Material encapsulation in poly(methyl methacrylate) shell: A review

Material encapsulation is a relatively new technique for coating a micro/nanosize particle or droplet with polymeric or inorganic shell. Encapsulation technology has many applications in various fields including drug delivery, cosmetic, agriculture, thermal energy storage, textile, and self-healing polymers. Poly(methyl methacrylate) (PMMA) is widely used as shell material in encapsulation due to its high chemical stability, biocompatibility, nontoxicity, and good mechanical properties. The main approach for micro/nanoencapsulation of materials using PMMA as shell comprises emulsion-based techniques such as emulsion polymerization and solvent evaporation from oil-in-water emulsion. In the present review, we first focus on the encapsulation techniques of liquid materials with PMMA shell by analyzing the effective processing parameters influencing the preparation of PMMA micro/nanocapsules. We then describe the morphology of PMMA capsules in emulsion systems according to thermodynamic relations. The techniques to investigation of mechanical properties of capsule shell and the release mechanisms of core material from PMMA capsules were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48039.     

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.     

A highly transparent and thermally stable copolymer of 1‐adamantyl methacrylate and styrene

Thermal and optical properties of copolymers of 1‐adamantyl methacrylate (AdMA) and styrene (St) prepared by free radical polymerization in the bulk are investigated. The copolymer forms an azeotrope when the composition is AdMA/St = 55/45 mol%. The glass transition temperature and decomposition temperature of the azeotropic copolymer are 170 and ca 340 °C, respectively. The refractive index increases nonlinearly with St content from 1.522 to 1.591. The light scattering loss at 633 nm is 28.1 dB km^?1, which is less than half of that of polystyrene. The total optical loss including molecular vibrational absorption, which is evaluated using a copolymer‐based optical fiber, is 292–645 dB km^?1 at 500–700 nm. These values correspond to transmittances of 86–93% for a 1 m optical path length. © 2014 Society of Chemical Industry     

Physico-chemical characterization of hybrid polymers obtained by 2-hydroxyethyl(methacrylate) and alkoxides of zirconium

Hybrid monolithic materials were prepared through polymerisation of 2-hydroxyethyl methacrylate (HEMA) mixed with zirconium alkoxides (Zr(OBuⁿ)₄, Zr(OPrⁿ)₄ and Zr(OEt)₄), modified by acetylacetonate groups. The molar ratio HEMA/Zr varied between 1 and 4. Thermo-Gravimetry coupled with Mass Spectroscopy (TG-MS) analyses, ¹³C MAS NMR and Dynamical Mechanical Thermal Analysys (DMTA) indicated the polymeric chains were interconnected by the inorganic component.The presence of zirconium alkoxides modified substantially the poly-HEMA properties. Glass transition temperature of hybrid materials derived from butoxy and propoxy was found in the range 50-80 °C, depending on the composition. The typical swelling of p-HEMA in the water, was suppressed by the presence of zirconium compounds. After immersion in distilled water, hybrid polymers showed an initial slight weight increase, followed by a small mass loss, which increases proportionally to the length of alkoxyl group (ethoxide(propoxide(butoxide) and reaches a constant value after about 40 days. The hybrids remained always rigid and transparent. Flexural modulus and strength of about 400-900 and 4-8 MPa were measured.     

十二酰胺丙基二甲基羟乙基氯化铵与十二烷基硫酸钠水溶液的表面吸附和胶束形成

利用十二酰胺丙基二甲胺和氯乙醇反应 ,合成了十二酰胺丙基二甲基羟乙基氯化铵 (DDHA)阳离子表面活性剂 ,将其与十二烷基硫酸钠 (SDS)以不同摩尔比进行混合 ,测定了混合系统的表面张力 ,计算了单一系统和混合系统的饱和吸附量、分子最小截面积 ,表面层和胶束中 DDHA的摩尔分率及分子间相互作用参数 ,目视观察了混合系统的浑浊情况。结果表明 :在降低γcmc和 cmc方面 ,DDHA SDS混合系统有协同效应 ,表面层和胶束的组成与二组分配比有关 ,但是非对称的 ,等物质的量混合物中 ,DDHA在胶束和表面层中具有较大的摩尔分数。DDHA与 SDS在实验测定的各混合系统中都不出现混浊     

甲基丙烯酸乙酯合成工艺研究

以大孔强酸性离子交换树脂为催化剂,甲基丙烯酸(MAA)与乙醇直接酯化合成甲基丙烯酸乙酯(EMA)。在MAA与乙醇摩尔比为1:3、反应温度89～93℃、空速0.3h~(-1)的条件下,MAA转化率不低于98％,EMA的选择性不低于99％。     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

新抗冲型ACR的合成与研究

采用种子乳液聚合法制备了含有PBA＼PMMA＼PS三种组分的丙烯酸酯类抗冲型改性剂ACR，在ACR的幔层结构中引入接枝剂甲基丙烯酸烯丙酯（ALMA）来完善幔层结构，从而实现核一壳之间良好的结合，用红外光谱（FTIR）和差示扫描量热法（DSC）对ACR的组成和结构进行表征。研究结果表明：由PBA＼PMMA＼PS三组分构成的ACR在抗冲击性能上要略优于由简单的PBA＼PMMA构成的ACR，苯乙烯单体（St）最多可以取代大约1／3壳层的甲基丙烯酸甲酯（MMA），甲基丙烯酸烯丙酯（ALMA）的引入对幔层结构的完善起了显著的作用。     

聚氨酯/聚(甲基丙烯酸甲酯-甲基丙烯酸丁酯)互穿聚合物网络聚合物的阻尼性能

采用本体聚合法合成出一系列阻尼性能良好的聚氨酯/聚(甲基丙烯酸甲酯-甲基丙烯酸丁酯)(PU/P(MMA-BMA))互穿聚合物网络(IPN)聚合物,通过动态力学分析方法表征了PU/P(MMA-BMA)IPN聚合物的阻尼性能。探讨了加入催化剂、高温后处理、交联剂用量及PU与P(MMA-BMA)的质量比对PU/P(MMA-BMA)IPN聚合物阻尼性能的影响。实验结果表明,经高温后处理后,以二月桂酸二丁基锡为催化剂、交联剂二乙烯基苯用量(占MMA和BMA的摩尔分数)为1.5%、PU与P(MMA-BMA)的质量比接近1或小于1时,PU/P(MMA-BMA)IPN聚合物具有良好的阻尼性能。