反应性复合乳液的合成、表征及其交联反应

利用种子半连续乳液聚合方法合成了核层或壳层带有环氧基以及壳层带有羧基的3种不同核/壳结构的乳胶粒子,通过物理共混带环氧基和羧基的乳胶粒子,得到了两种反应性复合乳液.利用透射电镜和激光动态光散射对乳胶粒子进行了表征,其粒径分布较窄,粒径分布的多分散系数为0.062,平均粒径约76 nm,乳胶粒子具有明显的核/壳结构.通过胶膜的凝胶率和膨胀率的测定和红外光谱分析对反应性复合乳液中乳胶粒子的扩散及交联反应进行了研究,并探讨了不同核壳结构复合乳液对涂膜机械性能的影响.研究表明,当反应性复合乳液中的环氧基和羧基分别分布在乳胶粒子的核层和壳层时,有利于聚合物分子链的充分扩散和化学交联反应的进行,从而提高涂膜的物理化学性能,当甲基丙烯酸缩水甘油酯(GMA)含量为10 wt%时,涂膜的拉伸强度达20.3 MPa.     

Design and analysis of the homogeneous and heterogeneous distribution of water confined within colloidal polymer particles

Water is known to distribute within polymeric films in multiple states differentiable by the energy of association. Potentiometric swelling of carboxylated latex samples and subsequent differential scanning calorimetry (DSC) and thermogravimetric analysis verified this distribution of water, specifically confined within colloidal nanoparticle dimensions. DSC cooling curves can delineate between the freezable bound and freezable unbound water at low total water content but become difficult to distinguish the freezable bound contribution at high total water content. Of note is that the ratio of weakly bound water in the secondary layer to the water strongly hydrogen-bound to the polymer is approximately constant regardless of carboxylic acid type and, in fact, is greater for the case of the hydrophobic base polymer. Aside from its distribution within the particles, the total water content also appeared to be more related to the hydroplasticized glass point of the polymer colloid as opposed to the polarity of the polymer.     

Synthesis and some properties of functionalized film-forming latexes

Semi-continuous emulsion copolymerization was used for preparation different colloid copolymers containig hydroxyl, carboxyl and amide functional groups. Copolymerization of hydroxyethyl methacrylate with styrene and butyl acrylate was investigated. Molecular weight increase in the copolymerization of methacrylamide indicated an extensive branching of macromolecules. Functionalized latexes have been used as binders in water borne paints. In addition to the crosslinking ability the hydrophilic functional monomers positively affect the film formation. The effect of dissociated carboxylic groups on lowering the minimum film forming temperature was much more pronounced if the polymer chains were more polar and softer. Some relationships between the latex flow properties and the film forming ability have been illustrated in this paper.     

Morphology and film formation of poly(butyl methacrylate)–polypyrrole core–shell latex particles

 Core–shell latex particles made of a poly(butyl methacrylate) (PBMA) core and a thin polypyrrole (PPy) shell were synthesized by two-stage polymerization. In the first stage, PBMA latex particles were synthesized in a semicontinuous process by free-radical polymerization. PBMA latex particles were labeled either with an energy donor or with an energy acceptor, in two different syntheses. These particles were used in a second stage as seeds for the synthesis of the core–shell particles. The PPy shell was polymerized around the PBMA core latex in an oxidative chemical in situ polymerization. Proofs for the success of the core–shell synthesis were obtained using nonradiative energy transfer (NRET) and atomic force microscopy (AFM). NRET gives access to the rate of polymer chain migration between adjacent particles in a film annealed at a temperature above the glass-transition temperature T _g of the particles. Slower chain migration of the PBMA polymer chains was obtained with the PBMA–PPy core–shell particles compared to rate of the PBMA polymer chain migration found with the pure, uncoated PBMA particles. This result is due to the coating of PBMA by PPy, which hinders the migration of the PBMA polymer chains between adjacent particles in the film. This observation has been confirmed by AFM measurements showing that the flattening of the latex film surface is much slower for the core–shell particles than for the pure PBMA particles. This result can again be explained by the presence of a rigid PPy shell around the PBMA core. Thus, these two complementary methods have given evidence that real core–shell particles were synthesized and that the shell seriously hinders film formation of the particles in spite of the fact that it is very thin (thickness close to 1 nm) compared to the size (750 and 780 nm in diameter) of the PBMA core. Transparency measurements confirm the results obtained by NRET and AFM. When the films are placed at a temperature higher than the T _g of PBMA, the increase in transparency is faster for films made with the uncoated PBMA particles than for films made with the coated PBMA particles. This result indicates again that the presence of the rigid PPy layer around the PBMA core reduces considerably the speed at which the structure of the film is modified when heated above the T _g of PBMA. Received: 02 September 1999 Accepted: 21 December 1999     

Submicron Sized Hollow Polymer Particles: Preparation and Properties

The considered method for obtaining hollow polymer particles is based on the following pathway: (1) preparation of a carboxylated core latex by emulsion copolymerization of acrylic monomers with methacrylic acid, (2) synthesis of a core-shell latex comprising a styrene (co)polymer shell, (3) neutralization of the core carboxylic groups with a base followed by the core ionization and hydration to a high degree, shell expansion and formation of water-filled hollows. A number of approaches to improve the hydrophilic core – hydrophobic shell compatibility and enlarge the hollow volume are considered. The synthesized hollow particles are of a submicron size with the relative hollow volume V_hol : V_part.= 0.43 – 0.64. Methods for cationic hollow particle latex preparation by anionic latex recharging with a cationic surfactant or acidic melamine resin are discussed. Recharging with a melamine resin is shown to afford hollow particles with an external polymer shell providing a high thermal stability of the particles.     

Preparation and clinical application of immunomagnetic latex

Magnetic poly(methyl methacrylate) (PMMA)/poly(methyl methacrylate‐co‐methacrylic acid) [P(MMA–MAA)] composite polymer latices were synthesized by two‐stage soapless emulsion polymerization in the presence of magnetite (Fe₃O₄) ferrofluids. Different types and concentrations of fatty acids were reacted with the Fe₃O₄ particles, which were prepared by the coprecipitation of Fe(II) and Fe(III) salts to obtain stable Fe₃O₄ ferrofluids. The Fe₃O₄/polymer particles were monodisperse, and the composite polymer particle size was approximately 100 nm. The morphology of the magnetic composite polymer latex particles was a core–shell structure. The core was PMMA encapsulating Fe₃O₄ particles, and the shell was the P(MMA–MAA) copolymer. The carboxylic acid functional groups (COOH) of methacrylic acid (MAA) were mostly distributed on the surface of the composite polymer latex particles. Antibodies (anti‐human immunoglobulin G) were then chemically bound with COOH groups onto the surface of the magnetic core–shell composite latices through the medium of carbodiimide to form the antibody‐coated magnetic latices (magnetic immunolatices). The MAA shell composition of the composite latex could be adjusted to control the number of COOH groups and thus the number of antibody molecules on the magnetic composite latex particles. With a magnetic sorting device, the magnetic immunolatices derived from the magnetic PMMA/P(MMA–MAA) core–shell composite polymer latex performed well in cell‐separation experiments based on the antigen–antibody reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1342–1356, 2005     

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 and characterization of emulsifier-free core–shell interpenetrating polymer network-fluorinated polyacrylate latex particles

The emulsifier-free core–shell interpenetrating polymer network (IPN) fluorinated polyacrylate latex particles with fluorine rich in shell were prepared by emulsifier-free seeded emulsion polymerization with water as the reaction medium. The fluorinated copolymer could be fixed on the particle surface due to the formation of interpenetrating polymer network. The resultant core–shell particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) analysis, Fourier transform infrared (FTIR) spectrometry, X-ray photoelectron spectroscopy (XPS) analysis and thermogravimetric analysis (TGA). The core–shell particles possessed very narrow monomodal particle size distributions. XPS analysis of the latex film displayed that perfluoroalkyl groups had the tendency to enrich at surface and there was a gradient concentration of fluorine in the structure of the latex film from the film–air interface to the film–glass interface. In addition, compared with the latex film of crosslinked polyacrylate prepared under the same condition, the emulsifier-free core–shell IPN-fluorinated polyacrylate latex film showed better thermal stability, higher contact angle and lower water uptake.     

Effect of the Shell Crosslinking Level andCore/Shell Ratio on the Morphology of LatexParticles in the Preparation of Hollow Latexes简

Three-layer core/shell latex particles with various shell crosslinking level and shell thickness were prepared by multistep emulsion polymerization, and the hollow latex particles with different morphologies were then obtained after alkali post-treatment. Influences of divinyl benzene(DVB) content and the core/shell mass ratio on emulsion polymerization and particle morphology were investigated. Results showed that with the increase of DVB content, the percentage of total amount of ―COOH on the particle surface and free in aqueous phase(PSFa) decreased, and the morphology of the post-treated particles underwent evolution from cracked, intact hollow to deficient swelling structure. Decreasing the core/shell mass ratio could not only make more carboxyl groups encapsulated by the shell, but also increase the shell resistance to the swelling of the core. The uniform hollow latex particles with intact morphology were obtained when the DVB content was 3.54 wt% and the core/shell mass ratio was 1/6.     

Tailoring of carboxyl‐decorated magnetic latex particles using seeded emulsion polymerization

In this research, submicron and carboxyl‐functionalized magnetic latex particles were elaborated by using seeded emulsion polymerization technique in presence of oil‐in‐water (o/w) magnetic emulsion as seed. The polymerization conditions were optimized in order to get well‐defined latex particles with magnetic core and polymer shell bearing carboxylic (–COOH) functionality. Starting from (o/w) magnetic emulsion as seed, synthesis process was performed by copolymerization of styrene (St) monomer with the cross‐linker divinylbenzene (DVB) in presence of 4,4′‐azobis(4‐cyanopentanoic acid) (ACPA) as a carboxyl‐bearing initiator. The prepared magnetic latex particles were first characterized in terms of particle size, chemical composition, morphology, magnetic properties, magnetic content, and colloidal stability using various techniques, e.g. particle size analyzer using dynamic light scattering (DLS) technique, Fourier transform infrared, transmission electron microscopy, vibrating sample magnetometer, thermogravimetric analysis, and zeta potential measurements as a function of pH of the dispersion media, respectively. The prepared magnetic latex particles were then used as second seed for further functionalization with methacrylic acid (MAA) in order to enhance carboxylic groups on the magnetic particle's surface. The results showed that final magnetic latex particles possessed spherical morphology with core‐shell structure and enriched carboxylic acid functionality. More importantly, they exhibited superparamagnetism with high magnetic content (58.42 wt%) and high colloidal stability, which considered as the main requirements for their application in the biomedical diagnostic domains. Copyright © 2017 John Wiley & Sons, Ltd.     

Influence of Side‐Chain Composition on Polythiophene Properties and Supramolecular Assembly of Anionic Polythiophene Derivatives

A series of 10 polythiophene derivatives is reported, in which each polymer has a different percentage of carboxylic acid‐bearing repeat units. The properties of these polymers are explored under acidic conditions, where the carboxylic acid moieties remain neutral, and under basic conditions, where the carboxylic acid units become anionic carboxylates. The properties that are examined for both solutions and films include UV–vis absorption spectroscopy, photoluminescence spectroscopy, and red‐edge optical band gaps. All the properties studied are strongly dependent both on protonation state and percentage of carboxylic acid/carboxylate side chains along the polymer backbone. The anionic form of each polythiophene derivative was also used in layer‐by‐layer film deposition with a cationic phosphonium polyelectrolyte. The film growth process was studied by spectroscopic techniques to assess the influence of side‐chain composition on the film growth and optical properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films

The effects of methyl methacrylate (MMA) grafting and in situ formation of silica particles on the morphology and mechanical properties of natural rubber latex (NRL) were investigated. MMA grafting on NRL was carried out using cumyl hydroxy peroxide/tetraethylene pentamine (CHPO/TEPA) as a redox initiator couple. The grafting efficiency of the grafted NR was determined by solvent extractions and the grafted NRL was then mixed with tetraethoxysilane (TEOS), a precursor of silica, coated by adherence to a glass surface to form a film and cured at 80°C. The resultant products were characterized by FT‐IR and transmission electron microscopy. The influence of varying the MMA monomer weight ratio on the surface morphology of the composites was investigated by scanning electron and atomic force microscopy. The PMMA (poly MMA) grafted NRL particles were obtained as a core/shell structure from which the NR particles were the core seed and PMMA was a shell layer. The silane was converted into silica particles by a sol–gel process which was induced during film drying at 80°C. The silica particles were fairly evenly distributed in the ungrafted NR matrix but were agglomerated in the grafted NR matrix. The root‐mean‐square roughness increased with an increasing weight ratio of MMA in the rubber. The in situ silica particles in the grafted NR matrix slightly increased both the modulus and the tear strength of the composite film. Copyright © 2008 John Wiley & Sons, Ltd.     

可控异质不对称微粒的制备与组装

以聚合物薄膜作为掩模层来掩蔽有序的单层二氧化硅微粒阵列, 通过等离子体刻蚀控制二氧化硅微粒暴露面积, 并在其上进行可控的化学修饰或可控气相沉积, 利用异质区域选择性组装碲化镉荧光量子点, 得到了具有稳定荧光功能的异质不对称微粒. 利用此方法, 还可以通过引入官能团或粒子进一步得到更高级的多功能不对称微粒.     

Production of micron-sized monodispersed core/shell composite polymer particles by seeded dispersion polymerization

 The effect of the weight ratio of seed polymer/monomer on the morphology of the poly(methyl methacrylate) (PMMA)/polystyrene (PS) monodispersed composite particles produced by batch seeded dispersion polymerization of styrene with 1.64-μm-sized monodispersed PMMA seed particles in a methanol/water medium (4/1 w/w) was examined. In the PMMA/PS weight ratios of 3/1 and 2/1, the composite particles had a clear morphology consisting of a PMMA core and a PS shell. In the ratio of 1/1, a lot of small PS domains were observed in the PMMA core though the PS shell was still formed. By stepwise addition of styrene monomer, the formation of the small PS domain was depressed and complete core/shell morphology was formed. Absorption/release treatments of toluene into/from the PMMA/PS (1/1 w/w) composite particles resulted in a drastic morphological change from the core/shell structure to a multi- layered one. Received: 2 February 1999 Accepted in revised form: 7 April     

Preparation of micron-sized composite polymer particles containing hydrophilic 2-hydroxyethyl methacrylate and their biomedical applications

Micron-sized polystyrene or PS particles were first prepared by dispersion polymerization. Then a series of polystyrene/poly(styrene-2-hydroxyethyl methacrylate) or PS/P(S-HEMA) composite polymer particles was prepared by seeded copolymerization using different amounts of 2-hydroxyethyl methacrylate (HEMA) at the constant core/shell ratio of 1/0.5. The produced PS seed and composite polymer particles were characterized by transmission electron microscopy. Adsorption behaviors of some biologically active macromolecules were studied under similar conditions. In each case the magnitude of adsorption on composite polymer particles decreased with the increase in HEMA content in the recipe, which means that the hydrophobic interaction between the surface of the particles and biomolecules decreased. The specific activities of trypsin aqueous solution and adsorbed trypsin on PS seed and composite polymer particles prepared with different HEMA contents were also measured and compared. The activity of adsorbed trypsin on composite polymer particles improved significantly with the incorporation of hydrophilic HEMA.     

交联苯乙烯/丙烯酰胺共聚微球的制备及其C_(60)功能化初探

以二乙烯基苯 (DVB)为交联剂 ,利用一次投料分散共聚合的方法合成了交联的苯乙烯 (St) /丙烯酰胺 (Am )共聚微球 .实验发现 ,共聚单体Am的投料量和介质的极性对微球的形态有着显著的影响 .在反应过程中交联PS链段和PAm链段发生相分离 ,使粒子产生异形 .随后 ,通过微球上的酰胺基团与C60 的反应 ,将C60 引入微球表面 .初步的光电导性能测试表明 ,带有C60 的微球具有较好的光电导性能     

Study of bulk morphology of polymer latex films using laser confocal fluorescence microscopy

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Effects of shell composition,dosage and alkali type on the morphology of polymer hollow microspheres

Polymer hollow microspheres were prepared by performing alkali treatment on the multilayer core/shell polymer latex particles containing carboxyl groups. Effects of the shell composition and dosage as well as alkali type on the morphology of the microspheres were investigated. Results showed that in comparison with acrylonitrile(AN) and methacrylic acid(MAA), using butyl acrylate(BA) as the shell co-monomer decreased the glass transition temperature(T_g) of shell effectively and was beneficial to the formation of uniform and big hollow structure. Along with the increase of the shell dosage, the alkali-treated microspheres sequentially presented porous and hollow morphology, and the size of microspheres increased, while the hollow diameter increased first and then decreased, and the maximum hollow ratio reached 39.5%. Furthermore, the multilayer core/shell microspheres had better tolerance to NH_3·H_2O than to NaOH. When the molar ratio of alkali to methacrylic acid(MR_(alkali/acid)) for Na OH ranged from 1.15 to 1.30 or MRalkali/acid for NH_3·H_2O ranged from 1.30 to 2.00, the regular polymer hollow microspheres could be obtained.     

Designs of latex particles' morphologies for toughening polymer matrices

The performance of the designed structured core/shell latex particles in toughening polycarbonate (PC) matrix was examined. The influence of parameters related to the core/shell latex particles on toughening PC such as: the particle size and levels of crosslinking of the core rubber particles, composition and molecular-weight of the shell polymer, the weight ratio of shell and core polymers as well as the particle morphology was evaluated. Core/shell structured latex particles with thinner shells of higher molecular-weight polymers were found to improve the impact resistance of PC. The role of chain entanglements in increased adhesion between the discrete rubbery phase and the continuous glass matrix are discussed.     

超支化聚负离子/超支化聚正离子自组装膜的制备及反应

自1991年以来,静电吸附自组装已发展成为制备具有特定纳米微结构聚电介质多层超薄膜的有效技术。近年来,由于树枝状聚合物和超支化聚合物独特的物理化学性质,文献中已将它们与线性聚电解质一起用于静电吸附自组装过程,但完全基于超支化聚合物分子间的自组装过程还鲜见报道,超支化聚合物所具有的大量末端和内部（如叔胺基）官能团,不仅可以用于调节自组装行为及组装膜的表面形貌,