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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Aldol Condensation of Methyl Propionate and Formaldehyde: Thermodynamics, Reaction Process, and Network

Bo Wang,Senlin Deng,Yuhang Bian,Guoliang Zhang,Chunshan Li

The aldol condensation of methyl propionate (MP) and formaldehyde (FA) is an environmentally friendly and sustainable route to produce methyl methacrylate (MMA). However, the side reaction is a huge barrier to achieving high selectivity to the target product. To strengthen the regulation of selectivity for the main reaction, a reaction network was established based on the validation and analysis of side reactions in the system through a combination of experimental and computational methods. The thermodynamics was analyzed through the Gibbs free energy (ΔrGTθ) of reactions. On the basis of a rigorous material balance of all components, the sources and reaction equations of 15 products were identified. The multivariate nonlinear model between the yield of different products and reaction conditions was established to predict the yield of each product. The mean relative error of the actual yield and predicted yield was less than 5%. The key influencing condition for the synthesis of MMA was the liquid hourly space velocity (LHSV).

研究领域: 化学工程 · 环境科学
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CHEMICAL PAPERS · 2023 ·Vol. 77 ·期 7 ·3713-3726 · IF 2.2

RAFT polymerization of MMA in channels of different mesoporous materials

Xue Tao,Wei Yan,Yu Caili,Zhou Zhongqun,Zhang Faai

A series of mesoporous silica (MS) materials, including rod-like and spherical SBA-15, spherical MCM-41, and MCM-48, was successfully synthesized and modified by silane coupling agent γ-aminopropyltriethoxysilane. The modified MS was utilized as a microreactor for solution reversible addition–fragmentation transfer (RAFT) polymerization of methyl methacrylate (MMA) using xanthate as a chain transfer agent and azodiisobutyronitrile as an initiator. Notably, modified MS had a low specific surface area and pore volume while maintaining the original morphological structure. Given to the confinement effects, poly(methyl methacrylate) (PMMA) prepared from internal mesoporous channels had higher molecular weight and initial thermal decomposition temperature than those from conventional RAFT polymerization. Moreover, PMMA obtained from spherical SBA-15 and modified MCM-48 exhibited the highest molecular weight ( M n  = 8.78 × 10 4 and M n  = 7.43 × 10 4 , respectively). This work provided a novel approach in designing a polymer microstructure for a more comprehensive application, such as in drug release. Graphical abstract

CAS / MDL: 535-11-5 140-89-6
研究领域: 材料科学 · 高分子化学
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POLYMER SCIENCE SERIES B · 2023 ·Vol. 65 ·期 4 ·409-418 · IF 1.2

Dispersion Polymerization of Methyl Methacrylate Using Poly(vinyl acetate/vinyl propionate) Based Copolymers as Stabilizers in Supercritical Carbon Dioxide

Shoucun Zhang,Wang Shengyan,Bian Yujing,Fang Guoli

Abstract Carbon dioxide is a well-known green solvent, and can be used instead of some organic solvent to prepare the polymer products. On the basis of its poor solubility, dispersion polymerization can be adopted to produce the polymer products in industry. Thus, low price, easily available stabilizers with good stabilization effect will be a must. In this paper, we are committed to designing and synthesizing stabilizers with these characteristics. Firstly, thiol ethanol is used as the chain-transfer agent to control the copolymerization of vinyl acetate/vinyl propionate, and the homopolymers or copolymers with the hydroxyl group at the chain terminal are obtained. These homopolymers or copolymers are then functionalized to prepare the stabilizers with methacrylate groups. The results indicate that these stabilizers can effectively control the dispersion polymerization of methyl methacrylate in supercritical carbon dioxide. The proportion of structural units in the copolymer and the concentration of stabilizer or initiator obviously affect the conversion percentage of methyl methacrylate and the molecular weight of polymers. The maximum conversion percentage of methyl methacrylate and the molecular weight of poly(methyl methacrylate) can reach 93%, and 56000 Da, respectively. SEM images show that most of the samples are free-flowing powders with a spherical structure.

研究领域: 材料科学 · 化学工程
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REACTIVE & FUNCTIONAL POLYMERS · 2023 · IF 5.1

Enhanced energy storage properties of all-polymer dielectrics by cross-linking

Leipeng Liu,Haochen Yun,Jie Xiong,Jiangtao Wang,Zhicheng Zhang

Polymer dielectrics with good energy storage properties are need for advanced electric devices. Herein, a new class of all organic dielectric cross-linkable polymers, poly(methyl methacrylate-glycidyl methacrylate) (P(MMA-GMA)) prepared by radical polymerization , is reported. A comprehensive investigation was conducted to examine the impact of the cross-linked monomer GMA content on the energy storage properties. The crosslinking significantly enhances the breakdown strength and suppresses the leakage currents . Consequently, the copolymer P(MMA-GMA) containing 7 mol% GMA exhibits a high discharge energy density of 16.5 J/cm 3 at 750 MV/m, coupled with a high discharge efficiency of 82%. Even at an elevated temperature of 100 °C, it still possesses a good energy performance of a discharge energy density of 12.1 J/cm 3 and a relatively high efficiency of 80.1% at 650 MV/m. This study offers a simple and effective approach to fabricating all-organic polymer dielectrics with good energy storage properties.

CAS / MDL: 78-67-1 106-91-2 80-62-6
研究领域: 材料科学 · 电气工程
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JOURNAL OF APPLIED POLYMER SCIENCE · 2016 ·Vol. 133 ·期 35 · IF 1.866

Preparation of poly(methyl methacrylate-co-butyl methacrylate) nanoparticles and their reinforcing effect on natural rubber

Jin Liu,Xiaohui Tian,Jinyu Sun,Yizhong Yuan

Poly(methyl methacrylate- co -butyl methacrylate) [P(MMA- co -BMA)] nanoparticles were synthesized via emulsion polymerization, and incorporated into natural rubber (NR) by latex compounding. Monodispersed, core-shell P(MMA- co -BMA)/casein nanoparticles (abbreviated as PMBMA-CA) were produced with casein (CA) as surfactant. The chemical structure of P(MMA- co -BMA) copolymers were confirmed by 1 H-NMR and FTIR analyses. Transmission electron microscopy demonstrated the core–shell structure of PMBMA-CA, and PMBMA-CA homogenously distributed around NR particles, indicating the interaction between PMBMA-CA and NR. As a result, the tensile strength and modulus of NR/PMBMA-CA films were significantly enhanced. The tensile strength was increased by 100% with 10% copolymer addition, when the molar ratio of MMA:BMA was 8:2. In addition, scanning electron microscopy and atomic force microscopy results presented that the NR/PMBMA-CA films exhibited smooth surfaces with low roughness, and PMBMA-CA was compatible with NR. FTIR-ATR analyses also suggested fewer PMBMA-CA nanoparticles migrated out of NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 43843.

研究领域: 材料科学 · 高分子化学 · 复合材料
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COMPOSITES PART B-ENGINEERING · 2021 · IF 9.078

Temperature adaptive microcapsules for self-healing cementitious materials

Jun Ren,Xianfeng Wang,Dongfeng Li,Ningxu Han,Biqin Dong,Feng Xing

The brittleness of microcapsule shell greatly restricts its self-healing performance since it is easily ruptured during the mixing process. Based on the heat releasing nature during cement hydration , a novel concept of temperature-adaptive microcapsule (TAM) was proposed, which can exhibit a switchable mechanical property with temperature. In this paper, a series of TAM with polymethylmethacrylate-methacrylate shell and magnesium oxide core was prepared with four designed transition temperature, and were characterised by Fourier transform infrared spectroscopy, nano-indentation tests, scanning electron microscopy, thermalgravity analysis and particle size analysis , which confirmed the success in preparing the TAM. Moreover, the performance of proposed microcapsules in cement was investigated by determining the breakage rate of microcapsule and recovery rate of cement paste under different mixing temperature. The results illustrated that compared to lower mixing temperature, a 75% reduction in breakage rate and a 5% increment in recovery rate was observed in TAM embedded cementitious paste at an elevated mixing temperature. This work should provide a promising approach to improve the performance of microcapsules for self-healing cementitious materials .

研究领域: 材料科学 · 土木工程
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JOURNAL OF APPLIED POLYMER SCIENCE · 2015 ·Vol. 132 ·期 32 · IF 1.768

Photo-Induced atom transfer radical polymerization with nanosized α-Fe2O3 as photoinitiator

Li-chao Liu,Mang Lu,Zhao-Hui Hou,Guo-Xiang Wang,Chang-An Yang,En-Xiang Liang,Hu Wu,Xian-Lei Li,Yi-Xue Xu

Photo-induced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved in poly(ethylene glycol)-400 with nanosized α-Fe 2 O 3 as photoinitiator. Well-defined poly(methyl methacrylate) (PMMA) was synthesized in conjunction with ethyl 2-bromoisobutyrate (EBiB) as ATRP initiator and FeCl 3 ·6H 2 O/Triphenylphosphine (PPh 3 ) as complex catalyst. The photo-induced polymerization of MMA proceeded in a controlled/living fashion. The polymerization followed first-order kinetics. The obtained PMMA had moderately controlled number-average molecular weights in accordance with the theoretical number-average molecular weights, as well as narrow molecular weight distributions ( M w / M n ). In addition, the polymerization could be well controlled by periodic light-on–off processes. The resulting PMMA was characterized by 1 H nuclear magnetic resonance and gel permeation chromatography. The brominated PMMA was used further as macroinitiator in the chain-extension with MMA to verify the living nature of photo-induced ATRP of MMA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 42389.

CAS / MDL: 1309-37-1
研究领域: 高分子化学 · 材料科学
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JOURNAL OF POLYMER RESEARCH · 2013 ·Vol. 20 ·期 7 ·1-11 · IF 2.019

UV cured polymer based on a renewable cardanol derived RAFT agent

Cheng Chuanjie,Bai Xiongxiong,Liu Shaojin,Huang Qinghua,Tu Yuanming,Wu Haiming,Wang Xiaoji

A cardanol-derived reversible addition-fragmentation chain transfer (RAFT) agent was synthesized in 57 % total yield, and a cardanol-based anionic surfactant was also facilely prepared. Emulsion polymerization of methyl methacrylate (MMA) was realized to form a cardanol-terminated PMMA polymer by using the novel RAFT agent as well as the cardanol-based anionic surfactant. To improve the properties of cardanol-terminated PMMA as a material, UV-curing was performed. According to the comprehensive behavior of the UV-cured resins, optimal irradiation time was 20 min.

研究领域: 材料科学 · 高分子化学 · 可持续化学
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JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY · 2023 · IF 5

Preparation of temperature-responsive PMMA-based microspheres encapsulating erythromycin in situ by emulsion photopolymerization

Siyuan Yu,Jinfeng Xing

Erythromycin (EM) was encapsulated into poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate- co - N -vinylcaprolactam) (P(MMA-NVCL)) microspheres in situ by oil-in-water emulsion photopolymerization under green LED irradiation. The physicochemical properties of PMMA-EM and P(MMA-NVCL)-EM microspheres were characterized by SEM, FTIR, TG-DSC and DLS. P(MMA-NVCL)-EM microspheres showed temperature sensitivity, and the EM loading content of PMMA-EM and P(MMA-NVCL)-EM microspheres reached 9.7% and 15.6%, respectively. In vitro release of EM from microspheres presented good controlled release behavior in 12 h. Further release kinetic and thermodynamic investigation revealed that the release process was mainly dominated by EM concentration, accompanied by microspheres relaxation and rupture of hydrogen bonds .

研究领域: 材料科学 · 药学 · 高分子化学
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COLLOID AND POLYMER SCIENCE · 2020 ·Vol. 298 ·期 10 ·1285-1291 · IF 1.536

Preparation of poly(methyl methacrylate) microspheres via photopolymerization initiated by LED light source

Xie Chuanbao,Leng Kangwei,Sheng Jie,Wang Xuemei,Li Qianmin,Song Liang,Liu Lei,Sun Hejing,Huang Xiaowen,Wang Zhongwei,Yu Qing

Poly(methyl methacrylate) (PMMA) microspheres were synthesized through visible light–induced photopolymerization of methyl methacrylate (MMA). 2,4,6-Trimethylbenzoyldipenylphosphine oxide (TPO), polyvinylpyrrolidone (PVP), and light-emitting diodes (LEDs) were used as the photoinitiator, stabilizer, and light source, respectively. No other additive was involved. The effect of LEDs, TPO, and PVP was discussed. Results showed that PMMA microspheres with the size of 0.5–0.8 μm could be obtained when LED@385 nm was the light source, and the content of TPO and PVP was 2 wt% and 30 wt% of MMA. Moreover, the possible formation pathway of PMMA microspheres was proposed based on the investigation of reaction time and addition method of PVP. Graphical abstract

研究领域: 材料科学 · 化学工程
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Processes · 2019 ·Vol. 7 ·期 6 ·377 · IF 1.963

Design and Optimization of a Process for the Production of Methyl Methacrylate via Direct Methylation

Taotao Liang,Xiaogang Guo,Abdulmoseen Segun Giwa,Jianwei Shi,Yujin Li,Yan Wei,Xiaojuan Wang,Xuansong Cao,Xiaofeng Tang,Jialun Du

Methyl methacrylate (MMA) plays a vital role in national productions with broad application. Herein, the production of MMA is realized by the improved eco-friendly direct methylation method using Aspen Plus software. Three novel kinds of energy-saving measures were proposed in this study, including the recycle streams of an aqueous solution, methacrolein (MAL), and methanol, the deployment of double-effect distillation instead of a normal one, and the design of a promising heat-exchange network. Moreover, MMA with a purity of 99.9% is obtained via the design of a MAL absorber column with an optimal stage number of 11 and a facile chloroform recovery process by using the RadFrac model. Thus, the proposed green process with energy-conservation superiority is the vital clue for developing MMA, and provides a reference for the production of MMA-ramifications with excellent prospects.Keywords:MMA;double-effect distillation;energy conservation;MAL;purity

研究领域: 化学工程 · 环境科学
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THERMOCHIMICA ACTA · 2021 · IF 3.115

Thermal hazard evaluation of styrene-methyl methacrylate bulk copolymerization by differential scanning calorimetry and accelerating rate calorimetry

Jihe Zhao,Xuefeng Gui,Wenhai Zhang,Shudong Lin,Yuanyuan Tu,Jiwen Hu,Daguang He,Xiaohua Huang

Thermal runaway primarily occurs during the course of copolymerization due to the release of large amounts of heat. In this paper, the thermal risk associated with styrene-methyl methacrylate bulk copolymerization was firstly investigated by differential scanning calorimetry (DSC) and accelerating rate calorimetry (ARC). The result found that the exothermic behavior was greatly affected by the initiator concentration, in contrast the exothermic enthalpy was not. This exothermic behavior was firstly illustrated via polymerization mechanism. The temperature and pressure have changed dramatically during the adiabatic runaway copolymerization, which demonstrated a great potential risk of thermal runaway. Kinetic parameters, such as T NR , T SADT was calculated accordingly, which provided guidance for the safety of storage and transportation. This study will provide a helpful safety assessment for the styrene-methyl methacrylate bulk copolymerization, which is widely used in industry.

研究领域: 化学工程 · 材料科学 · 安全科学
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