高的聚间苯二甲酰间苯二胺(PMIA)聚合物。对聚合过程中有机溶剂的选择、两种反应单体在各自相中的起始浓度、搅拌速率、缚酸剂的选择等进行了研究。最佳工艺为:以THF为有机溶剂,常温下,CMPD/CIPC比值约为1∶1.1,搅拌速率为750 r/min,以2-甲基吡啶为缚酸剂,制得的聚合物ηinh最大,可达到1.8 dL/g。利用热重法对PMIA的热稳定性进行了分析,结果表明,聚合物具有较好的热稳定性,符合高温使用的要求。     

Influence of system variables on the morphological and dynamic mechanical behavior of polydimethylsiloxane based segmented polyurethane and polyurea copolymers: a comparative perspective

The effect of the variables of polydimethylsiloxane (PDMS) soft segment (SS) length, hard segment (HS) type and content as well as choice of chain extender (its MW and symmetry) on the morphology of segmented polyurethane and polyurea copolymers was investigated. The methods of dynamic mechanic analysis, small angle X-ray scattering, atomic force microscopy, and mechanical testing were used in this analysis. Average PDMS MW of 900, 2500 or 7000 g/mol were utilized and the hard segment content ranged from 16 to 50 wt%. HMDI was used as the diisocyanate. All copolymers were synthesized via the prepolymer method. The PDMS MW had a marked effect on the morphology of the materials. Copolymers with PDMS MW of 2500 and 7000 g/mol were clearly found to be well microphase separated relative to those containing the 900 g/mol PDMS SS. The polyurea sample with a PDMS MW of 7000 and HS content of 25 wt% exhibited a remarkable service temperature window (for rubber-like behavior) of ca. 230 °C (from −55 to 175 °C) whereas it was ca. 200 °C wide (from −55 to 145 °C) for the equivalent polyurethane sample. In general, the degree of microphase separation was found to be greater in the polyurea samples due to their more cohesive bidentate hydrogen bonding.     

影响聚酯缩聚真空的因素及处理

介绍了聚酯生产真空系统的组成及特点,并对真空系统运行状况的表征方法进行了分析和总结。结合真空理论,重点分析了在聚酯生产过程中真空状况的各种影响因素,如:喷射泵组抽气能力、液环泵系统、真空通道、EG喷淋冷凝系统、系统严密性等。结合生产实践经验,提出了聚酯缩聚反应真空状况的日常维护及故障的处理方法。     

间歇缩聚真空系统带料的探讨

分析该系统产生带料的原因和应采取的措施。缩聚催化剂品种、加入量 ,导料压力和进料速度 ,真空管线过细 ,操作控制不合理 ,供热系统不稳定 ,酯化反应不充分等都会造成带料。选择和控制原辅料的质量和加入量 ,根据自身装置状况制定最佳控制方案 ,建立标准减压及温度变化曲线 ,指导生产。改造真空系统 ,增设预缩聚系统等可以保质增产。     

Molecular dynamics studies on the effects of water speciation on interfacial structure and dynamics in silica-filled PDMS composites

The effect of chemisorbed and physisorbed water on the interfacial structure and dynamics in silica-filled polydimethylsiloxane (PDMS) based composites have been investigated. Toward this end, we have combined molecular dynamics simulations and experimental studies employing dynamic mechanical analysis and nuclear magnetic resonance analysis. Our results suggest that the polymer-silica contact distance and the mobility of interfacial polymer chains significantly decreased as the hydration level at the interface was reduced. The reduced mobility of the PDMS chains in the interfacial domain reduced the overall, bulk, motional properties of the polymer, thus causing an effective ‘stiffening’ of the polymer matrix. The role of the long-ranged Coulombic interactions on the structural features and chain dynamics of the polymer were also examined. Both are found to be strongly influenced by the electrostatic interactions as identified by the bond orientation time correlation function, local density distribution and radial distribution functions. These results have important implications for the design and life performance behavior of nanocomposite silica-siloxane materials.     

Influence of molecular rigidity on interfacial ordering in diphenyl-based polysiloxane films

Synchrotron X-ray reflectivity (XRR) shows significant differences between the ordering in thin films of diphenyl-based siloxane oligomers with single versus double backbones of -Si-O- repeating groups. We show that the more restricted conformational arrangement of twofold-skeleton molecules results in a higher degree of molecular ordering indicated by 2-2.5 times higher value of intensity of the corresponding Bragg peak in thin solid films of poly(phenylsilsesquioxane) than in films of poly(diphenylsiloxane), regardless of the solvent used for film casting. In both cases, the ordered molecules are located within 40-50 Å of the substrate surface. The results indicate unambiguously that the chain stiffness of siloxanes governs the degree of ordering in the restricted geometry of the interfacial region.     

Performance of polyurea formulations against impact loads: A molecular dynamics and mechanical simulation approach

Today, polyurea is known as one of the most famous and widely used protective coatings in the world. The unique properties of polyurea are at such a high level that it is possible to use this coating in a wide range of applications. Although polyurea is generally made from the reaction between two types of precursors (diisocyanate and diamine), it is challenging to choose the right precursor pair for producing a coating with a specific application due to the great variety of introduced diisocyanate and diamine precursors. On the other hand, the experimental synthesis of the formulations and the study of their performance is also very costly and time-consuming. In this study and by examining a series of commercially available precursors for polyurea coatings synthesis, well-known materials have been introduced and classified. Then, a representative of each formulation family is simulated by a molecular dynamics and mechanical approach using a three-step method on atomic, meso, and continuum scales, and the mechanical properties of the formulations are extracted. Then, by examining the response of each formulation to the three types of dynamic load (earthquake, projectile impact, and air blast), the protective capabilities of these formulations have been compared, and the optimal formulation for each application has been introduced.     

Investigation of the thermal degradation of polyurea: The effect of ammonium polyphosphate and expandable graphite

Polyurea was compounded with ammonium polyphosphate and expandable graphite and the morphology was studied by atomic force microscopy. The thermal degradation of polyurea and polyurea compounded with the additives has been investigated using thermogravimetry coupled with Fourier Transform infrared spectroscopy and mass spectrometry. The study of the thermal degradation and the parameters affecting the thermal stability of PU is essential in order to effectively design flame retarded polyurea. In general, thermal decomposition of polyurea occurs in two steps assigned to the degradation of the hard segment and soft segment, respectively. Adding these additives accelerates the decomposition reaction of polyurea. However, it is clear that more char is formed. This char is thermally more stable than the carbonaceous structure obtained from neat PU. The intumescent shield traps the polymer fragments and limits the evolution of small flammable molecules that are able to feed the flame.     

Modifying montmorillonite clay via silane grafting and interfacial polycondensation for melt compounding of nylon‐66 nanocomposite

A trifunctional organo alkoxysilane (3‐aminopropyl)triethoxysilane (γ‐APS) has been used as reagent for the chemical modification of montmorillonite clay. Silane grafting was taken place in dry and hydrolyzing conditions. Silane grafted and pristine clay took part in interfacial polycondensation process to deposit a layer of nylon‐66 onto the clay lamellae and therefore, enhance their affinity with nylon‐66 matrix. Evidence of presence of grafted silane molecules and deposition of nylon‐66 on clay particles were provided by Fourier transform‐infrared, thermogravimetric analysis (TGA), and X‐ray diffraction (XRD). Such modified clays and pristine clays were melt compounded with nylon‐66. The structures of the resulting nylon composites were characterized using XRD and transmission electron microscopy and the results showed presence of both intercalation and exfoliation. TGA thermograms of nanocomposites indicated improved thermal stability upon the incorporation of silane grafted montmorillonite. Furthermore, differential scanning calorimetry scans showed that silane modified clays promoted crystallization in nanocomposites. Increase of storage modulus and depression of tan δ peak in nanocomposites in dynamical mechanical thermal analysis were observed. The rheological properties of nylon‐66 and nanocomposites were also evaluated and differences in values of complex viscosity of samples were noticed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing theory of the Aai–Bbj type polycondensation. (II) sol-gel distribution

An alternative way is proposed to approach the sol-gel distribution of A_ai–B_bj type polycondensation by taking into consideration intramolecular reaction. The equations deduced basically from the definition of the sol fraction and the chemical equilibrium of reactants in this paper can be reduced to those of Tang Au-chin's and Miller's expressions. Comparing experimental with theoretical values, we found that the results of this paper are closer to the real cases than those of other authors.     

High‐molecular‐weight aliphatic polycarbonates by melt polycondensation of dimethyl carbonate and aliphatic diols: synthesis and characterization

Aliphatic polycarbonates (APCs) synthesized by polycondensation of dialkyl carbonates and aliphatic diols have often been used as precursors for the preparation of novel polyurethanes. However, they could not be applied in plastics directly because of poor mechanical properties caused by low molecular weight. In the work reported in this paper, three kinds of fairly high molecular weight (M_w ≥ 166 000 g mol^?1) APCs with narrow dispersity ( ) were successfully synthesized via a successive two‐step polycondensation of dimethyl carbonate and diols, using a novel TiO₂/SiO₂‐based catalyst. This process gave a high yield of above 85%. ¹H NMR spectra indicated that there was no detectable decarboxylation happening during polycondensation at high temperature. The effects of molecular weight on the mechanical properties of the APCs are discussed. APCs with M_w greater than 70 000 g mol^?1 showed useful mechanical properties. Especially, poly(butylene carbonate) and poly(hexamethylene carbonate) exhibited excellent tensile strengths of 34.1 and 40.0 MPa, respectively, when their M_w was ca 170 000 g mol^?1. All the APCs showed appreciable biodegradability under enzymatic degradation. Copyright © 2011 Society of Chemical Industry     

Solid-state polycondensation of poly(ethylene terephthalate) modified with isophthalic acid: kinetics and simulation

The kinetics for the solid-state polycondensation (SSP) of poly(ethylene terephthalate) modified with isophthalic acid at the protection of nitrogen gas was studied in the paper. A kinetic model controlled by the reversible chemical reactions and the three dimension diffusions of small molecule by-products has been established. The kinetic parameters of the SSP of PET at different temperatures, including the forward rate constants of transesterification reaction (k₁) and esterification reaction (k₂), the diffusion coefficients of EG (D₁) and water (D₂), the concentrations of EG (g_s) and water (w_s) on the surface of PET chips in SSP, and the activation energies of these kinetic parameters were obtained by experiments and solution of the model. Using the model and the kinetic parameters, the SSP of poly(ethylene terephthalate) modified with isophthalic acid can be simulated with good accuracy. In addition, the influences of nitrogen gas flow rate, the chip dimension and the carboxyl end-group concentration of the PET prepolymer on the molecular weight of PET after SSP, and the change of the EG concentration of PET chips with reaction time were also studied by simulation.     

超临界CO_2中合成的聚丙烯腈的相对分子质量及其分布研究

用凝胶渗透色谱法测试了超临界CO_2下合成的聚丙烯腈的相对分子质量及其分布,并详细研究了各种反应条件如:单体浓度、引发剂浓度、时间及CO_2压力对聚丙烯腈的相对分子质量、相对分子质量分布及转化率的影响。     

锑系催化剂聚酯的熔融及固相聚合

对锑系催化剂中常用的醋酸锑(Sb(AC)3)、三氧化二锑(Sb2O3)和乙二醇锑(Sb2(EG)3)进行熔融及固相聚合试验,结果表明,三氧化二锑的有效锑含量比醋酸锑及乙二醇锑低;乙二醇锑在固相聚合时的催化作用略低于醋酸锑和三氧化二锑;3种锑系催化剂相比,乙二醇锑催化剂聚酯固相聚合速度略慢,但特性粘数增幅最为平稳;220℃下的反应速率常数以醋酸锑制得的聚酯最大。     

Preparation and characterization of polyurethane microcapsules containing n‐octadecane with styrene‐maleic anhydride as a surfactant by interfacial polycondensation

A series of polyurethane microcapsules containing a phase change material (PCM) of n‐octadecane was successfully synthesized by an interfacial polymerization in aqueous styrene‐maleic anhydride (SMA) dispersion with diethylene triamine (DETA) as a chain extender reacting with toluene‐2,4‐diisocyanate (TDI). The average diameter of microPCMs is in the range of 5–10 μm under the stirring speed of 3000–4000 rpm. Optical and SEM morphologies of microPCMs had ensured that the shell was regularly fabricated with the influence of SMA. FTIR results confirmed that the shell material was polyurethane and the SMA chains associated on core material reacted with TDI forming a part of shell material. The shell thickness was decreasing in the range of 0.31–0.55 μm with the molar ratio of DETA/TDI from 0.84 to 1.35 and the weight of core material increasing from 40 to 80% (wt %). By controlling the weight ratio of PCM as 40, 50, 60, 70, and 80% in microPCMs, it was found using DSC that the T_m and T_c of microPCMs were in the range of 29.8–31.0^oC and 21.1–22.0°C and an obvious phase change had been achieved nearly the same temperature range of that of PCM. The results from release curves of microPCM samples prepared by 1.4, 1.7, and 2.0 g of SMA indicated the release properties were affected by the amount of the dispersant, which attributed to the emulsion effect and shell polymerization structure. The above results suggest that the shell structure of microPCMs can be controlled and the properties of microPCMs determined by shell will perform proper practical usage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4996–5006, 2006