Influence of thermal runaway in styrene–acrylonitrile bulk copolymerization revealed by computational fluid dynamics modeling

The computational fluid dynamics (CFD) and kinetic-based moment methods coupled approach is adopted to simulate the bulk copolymerization of styrene–acrylonitrile (SAN) in a stirred tank reactor. Numerical simulations are carried out to investigate the impacts of impeller speed, monomer ratio, initiator ratio, and initial reaction temperature on the copolymerization process and product properties. Particularly, the Chaos theory is selected as a criterion for evaluating the occurrence of the thermal runaway. The Flory's and Stockmayer's distributions are employed to calculate chain length distribution and copolymer composition distribution of copolymer. The simulation results highlight that the appearance of thermal runaway can be postponed by properly increasing the rotation speed, decreasing the initiator loadings, initial acrylonitrile contents and initial reactor temperature. Furthermore, significant differences exist in the product properties that predicted by the ideal and non-ideal models, which demonstrates that the temperature heterogeneity plays a crucial role in SAN copolymerization. This study could offer references for the safe operation and design of polymerization processes.     

适用于“一步酸溶法”生产氧化铝工艺中稀释料浆的高分子絮凝剂的合成

为达到"一步酸溶法"生产氧化铝工艺中稀释料浆在高温、高酸度工况下进行固液高效分离的目的,以丙烯酰胺(AM)与阳离子(DMDAAC)为共聚单体,通过水溶液聚合法合成了阳离子聚丙烯酰胺(CPAM)絮凝剂。以转化率和相对分子质量为目标,通过单因素分析法确定了最优的合成工艺条件,即反应温度30℃,单体总质量分数为30%,阳离子度5%,K2S2O8和NaHSO3质量分数均为0.005%,2,2′-偶氮二(2-脒基丙烷盐酸盐)(V50)质量分数为0.0025%,乙二胺四乙酸(EDTA)质量分数为0.05%的条件下,反应时间为6 h,获得相对分子质量为1.2×107溶解性能较好的阳离子型聚丙烯酰胺(CPAM)。     

Core–shell type multi‐arm azide polymers based on hyperbranched copolyether as potential energetic materials in solid propellants

A series of novel multi‐arm azide copolymers (POGs) with the same hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] core (PEHO‐c) and different content of linear glycidyl azide polymer shell (GAP‐s) have been synthesized by sequential cationic ring‐opening polymerization and azidation. Detailed structural information of these copolyethers was deduced from Fourier transform infrared, ¹H NMR and inverse gated decoupled ¹³C NMR spectroscopies, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, gel permeation chromatography and elemental analysis. The molecular weight of POG having GAP‐s and PEHO‐c with a molar ratio 14.95:1 (R_s/c) was around 31 000 g mol^?1, far above that of linear GAP (around 4000 g mol^?1). The apparent viscosity and glass transition temperature (?51 to ?23 °C) decreased first and then slightly increased with increasing molecular weight. Thermal analysis revealed that all the obtained POGs exhibited excellent resistance to thermal decomposition up to 220 °C. Moreover, the energetic properties, investigated using oxygen bomb calorimetric measurements, indicated that the enthalpy of formation of the POGs was higher than that of general linear GAP, but similar to that of branched GAP under reasonable R_s/c. The compatibilities of the POGs with common materials used in solid propellants were studied using differential scanning calorimetry and the results indicated that the POGs had good compatibility with these materials. © 2017 Society of Chemical Industry     

Fabrication of core–shell nanocomposites with enhanced photocatalytic efficacy

The current study establishes the unprecedented involvement in the evolution and production of novel core–shell nanocomposites composed of nanosized titanium dioxide and aniline‐o‐phenylenediamine copolymer. TiO₂@copoly(aniline and o‐phenylenediamine) (TiO₂@PANI‐o‐PDA) core–shell nanocomposites were chemically synthesized in a molar ratio of 5:1 of the particular monomers and several weights of nano‐TiO₂ via oxidative copolymerization. The construction of the TiO₂@PANI‐o‐PDA core–shell nanocomposites was ascertained from Fourier transform IR spectroscopy, UV–visible spectroscopy and XRD. A reasonable thermal behavior for the original copolymer and the TiO₂@PANI‐o‐PDA core–shell nanocomposites was investigated. The bare PANI‐o‐PDA copolymer was thermally less stable than the TiO₂@PANI‐o‐PDA nanocomposites. The core–shell feature of the nanocomposites was found to have core and shell sizes of 17 nm and 19–26 nm, respectively. In addition, it was found that the addition of a high ratio of TiO₂ nanoparticles increases the electrical conductivity and consequently lowers the electrical resistivity of the TiO₂@PANI‐o‐PDA core–shell nanocomposites. The hybrid photocatalysts exhibit a dramatic photocatalytic efficacy of methylene blue degradation under solar light irradiation. A plausible interpretation of the photocatalytic degradation results of methylene blue is also demonstrated. Our setup introduces a facile, inexpensive, unique and efficient technique for developing new core–shell nanomaterials with various required functionalities and colloidal stabilities. © 2018 Society of Chemical Industry     

Multichromic polymers based on pyrene clicked thienylpyrrole

In this study, the effect of pendant pyrene on the optical and electronic properties of poly(2,5‐dithienylpyrrole)s was studied. For this purpose a new pyrene coupled 2,5‐dithienylpyrrole derivative (SNS‐pyrene) was synthesized through click reaction. SNS‐pyrene was electrochemically polymerized and its electrochemical and optical properties were investigated by electrochemical and optical techniques. The polymer had a band gap of 3.36 eV and displayed light green to blue color variation upon oxidation in less than 2.48 s. Additionally, electrochemical copolymerization of SNS‐pyrene with 3,4‐ethylenedioxythiophene was achieved whilst a detailed investigation was performed on the effect of electrochemical polymerization conditions on the optoelectronic properties of the copolymers. Studies revealed that the copolymers exhibit multichromic reversible redox behavior with lower band gaps and shorter switching times than their parent polymer, P(SNS‐pyrene) © 2014 Society of Chemical Industry.     

Utilization of bio‐sourced myrcene for efficient preparation of highly cis‐1,4 regular elastomer via a neodymium catalyzed copolymerization strategy

The depletion of fossil based chemicals and the associated pollution have presented huge challenges to sustainability. In this study, we report on bio‐available myrcene participating in copolymerization with isoprene and butadiene by using neodymium catalysts without disruption of the pristine polymer's properties. Efficient incorporation of myrcene into the copolymer was achieved with slightly retarded reactivity compared to the reactivities of butadiene and isoprene. Copolymerization of myrcene with hydroxyl myrcene still remained compatible with the catalyst systems when the cocatalyst was fed in excess, resulting in a novel type of full myrcene based functional elastomer. The high cis‐1,4 selectivity of the system maintained the same level as the homopolymerization. Significant affinity to polar substances was deduced from the remarkably reduced water contact angle, a strong indication of good compatibility with reinforcing fillers. All copolymers displayed over 93.2% cis‐1,4 regularity and high molecular weight with narrow ?. Good resistance to low temperature was also achieved as indicated by the low glass transition temperature for all copolymers. This study verified that myrcene can be used as a sustainable monomer substituent for general diene based elastomer preparation. © 2020 Society of Chemical Industry     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Modeling of sequence length distribution for olefin copolymerization with vanadium-based catalyst

Some thermodynamic and mechanical properties of a polyolefin, such as the melting temperature and the rigidity, are dependent on the nature of its sequence distribution. Accurate modeling of sequence length distribution (SLD) is important in precisely tuning and optimizing the properties of polymers produced. In this article, we proposed a model to predict the molecular weight distribution (MWD) and SLD for olefin copolymerization with vanadium-based catalyst. Due to the 2,1-insertion of α-olefin with vanadium-based catalyst, the SLD is expressed by uninterrupted methylene sequence distribution instead of conventional triad sequence distribution. To obtain a reliable model, parameter estimation with experimental data is first conducted. The SLD model along with the estimated kinetic parameters can be used to predict unmeasurable sequence length fraction. For the experimental conditions studied, the average methylene sequence length is predicted to change from 10 to 4 units as the propylene/ethylene mole feed ratio increases from 1.1 to 3.4.     

Polydimethylsiloxane/monomer casting nylon copolymers: Preparation,flame-retardant properties,and wear-resistant properties

In order to improve the toughness, wear resistance, and combustion properties of the monomer casting nylon (MC nylon) materials, the polydimethylsiloxane (PDMS) segment is bonded to the nylon molecular chain by copolymerization. PDMS/MC nylon copolymers are prepared via in situ anionic polymerization with macro-activator based on PDMS terminated with hexamethylene diisocyanate. The effects of different macro-activator content on the mechanical properties, water absorption, thermal stability, friction and wear properties, and combustion properties of the copolymers are characterized. The results show that the impact strength of the copolymer improves significantly (optimally increases by 2.6 times) and the water absorption rate decreases with the increase of PDMS content. The introduction of the silicon–oxygen structure reduces the peak heat release rate of copolymer materials (optimally decreases about 28.7%), while it promotes the decomposition of the system, resulting in a slight decrease in the thermal stability of the materials. Adding 5 wt % PDMS can decrease the wear loss of MC nylon from 6.2 mg of pure nylon to 1.6 mg. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48753.     

四氢呋喃对M-1催化剂性能的影响

结合乙烯气相流化床反应工艺的特点,深入探讨分析四氢呋喃对M-1催化剂的作用和影响,结果表明,四氢呋喃的含量直接影响M-1催化剂的活性和催化乙烯与丁烯-1共聚生产的树脂产品性能。为了生产性能优良的乙烯与丁烯-1共聚产品,需要将四氢呋喃的含量严格控制在较窄的范围。