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 hollow polymer microspheres with functional groups by distillation precipitation polymerization

<正>Monodisperse hollow polymer microspheres having various functional groups on the shell-layer,such as carboxylic acid,pyridyl and amide,were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive,during which monodisperse poly(methacrylic acid)(PMAA) afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization.The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene(DVB) or ethyleneglycol dimethacrylate(EGDMA) as crosslinker and the functional comonomers,in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers,including carboxylic acid,amide and pyridyl,played an essential role for the formation of monodisperse core-shell functional microspheres.The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition.Transmission electron microscopy(TEM) and scanning electron microscopy (SEM) were used to determine the morphology of the resultant PMAA core,functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups.FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.     

PREPARATION OF SILICA/POLY(METHACRYLIC ACID)/POLY(DIVINYLBENZENE-CO-METHACRYLIC ACID)TRI-LAYER MICROSPHERES AND THE CORRESPONDING HOLLOW POLYMER MICROSPHERES WITH MOVABLE SILICA CORE

<正>Hollow poly(divinylbenzene-co-methacrylic acid)(P(DVB-co-MAA)) microspheres were prepared by the selective dissolution of the non-crosslinked poly(methacrylic acid)(PMAA) mid-layer in ethanol from the corresponding silica/PMAA/P(DVB-co-MAA) tri-layer hybrid microspheres,which were afforded by a three-stage reaction.Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid(MAA) via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-(methacryloxy)propyl trimethoxysilane(MPS)-modified silica core,which was prepared by the St(o|¨)ber hydrolysis as the first stage reaction.The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene(DVB) erosslinker in presence of silica/PMAA particles as seeds,in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure.The morphology and the structure of silica core,silica/PMAA core-shell particles,the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy(TEM),Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy(XPS).     

SYNTHESIS AND CHARACTERIZATION OF HYBRID PROTON CONDUCTING MEMBRANES OF POLY（VINYL ALCOHOL） AND PHOSPHOMOLYBDIC ACID

Hybrid proton conducting membranes of poly（vinyl alcohol） （PVA） and phosphomolybdic acid （PMA） were prepared by solution casting method. The effect of PMA doping and PVA crosslinking density on the membrane properties and proton conductivity were investigated. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of glutaraldehyde （GA） was characterized by IR spectroscopy. Proton conductivity of the membranes increases with an increase in concentration of the doped PMA and also with an increase in crosslinking density of the membranes. Proton conductivity results indicate that a significant amount of PMA was maintained in the membranes even after several hours of immersion in water. A maximum conductivity of 0.0101 S cm^-1 was obtained for the membrane with 33.3 wt% PMA and crosslinking density of 5.825 mol%. X-ray diffraction studies were carried out to investigate the influence of PMA doping and crosslinking density on the nature of the membranes. These properties make them very good candidates for polymer electrolyte membranes for direct methanol fuel cell application.     

Preparation and Characterization of Chitosan Composite Membranes Crosslinked by Carboxyl-capped Poly（ethylene glycol）

In this study a series of chemically crosslinked chitosan/poly（ethylene glycol） （CS/PEG） composite membranes were prepared with PEG as a crosslinking reagent other than an additional blend. First, carboxyl-eapped poly（ethylene glycol） （HOOC-PEG-COOH） was synthesized. Dense CS/PEG composite membranes were then prepared by casting/evaporation of CS and HOOC-PEG-COOH mixture in acetic acid solution. Chitosan was chemically crosslinked due to the amidation between the carboxyl in HOOC-PEG-COOH and the amino in chitosan under heating, as confirmed by FTIR analysis. The hydrophilicity, water-resistance and mechanical properties of pure and crosslinked chitosan membranes were characterized, respectively. The results of water contact angle and water absorption showed that the hydrophilicity of chitosan membranes could be significantly improved, while no significant difference of weight loss between pure chitosan membranes and crosslinked ones was detected, indicating that composite membranes with amidation crosslinking possess excellent water resistanance ability. Moreover, the tensile strength of chitosan membranes could be significantly enhanced with the addition of certain amount of HOOC-PEG-COOH crosslinker, while the elongation at break didn＇t degrade at the same time. Additionally, the results of swelling behaviors in water at different pH suggested that the composite membranes were pH sensitive.     

Sphere-to-rod transition of short-chain PEO-b-PDMS-b-PEO in aqueous solution induced by copolymer concentration

A short-chain triblock copolymer EO9-DMS7-EO9 was synthesized by coupling reaction of allyl-terminated poly（ethylene oxide） and Si-H-terminated poly（dimethylsiloxane）. The structure and purity of synthesized copolymer was carefully characterized. Self-assembly behavior of EO9-DMST-EO9 triblock copolymer in water was investigated. And it was found that along with the increase of copolymer concentration, morphology of self-assembled aggregates transits from sphere to rod. A plausible understanding of the morphology transition for the investigated triblock copolymer was proposed.     

SYNTHESIS AND PROPERTIES OF ACRYLIC-BASED SUPERABSORBENTS WITH ENHANCED CROSSLINKING ON PARTICLE SURFACE

A series of acrylic-based superabsorbent resins were synthesized by inverse suspension polymerization, using potassium persulfate as the initiator, N, N＇-methylene bisacrylamide （BIS） and divinylbenzene （DVB） as the multiple crosslinking agents. The morphology of the resulting superabsorbent resins revealed by SEM demonstrated that a hard shell layer was indeed formed due to surface crosslinking. The swelling and deswelling properties, and the mechanical strength of superabsorbents were investigated. The results indicated that the adding time of DVB and the amount of DVB participated in the crosslinking show a significant influence on the properties of superabsorbents. When DVB was added in polymerization later, the amount of DVB participated in reaction decreases and the surface crosslinked shell becomes thinner. It is suitable for DVB to be introduced in the later stage of the polymerization process, because the absorption rate of resin is efficiently improved in conjunction with higher water absorption. Furthermore, it was found that the mechanical strength of swollen superabsorbent with surface crosslinking was indeed enhanced in comparison with that of the conventional one.     

Preparation of micron-sized nonspherical polystyrene/poly(styrene-<Emphasis Type="Italic">co</Emphasis>-ethyleneglycol dimethacrylate) particles by seeded soap-free emulsion polymerization

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene(St) and ethyleneglycol dimethacrylate(EGDMA,used as a crosslinker) on spherical, linear polystyrene(PS) seed particles.The morphology of the resulting PS/poly(St-co-EGDMA) particles was dependent on the crosslinker concentration and polymerization temperature.     

Phase behavior of charge stablized colloid dispersion with added water soluble polymers

Demixing and colloidal crystallization in the mixture of charge stabilized colloidal poly(methyl methacrylate) particles and soluble poly(ethylene oxide) were investigated by means of synchrotron small-angle X-ray scattering (SAXS) technique. Phase diagram of the mixture was obtained based on visual inspection and SAXS results. The phase behavior is determined as a function of the concentration of the polymer as well as the volume fraction of the colloidal particles. The system shows a one phase region when the concentration of the polymer is low, whereas a two-phase region is present when the concentration of the polymer is larger than a critical concentration at certain volume fraction of the colloids. Interestingly, a face centered cubic colloidal crystalline structure was formed under certain conditions, which has been rarely observed in experiments of colloid-polymer mixtures with competing interactions.     

PREPARATION OF POLYETHERSULFONE ULTRAFILTRATION MEMBRANES FOR MILK CONCENTRATION AND EFFECTS OF ADDITIVES ON THEIR MORPHOLOGY AND PERFORMANCE

Polyethersulfone membranes were prepared from quaternary systems containing N,N-dimethylacetamide （DMAc） as solvent, polyvinylpyrrolidone （PVP） as constant additive and acetic acid, acetone and water as variable additives. Phase inversion via immersion precipitation was employed for manufacturing of membranes. The prepared films were immersed in the mixture of pure water and 2-propanol （30/70 vol%） as the non-solvent. Acetic acid caused an increment in the flux at high polymer concentration （16 wt%） and a decline in the flux at low polymer concentrations （10 wt% and 13 wt%）. Acetone and water as the solvent in the casting solution declined the flux at any polymer concentration tested. The morphology and performance of the prepared membranes were investigated by scanning electron microscopy and separation experiments using milk as the feed.     

蒸馏沉淀聚合过程中交联度对单分散聚合物微球形成的影响书

以苯乙烯为单体、二乙烯基苯（DVB）为交联剂，过氧化二苯甲酰（BPO）为引发剂研究了蒸馏沉淀聚合法制备聚合物微球过程中交联单体二乙烯苯的用量对单分散聚合物微球成球的影响。结果表明，增加二乙烯基苯的比例，即提高交联度有利于形成单分散的聚合物微球。     

沉淀聚合法Poly(DVB-co-EGDMA-co-MAA)功能聚合物微球的制备及表征

采用二乙烯基苯-55(DVB-55)和乙二醇二甲基丙烯酸酯(EGDMA)作为混合交联剂,乙腈为溶剂,偶氮二异丁腈(AIBN)为引发剂,以甲基丙烯酸为功能单体采用沉淀聚合法合成了单分散或窄分散的、表面具有羧基的交联聚合物微球,所得微球的粒径变化范围为0.6～3.8μm.通过调节交联剂DVB-55和EGDMA的投料比,可以对微球的粒径、粒径分布、产率、热稳定性以及表面官能团含量进行有效控制.文中对混合交联剂DVB-55与EGDMA比例的改变对微球的粒径、粒径分布以及产率的影响机理给出了理论解释;对DVB和EGDMA的兼容性研究表明,制备的三元聚合物微球的核拥有比投料比稍多的DVB单元,而微球的外层则以在预聚混合物中占更大比例的交联剂为主.     

Reparation of silica/poly(methacrylic acid)/poly(divinylbenzene-co-methacrylic acid) tri-layer microspheres and the corresponding hollow polymer microspheres with movable silica core

 Hollow poly(divinylbenzene-co-methacrylic acid) (P(DVB-co-MAA)) microspheres were prepared by the selective dissolution of the non-crosslinked poly(methacrylic acid) (PMAA) mid-layer in ethanol from the corresponding silica/PMAA/P(DVB-co-MAA) tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid (MAA) via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified silica core, which was prepared by the Stöber hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene (DVB) crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS).     

Crosslinking‐induced morphology change of latex nanoparticles: A study of RAFT‐mediated polymerization in aqueous dispersed media using amphiphilic double‐brush copolymers as reactive surfactants

Amphiphilic double‐brush copolymers (DBCs) with each graft site quantitatively carrying both a hydrophilic poly(ethylene oxide) (PEO) graft and a hydrophobic polystyrene (PSt) graft are synthesized by sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization and ring‐opening metathesis polymerization (ROMP). These DBCs are used as both surfactants and polyfunctional RAFT agents in the radical polymerization of St in aqueous dispersed media. Miniemulsions with narrowly dispersed St‐based nanodroplets are readily obtained after ultrasonication of the reaction mixtures. Without the presence of crosslinker, chain‐extension polymerization of St from the DBCs yields well‐defined polymeric latexes with narrow size distributions. However, with the presence of divinylbenzene (DVB) as the crosslinker, vesicular polymeric nanoparticles are formed as the major product. Such crosslinking‐induced change in morphology of the resulting latex nanomaterials may be ascribed to the increase of interfacial curvature in the heterophase systems during crosslinking polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3250–3259     

两亲磁性高分子微球的合成与表征

在Fe3O4磁流体存在下 ,通过苯乙烯与聚氧乙烯大分子单体 (MPEO)分散共聚制备两亲磁性高分子微球 .研究了聚氧乙烯大分子单体对微球粒径的影响 .用扫描电子显微镜 (SEM)、原子力显微镜 (AFM)表征了磁性微球的粒径、表面形貌以及表面粗糙度 ,用傅立叶红外光谱 (FTIR)鉴定了共聚物的结构 .随着聚合物中聚氧乙烯大分子单体含量的增加 ,微球表面的粗糙度增加 ,通过改变共聚物中MPEO的含量 ,可以得到含有 0 4～ 3 5mg g羟值的两亲磁性高分子微球     

Synthesis of microspheres stabilized sterically with two-component grafted chains by dispersion copolymerizations using mixture of two macromonomers in nonaqueous media

The polymer microspheres were synthesized by dispersion copolymerization of divinylbenzene (DVB) with two vinylbenzyl-terminated poly(ethylene glycol methylether) (PEG)/poly(t-butyl methacrylate) (PBMA) macromonomer blends in methanol. In these systems of two macromonomer blends as the emulsifier, the polymer microspheres formed had a very narrow particle size distribution. Two macromonomers formed comicelles with DVB monomer and acted not only as the comonomer but also as the stabilizer. Such polymer microspheres were stabilized sterically with two-component grafted chains, such as PEG and PBMA, in methanol.     

A Useful Poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) Triblock Crosslinker in a Diffusion‐Controlled Polymerization Method

Monodisperse micron‐sized polystyrene particles crosslinked with a novel poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) triblock diol diacrylate (t‐BDDA) were produced via simple dispersion polymerization. It was established that the monomer‐diffusible surface characteristics of primary particles played a decisive role in producing the monodisperse crosslinked polymer particles. We named this concept a diffusion‐controlled polymerization method, DPM. Here in this study, particularly, t‐BDDA is proposed as a very useful crosslinker capable of self‐assembling and crosslinking in the process of particle formation and particle growth.     

Adsorption Properties of Uranium (VI) Ions on Reactive Crosslinked Acrylamidoxime and Acrylic Acid Copolymer Resins

Crosslinked acrylic acid (AA) acrylonitrile (AN) copolymer was prepared by suspension copolymerization in the presence of poly (vinyl alcohol) as suspending agent and N,N-methylenebisacrylamide (MBA) and divinylbenzene (DVB) as crosslinking agents. The molecular ratios between AN and AA was 95: 5 mol%. Different ratios 2, 5, and 10 wt% of crosslinkers was used. The nitrile group of the copolymer was converted to acrylamidoxime in the presence of hydroxylamine. Morphologies of the prepared resins were examined by scanning electron microscope (SEM). Recovery of uranium ions was investigated. The adsorption of uranium was occurred in nitric acid, hydrochloric acid and sulfuric acid solutions. Effect of pH, time of loading, type of acid, ratio, and type of crosslinker were investigated. Regeneration of eluted resins was determined.     

Preparation of narrow or monodisperse poly(ethyleneglycol dimethacrylate) microspheres by distillation-precipitation polymerization

Highly crosslinked narrow or monodisperse poly(ethyleneglycol dimethacryltae) (polyEGDMA) microspheres were prepared by distillation-precipitation polymerization in neat acetonitrile with 2,2′-azobis(2-methyl propinitrile) (AIBN) as an initiator. The polymer microspheres with clean surfaces due to the absence of any added stabilizer in the reaction system were formed simultaneously through a precipitation manner during the distillation of acetonitrile off the reaction system. The effects of the solvent, initiator concentration, monomer concentration and comonomer (divinylbenzene, DVB) fraction on the formation of the microspheres were investigated. Narrow- or monodisperse particles with spherical shape and smooth surface were obtained with diameters between 1.18 and 2.50 μm with monomer loading lower than 3.13 vol%. The surfaces of the microspheres became rougher, some elliptic particles and doublet or triplet appeared with the increase of monomer concentration (as high as 3.75 vol%). The yield of polymer microspheres was increased from 31% to 75% with the increase of EGDMA fraction from 0 to 100% when EGDMA was copolymerized with DVB. The resulting polymer microspheres were characterized with scanning electron microscope (SEM) and Fourier transform-IR spectra.