The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ev...

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

Effect of reaction solvent on the preparation of thermo-responsive stationary phase through a surface initiated atom transfer radical polymerization.

Polyacrylate latexes present good film-forming property, and therefore are used in a wide range of applications including coatings, adhesives, additives for paper, textiles, wood, and leather. However, some drawbacks, such as poor elasticity and low hardness have restricted their applications. This review summarizes recent development of polyacrylate latexes modified by polyurethane, organic fluorine, and inorganic nanoparticles, separately, which most often exhibit superior properties to those of their individual components. For each modification method, a comment is given based on our knowledge and related research experience. At last, some perspectives on the future research and development of modification of polyacrylate latexes are concluded.

Recent advances in the modification of polyacrylate latexes

Dispersity control in atom transfer radical polymerizations through addition of phenylhydrazine

Preparation and characterization of nano-SiO2/fluorinated polyacrylate composite latex via nano-SiO2/acrylate dispersion

Copper-based reverse ATRP process of styrene in mixed solvents

A series of copper-based reverse atom transfer radical polymerizations (ATRP) were carried out for methyl methacrylate (MMA) at same conditions (in xylene, at 80°C) using N,N,N′,N′-teramethylethylendiamine (TMEDA), N,N,N′,N′,N′-pentamethyldiethylentriamine (PMDETA), 2-2′-bipyridine, and 4,4′-Di(5-nonyl)-2,2′-bipyridine as ligand, respectively. 2,2′-azobis(isobutyronitrile) (AIBN) was used as initiator. In CuBr2/bpy system, the polymerization is uncontrolled, because of the poor solubility of CuBr2/bpy complex in organic phase. But in other three systems, the polymerizations represent controlled. Especially in CuBr2/dNbpy system, the number-average molecular weight increases linearly with monomer conversion from 4280 up to 14,700. During the whole polymerization, the polydispersities are quite low (in the range 1.07–1.10). The different results obtained from the four systems are due to the differences of ligands. From the point of molecular structure of ligands, it is very important to analyze deeply the two relations between (1) ligand and complex and (2) complex and polymerization. The different results obtained were discussed based on the steric effect and valence bond theory. The results can help us deep to understand the mechanism of ATRP. The presence of the bromine atoms as end groups of the poly(methyl methacrylate) (PMMA) obtained was determined by 1H-NMR spectroscopy. PMMA obtained could be used as macroinitiator to process chain-extension reaction or block copolymerization reaction via a conventional ATRP process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Copper‐based reverse ATRP process for the controlled radical polymerization of methyl methacrylate

The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO3/SiO2 two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO3 was encapsulated by the obtained SiO2. After being modified by silane coupling agent, the CaCO3/SiO2 composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO3/SiO2 three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO3/SiO2 two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO3/SiO2 composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.

Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

The invention discloses a method for preparing a high polymer ultraviolet absorbent, which is characterized by the following: preparing the dilute solution by dissolving narrow distribution (D<1.2)high polymer by (reverse direction)atom transferring free radical polymerization(ATRP)with the good solvent; proceeding with reflux reaction with 2, 4-dihydroxy benzophenone (UV-0)low molecule ultraviolet absorbent with equimolar ratio in the accelerant function for 30-70 hours; preparing narrow distribution high polymer ultraviolet absorbent. Nuclear magnetism result show that the method make the grafting ratio of UV-0 low molecule ultraviolet absorbent which is grafted by PMMA reach 25.4%; the molecular weight of PMMA film without high polymer ultraviolet absorbent reduces 32.7% after the same molecular weight PMMA and PMMA which is grafted by UV-0 low molecule ultraviolet absorbent are aged 740 hours quickly by the ultraviolet light, the distribution of the molecular weight changes from 1.17 to 1.42; the molecular weight of PMMA film with 27% high polymer ultraviolet absorbent reduces 6.7%, the distribution of the molecular weight changes from 1.17 to 1.23, so the test result shows that high polymer ultraviolet absorbent prepared with the method can improve the ultra-violet resistance property of the high polymer material.

Preparation method of macromolecule ultraviolet radiation absorbent

Atom transfer radical polymerization (ATRP) is a promising method to synthesize well-defined polymer/inorganic nanoparticles. However, the surface-initiated ATRP from commercially mass produced inorganic nanoparticles has seldom been studied. In this study, the surface-initiated ATRP of methylmethacrylate (MMA) from commercially mass produced fumed silica (SiO2) nanoparticles was investigated. Unlike the ATRP of MMA initiated from a free initiator, the controllability of ATRP of MMA from the surface of fumed silica nanoparticles was much better using ligand 2,2'-bipyridine (bpy) than N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the initiator was immobilized on the surface of the SiO2 nanoparticles and the presence of the SiO2 nanoparticles made the CuCl/bpy catalyst system a homogeneous catalyst system and CuCl/PMDETA a heterogeneous one. The appropriate molar ratio of monomer and initiator was essential for preparing controlled PMMA/SiO2 nanoparticles. The entire process of ATRP of MMA from the surface of SiO2 nanoparticles was controllable when using bpy as ligand, xylene as solvent and with a monomer to initiator ratio of 300:1. The 1H NMR results indicated that the PMMA on the surface of the SiO2 was prepared via ATRP initiated from 4-(chloromethyl)phenyltrimethoxysilane. The well-defined PMMA/SiO2 nanoparticles obtained have good thermal stability and are well dispersed in organic media as proved by TGA, dynamic light scattering and transmission electron microscopy. © 2013 Society of Chemical Industry

Kai Pan

Papers

Copper-based reverse ATRP process of styrene in mixed solvents

Copper‐based reverse ATRP process for the controlled radical polymerization of methyl methacrylate

Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

Preparation method of macromolecule ultraviolet radiation absorbent

Controlled polymerization of methylmethacrylate from fumed SiO2 nanoparticles through atom transfer radical polymerization