The effect of mixed diluent on the porous structure of crosslinked PMMA beads

Summary In this work copolymer beads, based on MMA (methyl methacrylate) and EGDM (ethylene glycol dimethacrylate), were prepared by suspension polymerization. A mixed solvent, composed of two different solvents, namely toluene and cyclohexane, was used as the diluent in the polymerization medium. The porous structure of the beads was found to be affected by the solvent composition used to dissolve the monomers initially. It was observed that the porosity and pore size increased gradually with the increase of cyclohexane content of the solvent composition. It was also detected that the pore radii changed from 2–10 nm to 700–1000 nm as the cyclohexane content of the diluent changed from nil to 100 % (v/v) respectively. These results indicate that pore size of the copolymer beads is a function of solvent composition. Received: 10 January 1999/Revised version: 15 February 2000/Accepted: 1 March 2000     

Pore memory of macroporous styrene–divinylbenzene copolymers

The variation of the pore structure of styrene–divinylbenzene (S–DVB) copolymer beads with the drying conditions was investigated. Macroporous S–DVB copolymer beads with various DVB contents were prepared in the presence of toluene‐cyclohexanol mixtures as a diluent. It was found that the pores of 10¹‐nm radius, corresponding to the interstices between the microspheres, collapse upon drying of the copolymers from toluene. The collapsed pores reexpand if the copolymers were dried from methanol. The collapse–reexpansion process of the pores was found to be reversible, indicating that the actual pore structure formed during the crosslinking copolymerization is memorized by the copolymer network. The magnitude of the pore structure variation increased on worsening the polymer–diluent interactions during the gel formation process due to the simultaneous increase in crosslink density distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1055–1062, 1999     

Synthesis and properties of solvent absorptive methyl methacrylate‐divinylbenzene copolymer beads

Methyl methacrylate‐divinylbenzene copolymer beads were synthesized by radical suspension polymerization. The effects of the divinylbenzene concentration and the composition of the toluene/heptane diluent were studied with regard to the polymer bead formation, surface morphology, solvent swelling ratio, and absorption kinetics. The crosslinking density and diluent composition were responsible for solvent swelling. The interaction between the polymer and the diluents is attributed to phase separation, which controls the formation of a network‐type or pore‐type polymer, or a combination. For the optimum bead swelling in toluene, a combined morphology of more flexible polymer networks and a small amount of pores is essential for the desired absorption–desorption behavior. Dynamic swelling behavior of the polymer beads was elucidated. The mechanism of toluene transport into the beads became more a relaxation control. POLYM. ENG. SCI., 47:447–459, 2007. © 2007 Society of Plastics Engineers.     

Styrene-Divinylbenzene Copolymers: Influence of the Diluents on Absorption and Desorption Properties

Styrene-divinylbenzene copolymers with porous structures were prepared by seeded suspension polymerization using toluene and heptane as diluents. The influence of each diluent on the formation of porous structure and the swelling ratio was investigated. The styrene-DVB beads are capable of absorption and desorption of organic solvents having solubility parameters in the range of 17.6–19.6 (MPa)1/2. Styrenic imbiber beads were swelled in toluene and the kinetics of absorption was studied. The imbiber bead could absorb toluene completely within 90 min and yielded a maximum swelling ratio of 12.7. The diffusion coefficient values of these beads were in the range of 1.55 × 10–5 to 3.68 × 10–5 cm2 · s–1.     

Formation and structural characteristics of porous ethylene glycol dimethacrylate networks

The relationships between the synthesis conditions and the morphology of ethylene glycol dimethacrylate (EGDM) networks were investigated. EGDM networks were prepared by free-radical polymerization in toluene as a diluent. The networks were characterized by swelling, porosity, and pendant vinyl group content measurements. The accessibility of pendant vinyls to low molecular weight compounds was tested using pyrrolidine as a model reactant. The results show that the polymerization of EGDM in toluene is accompanied by a phase separation in the system. The networks thus obtained are heterogeneous and exhibit an inhomogeneity in the porosity and swelling distributions. Both the weight swelling ratio and the pore volume of the networks increase with increasing monomer dilution. It was also found that the accessibility of pendant vinyls increases as the cross-linking density of the network decreases or as its porosity increases. The results can be explained with the formation of highly cross-linked microgels as the intermediates in the network formation processes. Two equations were derived to predict the equilibrium weight swelling ratio and the pore volume of heterogeneous networks. Satisfactory agreement of the results of measurements with the predictions of the equations was observed.     

Porous structure and swelling properties of styrene–divinylbenzene copolymers for size exclusion chromatography

Small spherical particles of styrene–divinylbenzene copolymers have been synthesized by modified suspension polymerization. The effects of divinylbenzene (DVB) contents, dilution degree of the monomers and diluent composition on the porous structure and swelling properties of the copolymers were investigated. Toluene uptakes of macroporous copolymers were considered as a result of three contributions: filling of the fixed pores, expansion of the fixed or collapsed pores, and nuclei swelling and heptane uptakes as a result of the two first contributions. The increase of DVB content in the copolymers synthesized in presence of a solvating diluent (toluene) provoked a decrease on the nuclei swelling. The increase of dilution degree with solvating diluents changed the toluene and heptane uptakes, and when the diluent–copolymer affinity was reduced, the fixed pore volume increased. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1257–1262, 1997     

Porous maleic anhydride–styrene–divinylbenzene copolymer beads

The formation of the porosity and the pore stability in maleic anhydride–styrene–divinylbenzene (MAn–St–DVB) copolymer beads were investigated using the apparent density measurements of the samples dried from methanol (maximum porosity) and from dioxane (stable porosity). The copolymer beads were prepared by the suspension polymerization method in glycerol instead of water as the dispersing medium. A toluene–dioxane (1:1) mixture was used as the diluent at a fixed volume fraction of the organic phase (0.47). Compared to St–DVB copolymers prepared in the presence of nonsolvating diluents, porous MAn–St–DVB copolymers are obtained at relatively low DVB concentration, i.e., at 1–3% DVB. The porosity of the copolymers increases with decreasing MAn concentration in the feed due to the decrease in the copolymer yield. The results of the elemental analyses and titrimetric methods indicate that approximately only half of the MAn units in the copolymer are able to react with amine or with water. A possible rearrangement of the MAn units into the cyclopentanone structures was suggested.     

Synthesis and characterization of styrene–divinylbenzene loaded with di(2-ethylhexyl)phosphonic acid. I. Influence of diluent mixture on the porous structure of the copolymer

Styrene–divinylbenzene copolymers were synthesized in the presence of di(2-ethylhexyl)phosphonic acid (EHEHPA) to be applied in the separation of rare earths by extraction chromatography. The copolymers were prepared by suspension polymerization in the presence of pure EHEHPA or in a mixture with isooctane, heptane, or toluene. The composition of the diluent mixture employed in the synthesis was varied. The apparent density, fixed pore volume, and surface area of the copolymers were determined. The content of EHEHPA retained in the copolymer beads was also determined, and it was found to be independent of the porous structure of the copolymer matrix. That content was only dependent on the amount of EHEHPA present in the diluent mixture. The toluene/EHEHPA mixtures produced the copolymers with the best properties required for extraction chromatography supports. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:781–787, 1998     

Synthesis of macroreticular copolymer beads having various phenolic derivatives immobilized via different bond and their radical scavenging activity

The macroreticular copolymer beads (RCS‐4G) were prepared by suspension copolymerization of chloromethylstyrene (CS) and tetraethyleneglycol dimethacrylate (4G) in water, using cyclohexane as a diluent. Then, the copolymer beads carrying phenolic derivatives immobilized via amide, methylene, or ether bond were prepared by subsequent reactions of RCS‐4G with various phenolic derivatives. The radical scavenging activity against 2,2‐Diphenypicrylhydrazil (DPPH) of the copolymer beads carrying phenolic derivatives immobilized was investigated in toluene. It was found that the copolymer beads had high radical scavenging activity against DPPH. The order of the radical scavenging activity against DPPH of the copolymer beads carrying phenolic derivatives immobilized did not coincide with the order of inhibition activity against the generation of 1,4‐dioxane hydroperoxide. The radical scavenging activity against DPPH of the copolymer beads having phenolic derivatives immobilized via methylene bond or ether bond was higher than that of the copolymer beads having phenolic derivatives immobilized via amide bond. It was found that the radical scavenging activity of the copolymer beads having phenolic derivatives was affected by not only the kind of phenolic derivatives immobilized and bond groups through which phenolic compounds were immobilized, but also the swelling ratio of the copolymer beads in toluene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4791–4800, 2006     

Swelling of porous copolymers based on alkyl methacrylate esters in water

Porous copolymers based on alkyl methacrylate esters (AMA) were prepared in the presence of toluene as the inert diluent, and their swelling properties in water were investigated by measuring the water uptake of the copolymers with or without being pretreated with methanol. With ethylene glycol dimethacrylate (EGDM) being used as the crosslinking agent, the obtained AMA/EGDM copolymers, regardless of their inherent hydrophobic nature, were found to be able to swell in water directly. The swelling was negligible in the lower degree of crosslinking region. However, once it increased to a value beyond a certain EGDM percentage, the swelling transition occurred, and the water uptake, which was measured by direct contact of the copolymers with water for all three kinds of AMA/EGDM copolymers based on methyl MA (MMA), ethyl MA (EMA), and butyl MA (BMA), reached very high values. The direct swelling of highly crosslinked AMA/EGDM copolymers in water was very fast at the beginning of the swelling with the swelling rate order of MMA/EGDM > EMA/EGDM > BMA/EGDM, but thereafter it progressed very slowly with most swelling being achieved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 250–258, 2000     

Water‐swelling behavior of hydrophobic porous copolymer resins composed of two kinds of crosslinkers

Hydrophobic, but water‐swellable, porous copolymer resins composed of divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDM) or ethylene glycol diacrylate (EGDA) were prepared by using purified DVB (98.8%) in the presence of toluene as porogen. The EGDM/DVB resins thus obtained, whose polarity was nearly identical to that of the resins based on DVB and methyl methacrylate (MMA) at the same DVB levels, were water‐swellable by direct contact with water up to a DVB content of 64%, whereas the latter did not swell in water at any DVB levels. EGDA is also hydrophobic, but with a polarity greater than that of EGDM. As a result, the EGDA/DVB resins were more water swellable than EGDM/DVB resins, and could also be prepared as water‐swellable materials by using technical DVB (79.3%), besides the use of the purified DVB. All these results were explained on the basis of the network rigidity (crosslinking density) and the polymer polarity of the resins that were formed in the presence of a well‐solvating porogenic solvent. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 997–1004, 2004     

Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

Kinetics of emulsifier–free emulsion polymerization of methyl methacrylate

The influences of polymerization temperature, initiator and monomer concentrations, ionic strength of the aqueous phase, as well as ethylene glycol dimethacrylate (EGDM) co-monomer, on the kinetics of the emulsifier-free emulsion polymerization of methyl methacrylate (MMA) and on the properties of the resulting poly(methyl methacrylate) (PMMA) lattices were studied. The polymerizations were carried out using potassium persulfate (KPS) as the initiator. Monodisperse PMMA lattices with particle diameters varying between 0.14–0.37 μm and polymer molecular weights of the order 0.4 × 10⁶ to 1.2 × 10⁶ g/mol were prepared. The initial rate of polymerization increases with increasing temperature, KPS-MMA mole ratio, EGDM content, or with decreasing ionic strength of the aqueous phase. It was shown that the bead size can be limited by reducing the monomer concentration or by using the cross-linking agent EGDM. The ionic strength of the aqueous phase has a dominant effect on final particle diameter and polymer molecular weight. The uniformity of the latex particles increases as the temperature increases or as the initiator concentration decreases. The experimental results can be reasonably interpreted by the homogeneous nucleation mechanism of the emulsifier-free emulsion polymerization of MMA. © 1996 John Wiley & Sons, Inc.     

Macroporous styrene-divinylbenzene copolymers: Formation of stable porous structures during the copolymerization

Summary The variation of the pore structure of styrene-divinylbenzene (S-DVB) copolymer beads depending on the polymerization time was investigated. Macroporous S-DVB copolymer beads with 10 mol % DVB content were prepared in the presence of cyclohexanol as a diluent. It was found that the stable pores in S-DVB copolymers mainly form at an early stage of the copolymerization, i.e., at the gel point. Thus, the early phase separated portions of the network, where the crosslink density is locally high, do not collapse on drying and illustrate the stable part of the porosity of S-DVB copolymers. The number of stable pores does not change much during the whole course of the copolymerization. The maximum porosity first decreases on rising the post-gelation time due to the decreasing degree of dilution of the gel phase. Then, it increases continuously due to the increasing crosslink density of the gel. The pores formed at a later stage of the copolymerization are unstable and they collapse during the drying process. This is due to the lower crosslink density of the network regions forming later. Received: 27 February 1998/Revised version: 18 June 1998/Accepted: 18 June 1998     

Styrene–divinylbenzene copolymers: Influence of the diluent on network porosity

The formation of the permanent porosity in the classical matrix, styrene–divinylbenzene copolymers, using cyclohexane, cyclohexanol, or cyclohexanone as diluent was studied. The data concerning porous networks were corroborated with the solvent–polymer interaction factor and the cohesive energy density which are important in the prediction of copolymer porosity. Between diluents there are noticeable differences, though the diluent volume and the divinylbenzene percent strongly influence the porous structure of the network. Cyclohexanal was the most efficient diluent for building up the highest porosity even at low percents of divinylbenzene.     

Particle features of a poly(methyl methacrylate) resin prepared by a new emulsion polymerization process

A new emulsion polymerization process, in which water acted as the dispersed phase and a mixture of methyl methacrylate (MMA) and cyclohexane acted as the continuous phase, was applied to the preparation of a poly(methyl methacrylate) (PMMA) resin. The primary (latex) particles were formed in the early stage of polymerization and coagulated as the polymerization conversion increased. Scanning electron micrographs showed that the final PMMA particles were porous and composed of loosely aggregated primary particles. The porosity characterized by cold di(2‐ethylhexyl) phthalate absorption increased as the water/oil and cyclohexane/MMA mass ratios increased. The PMMA primary particles were smaller than the primary particles in the PMMA resin prepared by suspension polymerization in the presence of cyclohexane. Because of the phase composition of the reaction system, the solubility of PMMA in a mixture of cyclohexane and MMA, and the particle morphology of PMMA, a particle formation mechanism, including the formation, growth, and coagulation of primary particles in dispersed water droplets, was proposed. The primary particles formed mainly through a homogeneous nucleation mechanism and increased in size as MMA diffused from the oil phase to the water phase to the primary particles. The coagulation of the primary particles occurred because of the lower colloidal stability and the space limitations of the primary particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1905–1911, 2004     

Preparation and characterization of amidoxime resins based on poly(acrylonitrile-co-vinylidene chloride-co-divinylbenzene)

The poly(acrylonitrile-co-vinylidene chloride-co-divinylbenzene) beads with macroporous morphology were synthesized by suspension polymerization. The use of dichloroethane as a solvating diluent resulted in copolymer beads having highly porous structures. These have been reacted with hydroxylamine in methanol, which generates amidoxime groups. The precursory resins were readily functionalized within 0.5–1 h. A detailed analysis is made of the pore structure of resins in the anhydrous state including pore size distribution and specific surface area. © 1994 John Wiley & Sons, Inc.     

Correlations for prediction of specific surface area and bulk and apparent densities of porous styrene‐divinylbenzene copolymers

Macroporous styrene‐divinylbenzene copolymers with different degree of crosslinking were prepared by suspension polymerization in presence of different binary mixtures of toluene and heptane, as diluent. Specific surface area, bulk and apparent densities, and pore volume of the resulting beads were determined experimentally. Applying the least square method to the experimental data, correlations for prediction of these properties were obtained. Effects of divinylbenzene concentration, diluent to comonomer volume ratio, and composition of the diluent mixture were considered in developing the aforementioned correlations. The influence of the reaction recipe on porous structure of the samples was also studied using scanning electron microscope (SEM). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PCR-g-MMA胶粘剂的制备及粘接性能

用乳液接枝聚合法合成了氯丁橡胶（OR）／甲基丙烯酸甲酯（MMA）接枝共聚物OR-g-MMA乳液;用凝聚法制备了粉末状PCR-g-MMA干胶，将其溶于甲苯中制备了胶粘剂。研究了CR／MMA接枝聚合反应条件对单体转化率的影响和PCR-g-MMA粒子在溶剂中的溶解速率及其胶粘剂的粘接性能。结果表明，在适宜的反应条件下，接枝体系的单体转化率接近100％。SEM分析表明．PCR-g-MMA粒子表面及内部存在许多宏观及微观孔洞，使产物易于洗涤、脱水和干燥．在溶剂中有极高的溶解速率．完全溶解时间为0．5～1h。仅为片状CR248完全溶解所需时间的1／10。PCR—g—MMA胶粘剂的粘接性能与CR／MMA乳液接枝聚合反应条件有关。用其粘合PVC人造革．其初粘力为20．4N／2．5cm，剥离强度为55N／2．5cm，与片状CR248／MMA溶液接枝制备所得的胶粘剂处于相同水平。     

Synthesis and heavy metal ion adsorptivity of macroreticular chelating resins containing phosphono and carboxylic acid groups

Macroreticular copolymer beads were prepared by suspension polymerization of 4-vinylbenzyl chloride (VBC), divinylbenzene (DVB) and monomers with carboxylic ester groups like dibutyl maleate (DBM), dibutyl fumarate (DBF) and dibutyl itaconate (DBI) in the presence of toluene as diluent. The copolymer beads were phosphorylated at the chloromethylated phenyl rings with triethyl phosphite and hydrolyzed by an aqueous sodium hydroxide solution; the hydrolysis on the bead surface converted carboxylic ester/phosphonate groups into carboxylic acid/phosphono groups, respectively. The investigations on the metal ion chelation characteristics of the H-form copolymer beads revealed that they have good adsorptivity toward heavy metal ions like Pb²⁺, Cd²⁺ and Cu²⁺, and poor adsorptivity toward ions like Hg²⁺ and UO₂²⁺. The adsorptivity caused by the three carboxylic ester monomer derivatives was in the order DBM > DBI > DBF. Especially, the Na-form copolymer beads neutralized by alkali treatment were very available for the adsorption of all the metal ions under investigation.