Microsphere Synthesis by Dispersion Copolymerizations Using Poly(t-butyl methacrylate) Macromonomers in Nonaqueous Media

Polymer microspheres were synthesized by dispersion copolymerization of divinylbenzene (DVB) with vinylbenzyl-terminated poly(t-butyl methacrylate) (PBMA) macromonomers in nonaqueous media (methanol and acetonitrile). The particle diameter increased gradually with an increase of the DVB concentration in methanol or acetonitrile. The particle size distribution was very narrow. PBMA macromonomers acted not only as a comonomer but also as a stabilizer. The particle diameters obtained in acetonitrile were smaller than those obtained in methanol. Thus, we observed a tendency in which the more soluble for PBMA macromonomer the media became, the smaller the particle size became. Copyright 2001 Academic Press.     

Preparation and Characterization of Polymeric Microspheres Having Isotactic Poly(methacrylic acid) on Their Surfaces

IntroductionUseful strategies for the synthesis of polymer-ic particles and their surface modification have re-ceived much attention. In recent years,authorshave been interested in the preparation and thecharacterization of sub- micron to micron- sizemonodisperse polymeric particles by the emulsifier-free radical dispersion copolymerization of hy-drophilic macromonomers and hydrophobicmonomers in polar solvents.Itwas found thatwa-ter- soluble polymer chains grafted on the surfacesof the partic…     

Graft copolymers having hydrophobic backbone and hydrophilic branches. X. Preparation and properties of water-dispersible polyanionic microspheres having poly(methacrylic acid) branches on their surfaces

The free radical copolymerization of poly(t-butyl methacrylate) (PBMA) macromonomer with styrene in ethanol give monodispersed microspheres with 0.8-1.6 μm diameter. The resulting microspheres were treated with HCl solution to convert into anionic microspheres having poly(methacrylic acid) chains. ESCA analysis of the microsphere surface suggested that PBMA chains were favorably located on the surface of the microspheres. The particle size of the microspheres decreased with increasing molecular weight and concentration of the macromonomer. Water dispersibilities of the microspheres were evaluated by measuring the relative turbidity of the suspension of microspheres as a function of pH. The results show that they were strongly dependent on pH. © 1995 John Wiley & Sons, Inc.     

PAm-g-PMAA亲水性聚合物微球的合成

利用链转移自由基聚合和端基置换反应法 ,合成了苯乙烯基单封端的聚甲基丙烯酸叔丁酯 (PBMA)大分子单体 .在N ,N′ 亚甲基二丙烯酰胺 (Bis A)存在的条件下 ,使PBMA大分子单体与亲水性单体丙烯酰胺(Am)在乙醇 水的混合介质中进行分散共聚反应 ,得到了表面为PBMA接枝的聚丙烯酰胺 (PAm g PBMA)聚合物微球 .将所得PAm g PBMA微球在酸性条件下水解 ,得到了整体亲水的聚甲基丙烯酸接枝的聚丙烯酰胺(PAm g PMAA)聚合物微球 .用激光光散射、透射电子显微镜和X射线光电子能谱仪等对聚合物微球的直径、形态及表面组成进行了表征 .研究结果表明 ,在共聚反应中PBMA大分子单体的分子量与浓度、Bis A浓度和介质的组成对微球的形成与颗粒直径的大小有明显影响 ;所形成的聚合物颗粒是以PBMA为壳、以交联PAm为核的核壳结构微球 .     

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.     

两亲高分子微球的合成与表征

通过苯乙烯和聚氧乙烯大分子单体的共聚,合成了粒径在0.5μm～1.5μm的两亲高分子微球.随着聚氧乙烯大分子单体浓度的增加,微球粒径减小.通过扫描电镜,IR等分析手段对微球进行了表征.     

醇/水介质对PEG大分子单体与BMA分散共聚反应的影响

通过端基反应法合成了苯乙烯单封端的聚乙二醇(St- PEG)大分子单体,使其与甲基丙烯酸丁酯(BMA)在乙醇 水混合介质中进行分散共聚,得到了聚乙二醇接枝的聚甲基丙烯酸丁酯(PBMA- g -PEG)高分子微球.PBMA- g -PEG共聚物的亲溶剂 疏溶剂平衡将影响微球的形成,反应结束时,体系随BMA浓度和介质中水含量的变化呈现出4种不同的状态,透明清液、乳液、伴有沉淀或凝胶的乳液和凝胶.用透射电子显微镜(TEM)和激光光散射(LLS)对乳液体系的粒径及其形态进行了表征,表明所得接枝高分子微球形态规整具有较好的单分散性.通过控制介质中水的含量和BMA的浓度可得粒径在4 0～5 0 0nm范围的PBMA -g -PEG微球.     

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.     

氨基两亲高分子磁性微球的制备与表征

采用分散聚合法,以乙醇水为介质,在Fe3O4磁流体存在下,通过苯乙烯与聚氧乙烯大分子单体(MPEO)共聚制备了同时具有两亲性和磁响应性的端基为氨基的高分子微球.改变聚合条件可以得到平均粒径范围在5～80μm,氨基含量为0.01～0.25mmolg的两亲磁性高分子微球.     

大分子单体聚N-乙烯甲酰胺与苯乙烯共聚合成热敏性功能高分子微球

用自由基聚合法合成了大分子单体聚N 乙烯甲酰胺和功能高分子微球 .用GPC、分光光度仪和扫描电子显微镜等对合成的聚合物进行了表征 .研究结果表明 ,大分子单体聚N 乙烯甲酰胺和功能高分子微球具有明显的热敏性特性 ,且合成的功能高分子微球具有单分散性 ,粒径在 1～ 5 μm之间     

In‐line monitoring of immiscible polymer blends in a rheometer with a fiber‐optics‐assisted fluorescence detection system

In‐line studies of the initial stages of shear‐induced coalescence in two‐phase polymer blends were carried out with a home‐built device combining a cone and plate rheometer and a fiber‐optic‐assisted fluorescence detection system. A blend of 90 wt % poly(2‐ethylhexyl methacrylate) (PEHMA) and 10 wt % poly(butyl methacrylate) (PBMA) was prepared by the casting of films onto a solid substrate from mixed aqueous latex dispersions of the two polymers. The dispersions were prepared via emulsion polymerization under conditions in which both components were formed as spherical particles with a very narrow size distribution. By using a 14:1 particle ratio of PEHMA to PBMA, we obtained films in which 120‐nm PBMA particles were surrounded by a PEHMA matrix. The blend contained phenanthrene‐labeled PBMA particles and anthracene‐labeled PBMA particles in a ratio of 4:1, whereas the PEHMA matrix polymer was unlabeled. We monitored the anthracene‐to‐phenanthrene fluorescence intensity ratio (I₄₇₀/I₃₆₀) as a measure of direct nonradiative energy transfer from phenanthrene to anthracene, whereas the blend was sheared at different shear rates and temperatures. Under no‐shear conditions, the results of in‐line experiments were in good agreement with the results of off‐line measurements of energy transfer by conventional techniques. In blends under shear, the two sets of experiments, in‐line and off‐line, did not agree with each other. The cause of this disagreement was associated with normal forces in the blend under shear that affected the optical path length and the relative intensities of the fluorescence signals of the phenanthrene and anthracene groups in the blend. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2302–2316, 2001     

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     

Solidification of non-halogen fire-retardant liquids by encapsulation within porous uniform PDVB microspheres for preparation of fire-retardant polymeric blends

Polystyrene/polydivinyl benzene (PS/PDVB) composite microspheres of narrow size distribution were prepared by a single-step swelling process of uniform PS microspheres with DVB and benzoyl peroxide, followed by polymerization of DVB within the microspheres. Dissolution of the PS template resulted in porous uniformly sized PDVB microspheres. New, solid, non-halogenated, fire-retardant composite microspheres of narrow size distribution were prepared by encapsulation of resorcinol bis (diphenyl phosphate) (RDP) within the pores of the PDVB microspheres. The encapsulation was performed by two different methods as follows: (1) vacuum and (2) heat/cool cycles. The loading capacity of the RDP into the PDVB particles was elucidated. PS/PDVB-RDP blends were prepared by mixing PS with the PDVB-RDP microspheres. Thermogravimetric analysis (TGA) illustrated that the thermal stability of the PS increases as the content (10–40 %) of the PDVB-RDP increased. Polycarbonate/poly(acrylonitrile-butadiene-styrene)/PDVB-RDP (PC/ABS/PDVB-RDP) blends were prepared by melting PC/ABS together with the PDVB-RDP microspheres at 250 °C and then pelleting it in an injection molding machine at 250 °C and 40 t. The improved thermal stability of the PC/ABS by blending it with PDVB-RDP was demonstrated by a vertical burn test on PC/ABS/PDVB-RDP bones.     

Miscibility window for the blends of poly(styrene-co-4-vinylphenymethylphenylsilanol) with poly(n-butyl methacrylate)

Polymer blends consisting of poly(styrene-co-4-vinylphenylmethylphenylsilanol) (ST-VPMPS) and poly(n-butyl methacrylate) (PBMA) have been investigated. The experimental results showed that miscible blends were formed when ST-VPMPS copolymers contained 9–56 mol % silanol functional groups. Comparison of the results with poly(styrene-co-4-vinylphenyldimethylsilanol) (ST-VPDMS)/PBMA blends revealed that the miscibility window was shifted to a higher silanol composition in the present system in which a stronger hetero-associated hydrogen bonding interaction was present. The results were discussed in terms of steric shielding and electron-withdrawing effects of the phenyl substituent bound directly to the silicon atom. © 1996 John Wiley & Sons, Inc.     

Novel Silanol-Containing Polymers and Their Blends

ABSTRACT

Novel 4-vinylphenyldimethylsilanol polymer (PVPDMS) and co-polymers (ST-VPDMS) were synthesized by the oxyfunctionalization re- action of the silane. The reaction was found to proceed efficiently and quantitatively. Miscibility studies indicated that about 4 molpercnt; of 4-vin- ylphenyldimethylsilanol (VPDMS) functional group in the copolymer could achieve miscibility with poly(n-butyl methacrylate) (PBMA) and poly(N-vinylpyrrolidone) (PVPr). However, for copolymers containingmore than 34 molpercnt; VPDMS, their blends with PBMA were immiscible. The observed miscibility window of ST-VPDMS/PBMA blends was as- cribed to the competition between the self-association of dimethylsilanol groups and intermolecular hydrogen bonding of dimethylsilanol groups with the carbonyl groups of PBMA. A comparison of the efficiency of the miscibility enhancement and the miscibility windows of VPDMS, p-(hexafluoro-2-isopropyl) styrene (HFPS), and phenolic-containing polymers was made in terms of such competition. The glass transition behavior of the miscible blends involving VPDMS and HFPS-containing styrene copolymers with PBMA were analyzed by the Schneider equation.     

Fractional crystallization behavior of PCL and PEG in blends

The crystallization behavior of poly(e-caprolactone)/poly(ethylene glycol) (PCL/PEG) blend was investigated by differential scanning calorimetry (DSC) and polarized microscopy (POM). Individual phase transition peaks in the DSC curves for both PEG and PCL in all the polymer blends with different PCL contents were observed. The crystallization and melting peak temperatures of PEG were at 41 and 65°C, respectively; while the crystallization and melting temperatures of PCL located at 28 and 56°C, respectively. In-situ POM results demonstrated that spherulites crystalline morphology was formed for both PCL and PEG homopolymers. In PEG/PCL blend, however, both the phase separation morphology and spherulitic morphology can be observed. In blends with 30 or 50 wt % PCL, the PCL component formed dispersed phase and crystallized at lower temperature. However, in blends with 70% PCL, the phase inversion behavior occurred. The continuous PCL phase crystallized at 35°C, while the PEG dispersed phase crystallized at a lower temperature. Fractional crystallization behavior of PEG and PCL was controlled by temperature. The spherulites growth rate of PEG was greatly influenced by temperature, instead of the content of PCL component in the PCL/PEG blends.     

Synthesis and characterization of poly(ethylene oxide) star polymers possessing a tertiary amino group at each arm end by organized polymerization using macromonomers

Functional poly(ethylene oxide) star polymers possessing a tertiary amino group at each arm end were prepared by free-radical copolymerization of poly(ethylene oxide) macromonomers with divinylbenzene (DVB) in water or ethanol. The poly(ethylene oxide) arm was prepared by anionic polymerization using 2-[2-(N,N-dimethylamino)ethoxy]ethanol potassium alkoxide as the initiator. The star polymers had narrow molecular weight distribution. The arm number was controlled by varying the feed ratio [DVB]/[M], the initial concentration of macromonomer [M], and solvent media. The branching factor g' in methanol ([eta]S/[eta]L are the intrinsic viscosities of the star and linear molecules, respectively) exhibited a power-law dependence on the arm number, f, with a negative exponent. This means that the dimensions of a star were in agreement with the Daoud-Cotton scaling model.     

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATION-PRECIPITATION POLYMERIZATION

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

Synthesis of core‐shell poly(divinylbenzene) microspheres via reversible addition fragmentation chain transfer graft polymerization of styrene

Styrene has been grafted from crosslinked poly(divinylbenzene) core microspheres by both reversible addition fragmentation chain transfer (RAFT) polymerization and conventional free radical polymerization. The core microspheres were prepared by precipitation polymerization. Crosslinked poly(DVB) core microspheres containing double bonds on the particle surface can be used directly to graft polymers from the surface by RAFT without prior modification of the core microspheres. The RAFT agent 1‐phenylethyl dithiobenzoate (PEDB) was used: Particle sizes increased from 2 μm up to 3.06 μm, and the particle weight increased by up to 6.5%. PEDB controls the particle weight gain, the particle volume, and the molecular weight of the soluble polymer. PEDB was also used to synthesize core poly(DVB) RAFT microspheres that contain residual RAFT end groups on the surface and within the particle. Styrene was subsequently grafted from the surface of these core poly(DVB) RAFT microspheres. The generated microspheres were characterized by ¹H‐NMR spectroscopy, focused ion beam (FIB) milling, Coulter particle sizing, and size exclusion chromatography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5067–5076, 2004     

分散共聚法制备特殊形态高分子微球的研究

以聚乙二醇 (PEG)大分子单体为反应性稳定剂 ,在丙烯腈的分散共聚反应中添加少量苯乙烯以形成疏水性核 ,制备得到了亚微米级高分子微球 .透射电子显微镜研究表明 ,该高分子微球具有特异的形态结构 .同时研究了分散共聚体系中各种反应因素对微球形态和直径的影响 ,结果表明 ,苯乙烯单体的添加量、PEG大分子单体的浓度及分子量、混合溶剂的组成对微球直径和形态均有明显的影响 .X 射线光电子能谱 (XPS)研究结果表明 ,微球表面聚集有亲水性PEG链 ,核为疏水的聚 (丙烯腈 苯乙烯 ) ,即形成的特异形态的PEG接枝高分子微球亦为复合型结构