Functionalized polystyrene latex particles as substrates for ATRP: Surface and colloidal characterization

In this work, the process for producing polystyrene particles surface functionalized with a thin shell of ATRP initiator polymerized alone or along with styrene and a crosslinker, is presented. Copolymerization of styrene and acrylic end-capped ATRP initiator to generate a thin shell on the fully polymerized core particles suffered from secondary nucleation owing to their possible incompatibility with the core particles and their own colloidal stability. One step functionalization processes, where the shell forming monomers are added directly to the 70% polymerized core particles, lead to significant changes in the resulting particle morphologies. The shot addition of these monomers led to a very uniform surface morphology without any secondary nucleation owing to quick coalescence of the secondary particles on the soft surface of the seed particles. Addition of crosslinker to the system helped in effectively eliminating the smaller particles generated due to secondary nucleation along with the chemical networking.     

End-capped polystyrene with 8-hydroxyquinoline group by ATRP method

8-Hydroxyqunioline end-capped polystyrene was prepared through atom transfer free radical polymerization (ATRP) with 8-(5-chloromethyl) quinolyl acetate as initiator. The results indicated that this polymerization is a first order reaction with respect to monomer conversion. The molecular weight increased linearly with monomer consumption and very narrow distribution of molecular weight was obtained (polydispersity index less than 1.2). The FT-IR and NMR results show that the 8-hydroxyquinloine group was chemically bonded to the polymer end and there is nearly one 8-hydroxyquinoline group in per polymer chain. All those data show that polymerization of styrene at such conditions displayed living characters. The polymer with 8-hydroxyqquinoline end group reacted with triethylaluminum to form polymeric light-emitting complex and single layer LED was prepared by common spin-coating method. The peak wavelength of LED based on synthesized polymeric complex was around 570 nm.     

DNA-functionalized thermoresponsive bioconjugates synthesized via ATRP and click chemistry

Diblock and miktoarm star-shaped thermoresponsive copolymers composed of single-stranded DNA (ssDNA) and poly(N-isopropylacrylamide) were successfully synthesized with combination of atom transfer radical polymerization (ATRP) and click chemistry. This approach should be generalizable to other DNA-functionalized copolymers. Such copolymers self-assemble into spherical micelles with ssDNA corona in aqueous solution above the lower critical solution temperature. The micellar size can be tuned from the macromolecular architecture. These DNA-encoded micellar particles are able to encapsulate and release hydrophobic guest molecules upon changing temperature.     

Viscoelastic characterization of moderately concentrated polystyrene solutions by dynamic light scattering

The dynamic light scattering measurements were performed for moderately concentrated entangled solutions of atactic polystyrene in benzene (BZ) at 25.0 °C, in cyclohexane (CH) at 34.5 °C (Θ), and in diethyl malonate (DEM) at 35.0 °C (Θ) to characterize their viscoelastic properties. The results have shown that while the mutual diffusion coefficient D increases in the BZ solutions and decreases in the CH and DEM solutions with increasing polymer mass concentration c, the friction coefficient ζ for the three solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for the CH and DEM solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but the L₀ values for these solutions are somewhat smaller than the values predicted from the relation. The terminal relaxation time τ_m for the two Θ solvent systems has been found to follow the power-law τ_m∝c^2.7, showing good correspondence to the relation established by rheological measurements.     

Preparation and characterization of polystyrene/graphite composite prepared by cationic grafting polymerization

A new graphite/polystyrene composite was produced with cationic grafting polymerization of styrene initiated by CO⁺ClO⁻₄ group on the surface of expanded graphite (EG). The structures of EG and the graphite/polystyrene composite were studied with SEM and optical micrograph. The spectra of XRD and IR were used not only for confirming whether the polymerization reaction took place, but also for determining whether the polystyrene in the composite covered the surface of EG particles or intercalated into EG particles. The electrical conductivity, thermal phase transitions and mechanical properties were also discussed.     

甲基丙烯酸甲酯的原子转移自由基沉淀聚合

以乙醇为溶剂,溴化亚铜(CuBr)为催化剂,溴乙酸乙酯为引发剂,1,10菲罗啉和N,N,N',N',N'-五甲基二乙烯基三胺(PMDETA)分别为配体的催化体系,进行了甲基丙烯酸甲酯的原子转移自由基沉淀聚合,通过GPC和称重量法对聚合物进行表征。结果表明,两种催化体系下MMA的转化速率较快,甲基丙烯酸甲酯的原子转移自由基沉淀聚合得到了较好的实现,得到了分子量分布较窄的聚合物。     

Preparation of functional poly(acrylates and methacrylates) and block copolymers formation based on polystyrene macroinitiator by ATRP

The polymerization by ATRP of hydroxy and amino functional acrylates and methacrylates with tert-butyldimethylsilyl (TBDMS) or tert-butyloxycarbonyl (BOC) protective groups has been studied for the first time achieving high control over molecular weight and polydispersity. Detailed investigation of the ATRP of 2-{[tert-butyl(dimethyl)silyl]oxy}ethyl acrylate (M2b) in bulk and 2-[(tert-butoxycarbonyl)amino]ethyl 2-methylacrylate (M3a) in diphenyl ether (DPE) showed that the type of ligand plays an important role on either the polymerization rate or the degree of control of the polymerization. Among the ligands used, N,N,N,′N″N″-pentamethyl diethylenetriamine (PMDETA) was the most suitable ligand for ATRP of all functional acrylates and methacrylates. The kinetics of M2b and M3a polymerization using PMDETA as a ligand was reported and proved the living character of the polymerization. Well-defined block copolymers based on a halogen terminated polystyrene (Pst) macroinitiator and the functional acrylate and methacrylate monomers were successfully synthesized by ATRP, and subsequent deprotection of the protective groups from the acrylate or methacrylate segment afforded amphiphilic block copolymers with a specific solubility behavior.     

原子转移自由基聚合制备生物材料的研究进展

原子转移自由基聚合(ATRP)在制备生物材料方面起着非常关键的作用,很多分散度低、结构规整、分子量可控的聚合物材料被制备并广泛应用于生物材料领域。基于ATRP技术,人们制备了各种各样的药物传输、基因传递、可降解聚合物、防污表面、医疗成像、抗菌表面、聚合物-蛋白杂合物等生物材料。     

ATRP法制备PVDF-g-PS共聚物及其表征

采用ATRP法制备了聚偏氟乙烯(PVDF)接枝苯乙烯共聚物(PVDF-g-PS),对产物的结构与性能进行了表征。结果表明:随着接枝率的提高,接枝共聚物的熔点和熔融焓下降,且PVDF在接枝后表面由光滑转变为凹凸不平的形貌。     

Grafting of poly(methyl methacrylate) or polyacrylonitrile onto polystyrene using ATRP technique

One of the most useful methods for synthesizing the graft and well‐defined copolymers is the atom transfer radical polymerization (ATRP) method. The polymerization was initiated by polystyrene (PS) carrying chloroacetyl groups as macroinitiator, in the presence of copper chloride (CuCl) and bipyridine (bpy). The macroinitiator (chloroacetylated PS) was prepared by successive chloroacetylation of PS under mild conditions and these reaction conditions overcome the problem of gelation and crosslinking in polymers. Successful graft copolymerizations were performed with methyl methacrylate (MMA) in toluene at 80°C and with acrylonitrile (AN) in tetrahydrofuran/ethylenecarbonate (62.5/37.5 v/v %) mixed solvent at 55°C. The characterization of the copolymers was investigated by ¹H‐NMR and FT‐IR spectroscopices. Gel permeation chromatography measurement indicated an increase of the molecular weight of the graft copolymers, as compared to that of the macroinitiator. This measurement also indicated the monomodal molecular weight distribution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2619–2627, 2006     

Fabrication of hybrid nanocomposites with polystyrene and multiwalled carbon nanotubes with well-defined polystyrene via multiple atom transfer radical polymerization

The PS-grafted multiwalled carbon nanotubes (MWNTs) were produced by the bromo-ended PS (PS-Br) and pristine MWNTs in 1,2-dichlorobenzene at 110 °C for 72 h via atom transfer radical polymerization (ATRP). Bromo-ended PS (PS-Br) used as an initiator for the functionalization of MWNTs was synthesized with styrene by ATRP conditions using CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine as catalyst. The PS-grafted MWNTs were fully characterized by ¹H-NMR, FT-IR, DSC, TGA, and SEM. The PS-grafted MWNTs were found to be highly soluble in a variety of organic solvents. The PS was chemically attached to the surfaces of MWNTs via ATRP approach, and the grafting amount of PS was 40–90%. From TGA and DSC measurements, the PS-grafted MWNTs were decomposed at lower temperature compared to that of PS-Br, and the functionalization of MWNTs increased the glass-transition temperature (T_g) of the grafted PS. The PS/PS-grafted MWNTs nanocomposites were prepared with PS and PS-grafted MWNTs by solution mixing in dimethylformamide (DMF). The resulting nanocomposites were found to be the homogeneous dispersion of PS-grafted MWNTs in PS matrix via aromatic (π–π) interactions between PS and PS-grafted MWNTs as determined by SEM and TEM.     

ATRP法合成低摩尔质量BPS的研究

采用ATRP法合成了一系列摩尔质量低（Mn=5×10^3～1×10^4g／mol）、分布窄（Mw／Mn=1．8～2．2）的聚苯乙烯（PS）,通过均相催化溴化法制得一系列摩尔质量低、分布窄、溴含量不同的溴化聚苯乙烯（BPS）,其中溴的质量分数最高可达75．59％,热分解温度达396℃。     

季铵化壳聚糖-聚苯乙烯共混膜的制备及表征

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,过硫酸钾为引发剂制备了聚苯乙烯微乳液,用共混法制备了3种不同质量比的季铵化壳聚糖和聚苯乙烯微乳液的共混膜.研究了该膜的温度和pH的敏感性及力学强度.结果表明,共混膜的拉伸强度与纯壳聚糖膜相比有较大提高,而且该膜仍然具有一定的温度敏感性和pH敏感性,有较好的应用价值.     

ATRP聚苯乙烯红外光谱研究

比较了ATRP方法制备的聚苯乙烯的红外光谱与传统自由基聚合方法所得的聚苯乙烯红外光谱。发现两类聚苯乙烯的红外光谱基本一致。但140cm^-1和1490cm^-1波数附近的2个吸收峰的相对强度存在较大的差异，这是由于ATRP方法所得的聚苯乙烯含有－CH2－Cl形式的化学键，在氯原子的影响下使得1440cm^-1波数附近的峰明显增强，这一现象也可以部分用于佐证ATRP反应生成了C－Cl键。     

原子转移自由基聚合的研究新进展——AGET ATRP

原子转移自由基聚合(ATRP)是目前高分子化学领域的研究重点之一,AGET ATRP又是在传统ATRP基础上衍生出的一种摒弃ATRP一些缺点的新型活性/可控聚合方法。重点介绍了AGET ATRP反应的机理、引发体系、催化体系、还原剂、反应介质及反应条件,以及对AGET ATRP技术的前景与展望。     

Synthesis,characterization, and property of end-functionalized telechelic PST via ATRP

Polystyrene incorporating carboxylate group as α-end was synthesized by using initiator 4-chloromethyl benzoic acid via atom transfer radical polymerization. Its ω-chlorine end-group was transformed by cumic acid, diethyl malonate, and thiol, respectively, to form end-functionalized telechelic polystyrenes. These PSts with different functionalized ω-end group (PSt 1 , PSt 2 , and PSt 3) were obtained and characterized by H NMR and TGA. This type of end-functionalized telechelic polymers can further act as polymeric ligands to form polymeric metal complexes. In this study, PSt 1 with carboxylate group at each end was allowed to react with Eu(DBM)₂Cl·2H₂O to afford a new polymeric complex PSt 1 -Eu(III) showing significant red-light emission. Moreover, the film of PSt 1 -Eu shows similar emission pattern with its DMF solution. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

还原剂对AGET ATRP乳液体系制备含氟涂料性能的影响

利用电子活化再生原子转移自由基聚合(AGETATRP)法,在Tween-80乳化体系下合成了甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-丙烯酸六氟丁酯(HFBA)的三元共聚物。由于AGETATRP反应体系中加入了还原剂来还原Cu2+,所以研究了还原剂的用量对聚合反应可控性的影响以及对共聚物涂料性能的影响。研究发现增加还原剂用量,涂料的防水性、防油性、力学性能略有降低,但仍然表现出优异的防水性和良好的力学性能。     

Polydopamine-melanin initiators for Surface-initiated ATRP

Thin films of polydopamine, a melanin-like material formed by the oxidative polymerization of dopamine in aqueous solution, have attracted much recent interest as functional coatings. Here we demonstrate the use of modified polydopamine as an initiator layer for surface-initiated polymerization, synthesized by reacting dopamine with 2-bromoisobutyryl bromide (BIBB) before deposition. Modified polydopamine films grew at a comparable rate to unmodified polydopamine, with a 45 nm being grown in 24 h. The presence of initiator groups was confirmed by XPS and FTIR and by the growth of PMMA and PHEMA polymer brushes. ARGET, the recently-developed oxygen-tolerant variant of ATRP, was used for surface polymerization with sodium ascorbate as the reducing agent. Polymerization was rapid, with PMMA brushes of nearly 240 nm thickness being grown in 24 h. A range of substrates could be coated in this way, including metals and hydrophobic polystyrene, demonstrating the broad applicability of this initiator.     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013