A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.

Synthesis of Monodisperse Poly(chloromethylstyrene divinylbenzene)Particle and Its Applications

Monodisperse poly (chloromethylstyrene divinylbenzene) particles were prepared by a two-step swelling method. It was demonstrated that the packings have comparative advantages for biopolymer separation with high column efficiency, low interstitial volume and low back pressure to the packings prepared with suspension polymerization method. Using size exclusionchromatography and weak ion exchange chromatography as examples, it was shown that these packings could be modified chemically more easily than poly (styrene divinylbenzene) packings.

Synthesis of Poly(styrene-co-divinylbenzene)-supported Dichloro Cyanuric Acid

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Preparation and Characterization of Poly(divinylbenzene) Microcapsules Containing Octadecane

Poly(divinylbenzene) (PDVB) microcapsules containing octadecane (OD) (PDVB/OD) used as heat storage material were synthesized by suspension polymerization at 70 Microencapsulation, Microcapsule, Heat Storage Material, Octadecane, Suspension Polymerization, Poly(Divinylbenzene)C using benzoyl peroxide and polyvinyl alcohol as initiator and stabilizer, respectively. Thermal properties and stability of PDVB/OD microcapsules were determined using differential scanning calorimeter (DSC) and thermogravimetric analyzer. The morphology and structure of microcapsules were characterized by optical microscope, scanning electron microscope and fourier transform infrared spectrophotometer. From DSC analysis, the melting temperature of encapsulated OD (28oC) was almost the same as that of bulk OD (30oC) while it was quite different in the case of the solidification temperature (19oC and 25oC for encapsulated and bulk OD, respectively). The latent heats of melting (184.0 J/g-OD) and solidification (183.2 J/g-OD) of encapsulated OD were reduced from those of bulk OD (241.7 and 247.0 J/g, respectively). However, the prepared PDVB/OD microcapsules are able to be used for heat storage applications.

Preparation of slightly crosslinked monodisperse poly(maleic anhydride-cyclohexyl vinyl ether-divinylbenzene)functional microspheres with anhydride groups via precipitation polymerization

Slightly crosslinked monodisperse poly（maleic anhydride-cyclohexyl vinyl ether-divinylbenzene） （MA-CHVE-DVB） microspheres were prepared via precipitation polymerization while using 2,2- azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and n-heptane without any stabilizer. The number-average diameter of the resultant poly（MA-CHVE-DVB） microspheres ranged from 0.478 to 1.386 μm with a polydispersity index of 1.00 to 1.02 that depended on the feed ratios of the MA/CHVE/DVB monomers. The introduction of one electron donor monomer cyclohexyl vinyl ether strongly affected the yield, size, and morphology of these slightly crosslinked microspheres. Quinoline- type chelating resins were obtained after combining the poly（MA-CHVE-DVB） with 8-hydroxyquinoline; the adsorption properties of these materials were measured through their ability to remove Cu^2＋ ions from water. The poly（MA-CHVE-DVB） microspheres with low degrees of crosslinking provided more effective functional groups and therefore better ion removal capabilities. These slightly crosslinked microspheres may have applications in water treatment as well as in sensing and drug delivery.

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATIONPRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.

PREPARATION OF POLY(ETHYLENEGLYCOL-co-ACRYLIC ACID) MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.

Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

A novel composite stationary phase composed of polystyrene/divinybenzene beads and quaternized nanodiamond for anion exchange chromatography

An approach for preparation of a novel composite anion exchanger composed of polystyrene/divinylbenzene (PS/DVB) beads and quaternized nanodiamods (QND) were proposed. Oxidized nanodiamonds (OND) were quaternized by the condensation polymerization between methylamine (MA) and 1,4-butanediol diglycidyl ether (BDDE), which were characterized by Fourier transform infrared (FTIR) spectra, X-ray phtoelectron spectroscopy (XPS), thermogravimetric analysis (TGA). QND with layers of cationic polyelectrolyte was attached onto the surface of sulfonated PS/DVB beads electrostatically. Subsequently, hyperbranched reaction of QND agglomerated on the PS/DVB bead surface was performed by the alternate reaction between MA and BDDE to increase the exchange capacity. The composite anion exchanger showed good stability in organic solvent and a wide pH range.The surface of these microspheres was characterized by scanning electron microscopy. In addition, ion exchange selectivity and separation efficiency of the anion exchangers were assessed using the mixtures of anions (F,Cl,NO_2,Br,NO_3,HPO_4~2 and SO_4~2) with carbonate/bicarbonate as eluent, and the anion exchanger with high exchange capacity could be used to analyze chloride in aqueous solution with high concentration of fluoride. This work explores the potential of nanodiamods as an agglomerated material for ion chromatography stationary phases for the separation of inorganic anions.

New Core-Shell Type Polymeric Supports Based on the Amberlite XAD-4 Adsorbent: A Novel Synthesis Procedure

The chloromethyl groups have been introduced into commercial S/DVB copolymer matrixes via interpenetratingpolymer networks (IPN) synthesis. The procedure involves impregnation of the Amberlite XAD-4 adsorbent,with use of the vinylbenzyl chloride (VBC) and divinylbenzene (DVB) monomers mixture, and suspensionpolymerization process. The syntheses were evaluated by FT-IR spectra and SEM analyses and furthermore bychlorine content determination as well as characterization of porous structure by nitrogen adsorption at liquid nitrogentemperature. Designed synthesis approach allowed determining organic and water phases composition. Furthermore,impact of an excess of the organic phase removal method has been investigated. Basing on the obtainedresults it could be stated that the chloromethyl groups, derived from VBC monomer, were successfully introducedinto the XAD-4 structure. Captured SEM images revealed significant changes in the beads’ surface morphology afterpolymerization processes. The presented studies reveal designed and executed synthesis processes, which involvethe use of a proper water phase and excess of organic phase removal. Observed changes in the beads’ morphologysuggest that introduced functionalities are concentrated on the porous surface of the XAD-4 adsorbent.