Layer-by-layer synthesis of multilayer core-shell latex and the film formation properties

Polymer latex particles were synthesized with multilayer core-shell structure via surface cross-linking emulsion polymerization. The latex core is coated with a five-layer shell. The polymerization was done in a semicontinuous fashion monitored by a dynamic laser scattering (DLS). The copolymer in each layer is designed with alternating high and low glass transition temperature (T(g)). Divinylbenzene (DVB) was added as the cross-linking agent in the synthesis of the "hard" layers to prevent the molecular diffusion from the adjacent "soft" layers. The layer-by-layer increment on the latex core is proved by the alternating changes on the film-formation capabilities of different latex emulsions at room temperature in correspondence with the variance in the T(g) of the outermost polymer layer. The detailed morphologies of the films formed by the latex with different number of layers were characterized by atom force microscopy (AFM). The deformation of the latex particles is largely depended on the nature of the polymer in the outermost layer of the latex particles. Further characterization carried out by multifrequency temperature-modulated differential scanning calorimetry (TOPEM-DSC) confirmed the layer-by-layer structure of the particles, although the molecular redistribution and the interlayer structures were observed. The work provides a routine toward the synthesis of multilayer polymer latexes.     

Synthesis of cationic core-shell latex particles

Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells were introduced by co-polymerizing styrene with the cationic monomers (vinylbenzyl)trimethylammonium chloride (VBTMAC), [(2-methacryloyloxy)ethyl] trimethylammonium chloride (METMAC) and [(2-(acryloyloxy)ethyl] trimethylammonium chloride (AETMAC) onto the polystyrene cores. The cationic monomer AETMAC, undocumented to our knowledge in colloid synthesis, produced the best cationic shells and could be incorporated at much higher concentrations in the shell compared to the commonly used VBTMAC and METMAC, which yielded undesired polyelectrolyte side products already at relatively low cationic monomer concentrations. In shell formation, feed concentrations of AETMAC between 1.3 mol% (2.4 wt%) and 10.7 mol% (20 wt%) in styrene could be employed, allowing us to control colloid surface charge density over a wide range. The influence of various polymerization parameters (initiator concentration, cross-linking agent, and ionic strength) on the co-polymerization process with AETMAC is discussed. Core-shell particles were characterized using HR-SEM, potentiometric titration and zeta potential measurements.     

Synthesis of a novel methacrylic monomer iniferter and its application in surface photografting on crosslinked polymer substrates

(Methacryloyl ethylenedioxycarbonyl) benzyl N,N‐diethyldithiocarbamate (HEMA‐E‐In) was synthesized and used as a monomer iniferter to develop a novel, photopatternable grafting technology. This molecule functions as both a methacrylic monomer and a photoiniferter (photoinitiator–transfer agent–terminator). The structure of HEMA‐E‐In was characterized by ¹H NMR, Fourier transform infrared, and ultraviolet–visible spectroscopies. In the presence of the monomer iniferter, methyl methacrylate was polymerized by exposure to 365‐nm ultraviolet radiation, confirming the initiation capability of HEMA‐E‐In. After the copolymerization of HEMA‐E‐In into a methacrylate‐based polymer, attenuated total reflectance Fourier transform infrared spectra revealed that the photoiniferter functionality was present at the surface of this polymeric substrate. Photografting of poly(ethylene glycol) monomethacrylate monomer from the surface caused a significant change in the hydrophobicity of the surface as demonstrated by contact angle measurements. The novel monomer photoiniferter HEMA‐E‐In initiates the polymerization of bulk monomer and provides a reactive functionality that facilitates further initiation and polymer modification by the polymerization of different monomers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1885–1891, 2002     

Synthesis and characterization of a novel,fluoride‐releasing dimethacrylate monomer and its dental composite

A novel, fluoride‐releasing dimethacrylate monomer containing zirconium fluoride chelate for use in dental composites was synthesized by an efficient four‐step procedure starting from 4,4‐bis‐(4‐hydroxyphenyl)‐pentanoic acid and was characterized by electrospray mass spectrometry, Fourier transform infrared (FTIR), and ¹H and ¹³C NMR spectroscopies. The synthesized monomer was photopolymerized with camphorquinone and 1‐phenyl‐1,2‐propane‐dione as initiators and N,N‐dimethylaminoethyl methacrylate as an accelerator. The photopolymerization process was investigated by FTIR spectroscopy. The experimental composite containing 13.7 wt % of the synthesized monomer was tested for fluoride release, fluoride recharge, compressive strength, and flexure strength, each in comparison to three commercial flowable dental composites. The results showed that the experimental composite had significantly higher fluoride release and fluoride recharge capabilities than the commercial flowable composites. The flexure strength was comparable to the commercial materials. The water sorption and solubility met the requirements of the International Organization for Standardization 4049 and the American National Standards Institute/American Dental Association Specification Number 27. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 985–998, 2004     

Synthesis of difluoroethyl perfluorosulfonate monomer and its application

The novel difluoroethyl perfluorosulfonate monomer 20 and its application have been developed. The difluoroethyl perfluorosulfonate monomer 20, which was prepared by the reaction of the vinyl sulfonic acid 19 with vinylidene fluoride, was copolymerized with tetrafluoroethylene (TFE) to give the difluoroethyl perfluorosulfonate copolymer 21. The copolymer 21 was easily converted to the perfluorosulfonic acid ionomer 2 in one step by heating and/or alcoholysis. This property of 21 enables the efficient preparation of the polymer solution of 2.     

Synthesis and characterization of a novel organophosphorus flame retardant and its application in polypropylene

A novel organophosphorus containing spiro and caged bicyclic phosphate, 3,9‐Bis‐(1‐oxo‐2,6,7‐trioxa‐1‐phospha‐bicyclo[2.2.2]oct‐4‐ylmethoxy)‐2,4,8,10‐tetraoxa‐3,9‐diphospha‐spiro[5.5]undecane 3, 9‐dioxide (SBCPO), was synthesized and characterized by Fourier transform infrared (FTIR), hydrogen‐1 nuclear magnetic resonance (NMR) and phosphorus‐31 NMR. The flame retardancy of polypropylene (PP) containing the novel intumescent flame retardant (IFR) based on the combination between SBCPO and melamine (MA) was studied by limiting oxygen index (LOI), UL‐94 test and cone calorimeter test. Results indicated that this combination showed the excellent flame retardancy for PP at appropriate proportions (with the total loading of 30 wt. % and SBCPO: MA = 4:1). The value of LOI was as high as 31.6, and the rating in UL94 reached to V‐0. Moreover, the HRR and THR of IFR/PP decreased significantly in comparison with that of neat PP. The scanning electron microscopy results indicated that the incorporation of SBCPO could induce the formation of intumescent char layer, which retarded the degradation and combustion process of PP. The thermal oxidative degradation of the PP samples at different temperature was analyzed by FTIR. The thermal stabilities of the composites were further investigated by thermogravimetric analysis. It was found that the amount of residues was increased greatly with the addition of SBCPO that remained in the form of polyaromatic stacks and phosphoric or polyphosphoric acid at the residual chars. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis, characterization and gold loading of polystyrene-poly(pyridyl methacrylate) core-shell latex systems

In this research, novel 3-(2-pyridyl)propyl methacrylate and 3-(3-pyridyloxy)propyl methacrylate monomers were synthesized and emulsion polymerized on colloidal polystyrene seeds, resulting in core-shell latex systems. The cores and the core-shell particles were characterized by static light scattering and scanning electron microscopy. Transmission electron microscopy was used to study the morphology of the core-shell particles. Monodisperse beads with a regular core-shell internal structure were found. The pyridine-functional shells were loaded with HAuCl₄ and irradiated with UV light to reduce the salts to metallic gold. FTIR, UV-Vis, TEM and XPS were employed to monitor the metal loading and reduction processes. Core-shell systems, decorated with gold nanoparticles, were obtained.     

Synthesis and polymerization of a novel perfluorinated monomer

Perfluoro(5-methylene-2,2-dimethyl-1,3-dioxolane) (1) was synthesized by utilizing a direct fluorination reaction. Compound 1 was an entirely novel monomer with difluoromethylene at position 5 on the dioxolane ring as an unprecedented polymerization site. It successfully polymerized with tetrafluoroethylene to afford copolymers, which had T_g values in the range of 60-90 °C. The content of monomer 1 in the obtained polymers was less than 20 mol%, which seemed insufficient for giving various unique properties to polymers. However, each polymer was expected to be a superior material because of their advanced thermal stability. Comparison with copolymers of 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole and tetrafluoroethylene is also discussed.     

Synthesis of polystyrene latex with amphoteric surfactant and its characterization

An emulsion polymerization of styrene in the presence of an amphoteric surfactant; N,N-dimethyl-n-laurylbetaine (LNB) was carried out at pH 7.0. The polymerization rate and the concentration of the latex particle were proportional to the LNB concentration of 0.6 power. The latex particle sizes became smaller with increasing concentrations of LNB. The molecular weights of polystyrene latices increased with the concentration of LNB. The zeta-potentials of latex particles were significantly dependent on the pH, and showed the existence of an isoelectric point.     

Synthesis of polyacrylate core-shell structure latex by radiation techniques

A series of poly(butyl acrylate-co-methyl methacrylate)/poly (ethyl acrylate-co-acrylic acid) interpenetrating polymer network (IPN) was synthesized in latex form by emulsion polymerization. The multiphase morphology of the latex particles was studied after two-stage polymerization by using transimission electron microscope (TEM), the result indicated that the morphology of the particles comprises gradient shell structure, cellular structure and core-shell structure. The change of morphology might stem from emulsion polymerization by radiation initiation or chemical initiation and the weight composition of poly(EA-co-MMA) seed latex which formed the core. By radiation techniques, we successfully synthesized poly( BA-co-MMA)/poly(EA-co-AA) latex of core-shell structure having (42-8)/(46-4) weight compositions. The PA core-shell structure latex applied to textile as a water proofing coating showed higher water-pressure and easier handling than that with PA homogeneous phase structure latex.     

Synthesis and characterization of novel polyamides from new aromatic phosphonate diamine monomer

New aliphatic-aromatic and fully aromatic phosphonate polyamides were prepared by polycondensation reaction of our synthesized aromatic diamine: tetraethyl[(2,5-diamino-3,6-dimethylbenzene-1,4-diyl)dimethanediyl]bis(phosphonate) with the specific di-acylchloride (adipoyl chloride, isophthaloyl chloride and terephthaloyl chloride). The chemical structure of all samples were characterized by (¹H and ³¹P) NMR, MALDI-TOF MS, FT-IR tools, whereas their thermal properties were determined by DSC and TGA techniques. The phosponate polyadipamide (referred as PAP) is a semi-crystalline sample with a melting temperature at about 261 °C and glass transition (T_g) of 71 °C. All polymers show two thermal degradation steps in the temperature range 270-550 °C. Each polymer, independently its structure, shows the first maximum rate of thermal decomposition temperature (PDT) around 300-310 °C, which may be due to thermal degradation of phoshonate groups. MALDI-TOF spectra, beside the linear oligomers terminated with the specific groups expected in accord to the synthesis procedure, reveals the presence of cyclic oligomers in the polyadipamide and polyisophthalamide samples.     

Synthesis of water-soluble hyperbranched polymer and its application in acrylic latex

A water-soluble hyperbranched polymer (WHBP), obtained from a second generation of hyperbranched polyester and maleic anhydride, was studied. Its effects on the properties of acrylic latexes, which were based on emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and WHBP, and latex film were discussed. The characteristics of WHBP were determined by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Particle size and morphology of latex particles were confirmed by dynamic light scattering (DLS) and transmission electron microscope (TEM). The investigation showed that WHBP could be used in emulsion polymerization, and that latex of poly(BA-MMA-WHBP) was more stable than that of poly(BA-MMA-AA). The hardness of latex film increased from 2B to HB when WHBP was used.     

Synthesis and characterization of a novel polyazomethine ether for NLO application

Polymer containing azomethine and ether linking groups between phenylene rings has been prepared. It is a polycondensation reaction of a single monomer containing nitro as well as hydroxyl group in p,p^′ position from 4-nitroaniline and 4-hydroxy benzaldehyde. The polymer has been characterized by elemental analysis, IR, UV and NMR spectroscopies, viscometry and thermal studies. The thermotropic liquid crystalline behaviour of the polymer is investigated by optical polarizing microscopy. The crystalline behaviour of the polymer is confirmed by XRD study. The polymer shows good second harmonic generation for non-linear optical application.     

新型核壳型亲水聚合物-硅胶杂化填料的合成及其在蛋白质N-糖链富集中的应用

蛋白质的N-糖基化修饰与多种重要的生理、病理进程密切相关,是多种重大疾病诊断标志物研究的热点。由于糖蛋白本身多是低丰度表达的蛋白质,且糖链结构具有高度微不均一性,这使得蛋白质糖基化修饰的分析具有一定的挑战。本研究利用表面引发-原子转移自由基聚合(SI-ATRP)法,以带有双键的氨基葡萄糖为单体(GMAG),成功制备了新型核壳型亲水聚合物-硅胶杂化填料(pGMAG-SiO₂)。由于在硅胶表面引入致密的亲水聚合物层,该填料不仅保持了硅胶良好的机械强度,而且显著提高了其亲水性,因此非常适合作为亲水填料用于蛋白质的N-糖链富集。以麦芽七糖和鸡卵清蛋白的N-糖链为研究对象,考察了该填料对N-糖链的富集效果,并将该杂化填料成功用于人血浆中糖蛋白N-糖链的富集检测,共鉴定了47种糖型。以上结果表明,pGMAG-SiO₂填料对N-糖链具有较高的亲和性,可以用于N-糖链的高覆盖率鉴定。     

Synthesis and characterization of novel soluble and thermally stable polyamides based on pyridine monomer

Nucleophilic aromatic substitution reaction of 4-aminophenol and also 5-amino-1-naphthol with 2,6-dichloropyridine in N-methyl-2-pyrrolidone (NMP) as solvent, in the presence of potassium carbonate, afforded two aromatic ether diamines. Eight soluble, thermally stable polyamides were prepared by polycondensation reaction of the obtained diamines with aromatic and aliphatic diacid chlorides including terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), adipoyl chloride (AC), and sebacoyl chloride (SC). The prepared monomers and polymers were characterized by conventional spectroscopic methods. Physical and thermal properties of the polymers, such as thermal behavior, thermal stability, solution viscosity, and solubility behavior were also studied.     

Synthesis and characterization of novel core-shell colloidal particles ZnO/poly(ethylcyanoacrylate)

Here we report the synthesis and physicochemical characterization of novel hybrid core/shell type ZnO/poly(ethylcyanoacrylate) colloidal particles. It is expected that coating ZnO colloidal particles with biocompatible and biodegradable poly(alkylcyanoacrylates) will pave the way toward the potential application of ZnO colloidal particles in biomedical research. Recent findings of cell selective toxicity indicate a potential utilization of ZnO colloidal particles in the treatment of cancer. For this purpose, ZnO colloidal particles have to be selectively delivered to the site of action by a suitable biocompatible and biodegradable carrier system. Toward this goal, poly(alkylcyanoacrylates) meet ideally the requirements for carrier systems in drug delivery due to their biocompatibility, biodegradability, low toxicity, and ability to overcome the multidrug resistance in cancer cells.     

Synthesis and characterization of a bifunctional amido-thiophene monomer and its copolymer with thiophene and electrochemical properties

A bifunctional amido-thiophene namely hexamethylene (bis-3-thiophene acetamide) (HMTA) was synthesized by the reaction of 3-thiophene acetic acid with hexamethylene diamine. Copolymerization in the presence of thiophene was achieved electrochemically in tetrabutylammonium tetrafluoroborate/acetonitrile (TBAFB/AN). Spectroelectrochemical analysis of the resulting copolymer [P(HMTA-co-Th)] reflected electronic transitions at 505 nm, 740 nm and ∼1000 nm, revealing π to π* transition, polaron and bipolaron band formation respectively. Switching ability was evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast. Dual type polymer electrochromic devices (ECDs) based on P(HMTA-co-Th) and poly(ethylene dioxythiophene) (PEDOT) have been constructed. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-vis spectroscopy and cyclic voltammetry. These devices exhibit low switching voltages (between 0.0 V and +1.6 V), short switching times with reasonable switching stability under atmospheric conditions.     

Synthesis and characterization of benzocyclobuten-4-yl acrylate monomer and its radical polymerization

<正>A benzocyclobuten-4-yl acrylate(1) monomer was prepared by esterification of 4-hydroxybenzocyclobutene with acryloyl chloride.The radical homopolymerization of 1 and copolymerization of 1 with styrene or n-butyl acrylate were carried out to produce linear polymers 2a,2b and 2c.Heating of these linear polymers under thermal initiation gave corresponding cross-linked polymers 3a,3b and 3c.The ring-opening reaction in the cross-linking process was confirmed by on-line infrared spectra.Differential scanning calorimetry showed that the glass transition temperatures of linear polymers 2a and 2b were 83.2℃and 68.1℃,respectively.Thermogravimetric analysis of the cross-linked polymers showed that they all exhibited good thermal stability.