Fabrication of ZIF-8@super-macroporous poly(glycidyl methacrylate) microspheres

ZIF-8@super-macroporous poly(glycidyl methacrylate) (SM-PGMA) microspheres were synthesized. The SM-PGMA microsphere was a novel material with high surface areas and large pore size. Here, ZIF-8 was loaded effectively both on the surface and inside of the macro-pores of microspheres by a facile way. The ZIF-8@SM-PGMA microspheres were characterized by SEM, TEM, XRD and FTIR. Additionally, they were used as an adsorbent material for the adsorption of phenol from aqueous solutions. The results indicated that the ZIF-8@SM-PGMA microspheres possessed apparently higher adsorption capacity for phenol than that of SM-PGMA microspheres. The ZIF-8@SM-PGMA microspheres obtained in this study have great potential for adsorption, separation, catalysis etc.     

Poly(aspartic acid) surface modification of macroporous poly(glycidyl methacrylate) microspheres

Novel macroporous, hydrophilic microspheres with a surface layer of crosslinked poly(aspartic acid) were synthesized. In this study, macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [poly(GMA-co-EGDMA)] microspheres with pore size around 370 nm were first obtained through the surfactant reverse micelle swelling method, and the poly(GMA-co-EGDMA) was aminated by ethylene diamine to form poly(GMA-NH₂). The polysuccinimide was grafted onto the surface of poly(GMA-NH₂) microspheres and crosslinked by hexamethylendiamine and γ-aminopropyltriethoxysilane, respectively, and then hydrolyzed to obtain the poly(aspartic acid)-functionalized macroporous microspheres. The functionalized hydrophilic microspheres were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, mercury porosimetry, and elemental analysis. The metal ion adsorption capacity was also studied. The FTIR, XPS, and elemental analysis confirmed the poly(aspartic acid) functionalization of the poly(GMA-co-EGDMA) microspheres. SEM and mercury porosimetry showed there was little effect of this surface chemical modification on microsphere porosity, and the obtained macroporous microspheres exhibited excellent thermal stability and adsorption for Ag(I), presenting great potential for applications in adsorption, fixation, and separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47441.     

Monodisperse macroporous poly(glycidyl methacrylate) microspheres coated with silica: Design,preparation and characterization

Monosized macroporous poly(glycidyl methacrylate) (PGMA) microspheres that were 9.3 μm in size were synthesized by multistep swelling polymerization using a modified Ugelstad technique. The PGMA microspheres and their hydrolyzed analogs derived from poly(2,3-dihydroxypropyl methacrylate) (PDHPMA) were coated by silanization with tetraethoxysilane (TEOS) and (3-aminopropyl)triethoxysilane (APTES), respectively. The particles were characterized by elemental and thermogravimetric (TGA) analysis, scanning and transmission electron microscopy (SEM and TEM) coupled with an energy dispersive X-ray analysis (EDAX) and FT-IR spectroscopy to determine the SiO₂ content, morphology, particle size, polydispersity and structure. These types of particles are expected to have improved biocompatibility relative to their starting polymers.     

Concanavalin A immobilized magnetic poly(glycidyl methacrylate) beads for antibody purification

Concanavalin A (Con A) immobilized magnetic poly(glycidyl methacrylate) (mPGMA) beads in monosize and spherical for (1.62 μm in diameter) were used for the purification of human immunoglobulin G (IgG) from human plasma. Con A was immobilized by covalent binding onto the mPGMA beads. The maximum IgG adsorption on the mPGMA-Con A beads was observed at pH 6.0. The nonspecific IgG adsorption onto the plain mPGMA beads was very low (0.22 mg/g). Scatchard analysis of the adsorption isotherm for IgG on mPGMA-Con A beads showed an affinity constant (K_a) of 1.39 × 10⁵ M⁻¹ and a theoretical maximum adsorption capacity of 109.1 mg/g. An apparent IgG adsorption capacity of 66.2 mg/g was observed under the experimental conditions. IgG adsorption capacity from human plasma was observed as 48.0 mg/g. The adsorption of human serum albumin from plasma was 2.0 mg/g. The total protein adsorption was determined to be 50.0 mg/g. IgG molecules could be repeatedly adsorbed and eluted with the mPGMA-Con A beads without noticeable loss in the IgG adsorption capacity. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of magnetic poly(glycidyl methacrylate) microspheres by emulsion polymerization in the presence of sterically stabilized iron oxide nanoparticles

With the aim to synthesize water‐dispersible superparamagnetic nanoparticles, iron oxide was precipitated in aqueous solution of dextran, (carboxymethyl) dextran (CM‐dextran), (DEAE‐dextran), or D ‐mannose. Glycidyl methacrylate (GMA) was emulsion‐polymerized in the presence of the nanoparticles and the effect of iron oxide modification on the product properties was investigated. The main factors affecting the morphology, size, and size distribution of the latex particles are the type and concentration of emulsifier (Disponil AES 60, Tween 20, Triton X‐100) and initiator [ammonium persulfate (APS) and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA)]. Disponil AES 60 and ACVA are the preferred emulsifier and initiator, respectively, because oxirane groups hydrolyzed during the APS‐initiated polymerization. Up to some 5 wt % of iron was found in poly(glycidyl methacrylate) (PGMA) microspheres obtained by emulsion polymerization in the presence of dextran‐coated iron oxide and emulsified with Disponil AES 60. The size of magnetic PGMA microspheres could be controlled in the range ? 70–400 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4348–4357, 2006     

Preparation and characterization of magnetic poly(styrene–glycidyl methacrylate) microspheres for highly efficient protein adsorption by two‐stage dispersion polymerization

Micrometer‐sized superparamagnetic poly(styrene–glycidyl methacrylate)/Fe₃O₄ spheres were synthesized by two‐stage dispersion polymerization with modified hydrophobic Fe₃O₄ nanoparticles, styrene (St), and glycidyl methacrylate (GMA). The morphology and properties of the magnetic Fe₃O₄–P (St‐GMA) microspheres were examined by scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, and attenuated total reflectance. The average size of the obtained magnetic microspheres was 1.50 μm in diameter with a narrow size distribution, and the saturation magnetization of the magnetic microspheres was 8.23 emu/g. The magnetic Fe₃O₄–P (St‐GMA) microspheres with immobilized iminodiacetic acid–Cu²⁺ groups were used to investigate the adsorption capacity and selectivity of the model proteins, bovine hemoglobin (BHb) and bovine serum albumin (BSA). We found that the adsorption capacity of BHb was as high as 190.66 mg/g of microspheres, which was 3.20 times greater than that of BSA, which was only 59.64 mg/g of microspheres as determined by high‐performance liquid chromatography. With a rather low nonspecific adsorption, these microspheres have great potential for protein separation and purification applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43005.     

Preparation of amidoximated poly(glycidyl methacrylate) microbeads

Poly(glycidyl methacrylate) (PGMA) microbeads were synthesized by a simple suspension polymerization of glycidyl methacrylate and ethylene glycol dimethacrylate. The epoxy groups of the microbeads were firstly modified with 3,3′‐iminodipropionitrile (IDPN) and the resulting nitrile groups were then converted to amidoxime. From scanning electron microscopy studies, the average size of the PGMA microbeads was determined as 170 µm, which was not changed by the modification processes. For the modification of epoxy groups with IDPN, the intensity of the C≡N absorption band at 2249 cm^?1 increased proportionally with reaction time; for the conversion of nitrile groups to amidoxime, it decreased. Attenuated total reflectance Fourier transform infrared spectroscopy measurements clearly showed the disappearance of the original nitrile groups and the formation of amidoxime groups through treatment with hydroxylamine under the reaction conditions specified. The microbeads possessed good thermal and morphological properties and chemical stability suitable for practical use. Therefore, the amidoximated PGMA microbeads could be used in batch and continuous processes for the adsorption of uranyl ions from seawater or aqueous media. Copyright © 2010 Society of Chemical Industry     

Preparation and use of magnetic poly(glycidyl methacrylate) resin in drinking water treatment

Magnetic poly(glycidyl methacrylate) (m‐PGMA) was synthesized and characterized, and its efficiency in removing natural organic matter (NOM) and carbamazepine (CBZ) from synthetic water was studied. The effects of factors such as time and m‐PGMA dosage on NOM removal were investigated. Furthermore, magnetic ion exchange resin (MIEX®) was used for comparison with m‐PGMA in CBZ removal. m‐PGMA was found to have a strong magnetic character whose specific saturation magnetization and mass fraction of magnetite were 10.79 emu g^?1 and 6.166 wt %, respectively, thus providing additional utility for m‐PGMA in slurry form in completely mixed continuous‐flow reactors. Lab‐scale studies showed that the removal rate rose rapidly with time and reached a pseudo‐equilibrium after 30 min. In addition, the highest doses of m‐PGMA achieved the highest removal efficiency. After 30 min of contact with 5, 10, and 15 mL L^?1 of m‐PGMA, the removal rates, based on UV absorbance measurements at 254 nm (UV₂₅₄), were 56%, 67%, and 79%, respectively, whereas the removal rates of dissolved organic carbon (DOC) were 53%, 60%, and 72%, respectively. Additionally, the scale ultraviolet absorbance values (SUVA) decreased during a 30 min contact time, thereby suggesting that the NOM removed by m‐PGMA had greater aromatic character. In multiple‐loading tests, UV₂₅₄ removal gradually decreased and achieved 18.39% at 1600 bed volume; it was kept constant at this level. Compared to MIEX®, m‐PGMA had a higher CBZ removal rate (27.8% and 34.7% for 20 mL L^?1 and 25 mL L^?1 of m‐PGMA, corresponding to the removal of 200 μg L^?1 CBZ). The resulting higher removal rate of CBZ contributed to stronger adsorption, a higher specific surface area, and larger pore volume. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Immobilization of Myceliophthora thermophila laccase on poly(glycidyl methacrylate) microspheres enhances the degradation of azinphos-methyl

Laccase enzymes are multicopper oxidases capable of oxidizing different compounds. However, to be able to use this biocatalyst for industrial applications, their immobilization is needed. The present work investigates the immobilization of Myceliophthora thermophila laccase (MtL) on monodisperse microspheres of poly(glycidyl methacrylate) (PGMA) to be used in azinphos-methyl degradation. The immobilization was optimized to achieve the highest activity of the immobilized enzyme. As result, the protein load obtained was 2.5 mg protein g⁻¹ carrier (35 U g⁻¹ of carrier). The immobilized enzymes showed a broadened pH and temperature range of optimum activity and significantly improved the storage and operational stability. Finally, the complete degradation of azinphos-methyl using immobilized laccase was achieved after 1 h of reaction. The collected data indicate that the immobilization of MtL on PGMA microspheres is an excellent alternative to improve biochemical properties in the enzyme and to allow their efficient use in pesticides degradation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47417.     

Preparation of uniform poly(glycidyl methacrylate) porous microspheres by membrane emulsification–polymerization technology

Uniform poly(glycidyl methacrylate‐divinyl‐benzene) (P(GMA‐DVB)) and poly(glycidyl methacrylate‐ethylene dimethacrylate) (P(GMA‐EGDMA)) porous microspheres with several 10 μm were successfully prepared by membrane emulsification–polymerization technology. Conventional suspension polymerization method was first investigated by examining the effects of recipe components on the morphologies of P(GMA‐DVB), including stabilizer, diluent, and crosslinker to select a optimum recipe. The membrane emulsification–polymerization process was developed to prepare uniform PGMA porous microspheres as the following: the oil phase composed of monomer, diluent and initiator was pressed through membrane pores into the aqueous phase to form uniform droplets, and subsequent suspension polymerization was carried out. GMA and 4‐methyl‐2‐pentanol in the selected recipe were relatively hydrophilic, and therefore oil phase could wet the hydrophilic glass membrane and bring about polydispersed droplets. However, when isooctane was added as a component of diluents, the uniform droplets could be prepared by membrane emulsification method. In the membrane emulsification–polymerization, the coagulation between microspheres obviously decreased while yield of microspheres slightly increased. To extend the application of PGMA, as a trail, uniform P(GMA‐EGDMA) porous microspheres were also successfully prepared by membrane emulsification–polymerization with a isooctane contained diluent, even though EGDMA was more hydrophilic than DVB. Therefore, recipe was found the important factor to prepare uniform PGMA porous microspheres using membrane emulsification–polymerization method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5018–5027, 2006     

Textural properties of poly(glycidyl methacrylate): acid-modified bentonite nanocomposites

The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modified bentonite (B_A) into the reaction system. All samples were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), mercury intrusion porosimetry, and low temperature physisorption of nitrogen. The FTIR and TEM analysis confirmed incorporation of B_A into the copolymer structure and the successful formation of nanocomposites. TEM images confirmed formation of nanocomposites having both intercalated and exfoliated acid-modified bentonite in copolymer matrix. A significant increase of specific surface area, pore volume, and porosity of the nanocomposites in comparison to the copolymer were obtained. The difference between textural properties of nanocomposites with different amounts of incorporated acid-modified bentonite was less prominent.     

聚甲基丙烯酸缩水甘油酯疏水纳凝胶的制备与表征

采用乳液聚合法制备了聚甲基丙烯酸缩水甘油酯疏水纳凝胶。通过透射电子显微镜、傅里叶红外光谱和动态激光光散射等测试对其结构和形貌进行了表征,对疏水纳凝胶形成过程规律和对温度、pH和时间稳定性进行了考察,并探究了单体浓度、交联剂含量和乳化剂浓度对纳凝胶粒径的影响规律。结果表明：所得疏水纳凝胶具有粒径均一、分散稳定和溶胀性能好等优点。疏水纳凝胶粒径在一定温度和pH范围内无变化,在30天内粒径从76nm增至116nm,zeta电位随温度升高而增加,其值稳定在-90~-30mV之间,说明是一种较为稳定的凝胶体系。在实验范围内,纳凝胶粒径随单体甲基丙烯酸缩水甘油酯和交联剂二甲基丙烯酸乙二醇酯浓度的增加从80nm增至250nm,随乳化剂浓度增加从230nm降至60nm。     

用于单克隆抗体纯化的仿生多肽超大孔PGMA微球制备及其性能

以仿生多肽配基FYEILHC为亲和配基、以葡聚糖修饰的聚甲基丙烯酸缩水甘油酯[Dextran-poly(glycidyl methacrylate), Dextran-PGMA]超大孔微球为基质,制备用于单克隆抗体纯化的仿生多肽超大孔PGMA微球,在环氧氯丙烷中滴加2 mol/LNaOH使其表面衍生出环氧基,在表面修饰FYEILHC;用扫描电镜表征微球表面形貌,用AKTA蛋白纯化系统考察了Dextran-PGMA微球和琼脂糖微球对抗体的动态吸附量随线性流速的变化。结果表明,偶联FYEILHC后Dextran-PGMA微球仍能保持其大孔结构,在923 cm/h线性流速下,其对抗体的动态吸附量仅下降约8%,而琼脂糖微球的动态吸附量则迅速下降25%。表明在较高流速下,抗体在Dextran-PGMA微球上的传质性能较好。吸附?用0.1 mol/L NaOH原位清洗重复40次后,Dextran-PGMA微球对抗体的动态吸附量约为(21?1) mg/mL,表明微球具有良好的化学稳定性;血清中回收的抗体纯度为95.0%,表明仿生多肽亲和介质具有从复杂生物样品中纯化抗体的巨大潜力,可满足高流速、高通量抗体分离纯化需求。     

功能性甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯嵌段聚合物ATRP合成

以2-溴代丙酸乙酯(EPN-Br)为引发剂,CuCl和2,2’-联二吡啶(BPY)为催化剂,以甲基丙烯酸甲酯(MMA)为原料,用原子转移自由基(ATRP)的方法,在80℃下合成带有卤原子的聚甲基丙烯酸甲酯大分子引发剂,在20～50℃下,以丁酮和正丙醇的混合液为溶剂,引发甲基丙烯酸缩水甘油酯(GMA)聚合,制得侧链含有环氧基团的PMMA-b-PGMA嵌段共聚物,分子量分布较窄,聚合物的分子量可通过单体与引发剂的比例进行控制。     

A new type of poly(glycidyl methacrylate) microbeads with surface grafted iminodiacetic acid: Synthesis and characterization

In this study, firstly, uniform poly(glycidyl methacrylate) (PGMA) microbeads with an average diameter of 230 μm were synthesized by suspension polymerization of GMA monomer and ethylene glycol dimethacylate (EGDMA) crosslinker in the presence of benzoyl peroxide (BPO) initiator . Secondly, the PGMA microbeads obtained were modified with iminodiacetic acid (IDA) to afford a new type of microbeads carrying two pendant carboxylic acid groups on the surface. The IDA modification was followed by Attenuated Total Reflectance Fourier Transformed Infrared (ATR-FTIR) measurements. The surface morphology and thermal behavior of the PGMA and their modificated form were also characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) techniques further confirming modification.     

Synthesis of monodisperse nonporous crosslinked poly(glycidyl methacrylate) particles with metal affinity ligands for protein adsorption

Monodisperse nonporous crosslinked poly(glycidyl methacrylate) (PGMA) particles with immobilized metal affinity ligands were prepared for selective recovery of proteins. The PGMA particles, with an average size of 2.2 µm, were prepared by a simple dispersion polymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA). The particles were characterized by scanning electron microscopy (SEM) and Fourier‐transform infrared spectroscopy (FTIR). The epoxy groups of the particles were modified with the metal chelating agent iminodiacetic acid (IDA), which forms metal–IDA chelates at the active sites. After charging with copper ions, the particles were used to recover a model protein, bovine hemoglobin (BHb), in a batchwise manner. The particles had the adsorption capacity of 218.7 mg g⁻¹ with little nonspecific adsorption. The adsorption behavior could be described with the Langmuir equation. The effect of pH on the adsorption was also studied. Regeneration of the metal‐chelated particles was easily performed with 50 mmol L⁻¹ ethylenediaminetetraacetic acid (EDTA), followed by washing with water and reloading with Cu²⁺. The particles could be very useful as an affinity separation adsorbent. Copyright © 2005 Society of Chemical Industry     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Swelling of poly(glycidyl methacrylate) gel particles by organic solvents

Fine particles of poly(glycidyl methacrylate) (PGMA) were prepared by suspension polymerization and crosslinked via the ring-opening reaction of the epoxide group with formic acid. A fraction of the spherical gel particles averaging about 70°m in diameter was examined under an optical microscope with its swelling behavior in a number of solvents. Equilibrium degrees of swelling were established with accuracy to show that this polymer gel has rather unusual affinities for solvents: (i) It is swollen (and, without the crosslinks, soluble in most cases) in many types of solvents, (ii) it cannot be represented by a single value of solubility parameter, and (iii) it is not swollen at all in water nor in aliphatic alcohols, in spite of the presence of hydroxy groups in the chain.     

Thermal stabilization of poly(3‐hydroxybutyrate) by poly(glycidyl methacrylate)

Poly(3‐hydroxybutyrate) (PHB)/poly(glycidyl methacrylate) (PGMA) blends with the PGMA content up to 30 wt % were prepared by a solution‐precipitation procedure. The thermal decomposition of PHB/PGMA blends was studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and differential thermal analysis (DTA). The thermograms of PHB/PGMA blends contained a two‐step degradation process, while that of pure PHB sample exhibited only one‐step degradation process. This degradation behavior of PHB/PGMA blends, which have a higher thermal stability as measured by maximum decomposition temperature or residual weight after isothermal degradation for 1 h, is probably due to crosslinking reactions of the epoxide groups in the PGMA component with the carboxyl chain ends of PHB fragments during the degradation process, and the occurrence of such reactions can be assigned to the exothermic peaks in their DTA thermograms. An isothermal study of these blends at 200–250°C for 1 h indicated that the residual weight was directly correlated with the amount of epoxide groups in the PHB/PGMA blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2945–2952, 2002; DOI 10.1002/app.10318     

Thermal degradation behavior of poly(vinyl chloride) in the presence of poly(glycidyl methacrylate)

The thermal degradation behavior of poly(vinyl chloride) (PVC) in presence of poly(glycidyl methacrylate) (PGMA) has been studied using continuous potentiometric determination of the evolved HCl gas from the degradation process from one hand and by evaluating the extent of discoloration of the degraded samples from the other. The efficiency of blending PGMA with dibasic lead carbonate (DBLC) conventional thermal stabilizer has also been investigated. A probable radical mechanism for the effect of PGMA on the thermal stabilization of PVC has been suggested based on data reported by FTIR and elemental analyses. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008