Polypropylene surface peroxidation with heterofunctional polyperoxides

Method of polyolefin surface activation via covalent grafting of polyperoxide nanolayer by free radical mechanism has been presented. The features of such the nanolayer formation under the thermoprocessing conditions, i.e.: formation of 3D crosslinked network in polyperoxide bulk; and its grafting with complete coating of polyolefin surface, -- is considered. The method provides an availability of uniformly placed peroxide groups of one type over the polyolefin surface activated, which may further be utilized for the tailored modification of polymer surfaces using the “grafting to” and “grafting from” techniques in that time when it is necessary.     

Strategy for Good Dispersion of Well‐Defined Tetrapods in Semiconducting Polymer Matrices

The morphology or dispersion control in inorganic/organic hybrid systems is studied, which consist of monodisperse CdSe tetrapods (TPs) with grafted semiconducting block copolymers with excess polymers of the same type. Tetrapod arm‐length and amount of polymer loading are varied in order to find the ideal morphology for hybrid solar cells. Additionally, polymers without anchor groups are mixed with the TPs to study the effect of such anchor groups on the hybrid morphology. A numerical model is developed and Monte Carlo simulations to study the basis of compatibility or dispersibility of TPs in polymer matrices are performed. The simulations show that bare TPs tend to form clusters in the matrix of excess polymers. The clustering is significantly reduced after grafting polymer chains to the TPs, which is confirmed experimentally. Transmission electron microscopy reveals that the block copolymer‐TP mixtures (“hybrids”) show much better film qualities and TP distributions within the films when compared with the homopolymer‐TP mixtures (“blends”), representing massive aggregations and cracks in the films. This grafting‐to approach for the modification of TPs significantly improves the dispersion of the TPs in matrices of “excess” polymers up to the arm length of 100 nm.     

Combining Spontaneous Polymerization and Click Reactions for the Synthesis of Polymer Brushes: A “Grafting Onto” Approach

Two novel benzofulvene monomers bearing propargyl or allyl groups have been synthesized by means of readily accessible reactions, and were found to polymerize spontaneously by solvent removal, in the apparent absence of catalysts or initiators, to give the corresponding polybenzofulvene derivatives bearing clickable propargyl or allyl moieties. The clickable propargyl and allyl groups were exploited in appropriate click reactions to develop a powerful and versatile “grafting onto” synthetic methodology for obtaining tailored polymer brushes.     

Nanosegregated polymeric domains on the surface of Fe3O4@SiO2 particles

Multifunctional, biocompatible, and brush‐grafted poly(ethylene glycol)/poly(ε‐caprolactone) (PEG/PCL) nanoparticles have been synthesized, characterized, and used as vehicles for transporting hydrophobic substances in water. For anchoring the polymer mixed brushes, we used magnetic‐silica particles of 40 nm diameter produced by the reverse microemulsion method. The surface of the silica particle was functionalized with biocompatible polymer brushes, which were synthesized by the combination of “grafting to” and “grafting from” techniques. PEG was immobilized on the particles surface, by “grafting to,” whereas PCL was growth by ROP using the “grafting from” approach. By varying the synthetic conditions, it was possible to control the amount of PCL anchored on the surface of the nanoparticles and consequently the PEG/PCL ratio, which is a vital parameter connected with the arrangement of the polymer brushes as well as the hydrophobic/hydrophilic balance of the particles. Thus, adjusting the PEG/PCL ratio, it was possible to obtain a system formed by PEG and PCL chains grafted on the particle's surface that collapsed in segregated domains depending on the solvent used. For instance, the nanoparticles are colloidally stable in water due to the PEG domains and at the same time are able to transport, entrapped within the PCL portion, highly water‐insoluble drugs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2966–2975     

Topological Polymer Chemistry Enters Surface Science: Linear versus Cyclic Polymer Brushes

The cyclic polymer topology strongly alters the interfacial, physico‐chemical properties of polymer brushes, when compared to the linear counterparts. In this study, we especially concentrated on poly‐2‐ethyl‐2‐oxazoline (PEOXA) cyclic and linear grafts assembled on titanium oxide surfaces by the “grafting‐to” technique. The smaller hydrodynamic radius of ring PEOXAs favors the formation of denser brushes with respect to linear analogs. Denser and more compact cyclic brushes generate a steric barrier that surpasses the typical entropic shield by a linear brush. This phenomenon, translates into an improved resistance towards biological contamination from different protein mixtures. Moreover, the enhancement of steric stabilization coupled to the intrinsic absence of chain ends by cyclic brushes, produce surfaces displaying a super‐lubricating character when they are sheared against each other. All these topological effects pave the way for the application of cyclic brushes for surface functionalization, enabling the modulation of physico‐chemical properties that could be just marginally tuned by applying linear grafts.     

梯度引发自由基聚合体系(Ⅰ)——基原法合成超高分子量聚合物

90年代在自由基聚合基础研究领域的一个重要成是“长 短终止”理论被进一步确认和接受[1 ,2 ] .按照该模型 ,聚合反应中的终止反应主要发生在长链自由基与短链自由基或初级自由基之间 ,即长链自由基之间很难进行终止反应 ,链终止常数随链长增加而急剧下降 .80年代初 ,Ｓｉｍｉｏｎｅｓｃｕ等[3] 曾报道了用等离子体照射封有单体的玻璃管 ,尔后放入暗处聚合的工作 ,发现不仅可得到分子量上千万的聚丙烯酸或聚丙烯酰胺 ,而且聚合活性可保持几十个小时 ;国内学者[4] 利用该法也得到了分子量接近千万的聚丙烯酰胺 .基于这种终止模型和实验结果 ,…     

“Grafting through” polymerization involving surface-bound monomers

“Grafting through” polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surface-bound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out “grafting through” free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the “grafting through” process but prevents more free growing chains to “graft through'' the polymerizable units. The “grafting through” process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 263–274     

A “Polymer Template” Strategy for Carbonized Polymer Dots with Controllable Properties

Limited avenues are available for property control of carbonized polymer dots (PDs) owing to the unsatisfactory understanding of PDs“ formation. Herein, a de novo ”polymer template“ strategy is presented for PDs with customizable functional surface groups (FSG), size, and underlying fluorescence, with a detailed mechanism. The strategy relies on novel di-active site polymers (DASPs) prepared from alkenyl azides via [3+2] cycloaddition and guanidino hydrolysis. Benefiting from these specific reactions, the DASPs were convenient for mass production and stable for storage, and could be transformed to PDs upon addition of nucleophilic agents through nucleophilic addition and substitution at 70 °C. By regulating the types of alkenyl azides, nucleophilic agents, and reaction conditions, the as-prepare PDs could be tailored with controlled types of core, FSG, and particle size, as well as fluorescence properties of quantum yield from 8.2–55.6 %, and emission maximum from 380–500 nm. These specialties make this ”polymer template“ strategy a promising start for building PDs-based sensor platforms. Moreover, the strategy could further our understanding towards PDs’ formation, and open up a new way to customize PDs for specific needs in the fields of analysis, catalysis, images, etc.     

两亲性树状聚合物*

树状聚合物及其功能化是近年来高分子科学界的研究热点之一。本文综述了不同类型的树状聚合物,分别有聚酯、聚丙三醇、聚乙烯亚胺等超支化聚合物,聚酰胺-胺、聚丙烯亚胺等树枝状聚合物。通过对树状聚合物末端大量官能团的亲水（亲油）改性可以制备两亲性树状聚合物,改性方法主要有酰胺化反应、酯化反应、麦克尔加成反应等。与通过缩聚反应所得到的上述树状聚合物不同,近年来配位聚合领域出现的通过“链行走”机理形成的树状聚乙烯,引起了高度关注,这方面着重介绍了乙烯与极性单体直接共聚合或者采用链行走与原子转移自由基聚合联用制备两亲性树状乙烯聚合物。最后对两亲性树状聚合物领域的发展前景进行了展望。     

Formation of Hollow Polymeric Microspheres with Functionalized Surface on the Basis of Latex Particles with Multilayered Structure

Summary: Latices with “core-shell” particle morphology containing polar “core” and a shell on the basis of copolymer of styrene and functional vinyl monomer (allyl alcohol, vinyl acetate, methacrylic acid) has been obtained as a result of graft-copolymerization initiated from the surface of (meth)acrylate latex particles previously modified with functional polyperoxides. The processes of functional shell grafting as well as the processes of latex particle swelling with obtaining hollow microspheres due to neutralization of core carboxylic groups have been studied.     

Transport Polymerization of Gaseous Intermediates and Polymer Crystals Growth

Man is always enchanted with discoveries of new and better ways of making things. Even after more than a hundred years of synthetic chemistry, scientists are today still as enthusiastic as ever looking for “novel” reactions and “novel” syntheses. One of the great achievements of the last decade was the development and usage of “intermediates” for syntheses. Knowing the extensive applications [1-4] of these intermediates in modern synthetic chemistry, it is, however, surprising to find that only few groups of these intermediates have been used in polymer syntheses. For instance [5], even though there are radical polymerizations and polymerizations involving carbanions and carbonium ions, there are practically no polymer syntheses using benzynes [2], carbenes [3], or nitrenes [4].     

Polymerization of Vinyl Monomers on Mineral Surfaces; A Novel Method of Preparing Reinforcing Fillers

A novel method for producing modified mineral fillers is reported: The mineral surface is first made “acidic” and this acidic surface is used to initiate the cationic polymerization of vinyl or preferably divinyl monomers, the residual acidic sites being subsequently neutralized with ammonia or an organic base. During compounding, grafting occurs between the encapsulating polymer layer and the matrix polymer via previously formed peroxidic groups in this layer or via radical attachment at unsaturated centers in the polymer coating. The incorporation of these modified fillers in various grades of polyethylene results in significant improvements in processability and in tensile and impact strength relative to the properties of equivalent composites using untreated or merely hydrophobic fillers.     

From Random Coil to Extended Nanocylinder: Dendrimer Fragments Shape Polymer Chains

Wedgelike dendrimer fragments , “dendrons”, attached to linear polymers as side groups, can be used to create anisotropic “nanocylinders”, leading to uncoiling and extension of the polymer chains. Synthetic macromolecules of this type can be visualized directly on surfaces and their contour length determined from scanning force micrographs. Unexpected acceleration effects in the polymerization of dendron monomers as well as the structural consequences of dendritic “pieces of cake” (shown schematically) on linear polymer chains are discussed.     

Hydrobromination of residual vinyl groups on divinylbenzene polymer particles followed by atom transfer radical surface graft polymerization

Rigid and monodisperse spherical polymer particles with 2.36 ± 0.18 μm diameter containing residual surface vinyl groups were prepared by photoinitiated precipitation polymerization of divinylbenzene. Anti‐Markovnikov addition of HBr to the surface vinyl groups yielded a 2‐bromoethyl functionality that was used as macroinitiator for atom transfer radical polymerization (ATRP), providing the possibility for further functionalization by controlled “grafting from” processes. This was demonstrated by grafting of glycidyl methacrylate brushes from the particle surface, using an ATRP system based on CuBr and pentamethyl diethylenetriamine. Existence of a methacrylic overlayer was verified by FTIR and XPS measurements, and the grafted particles were easily dispersed in water, confirming conversion of the particle surface from hydrophobic to hydrophilic. Hydrobromination of residual vinyl groups yields a macroinitiator that can be used for grafting of glycidyl methacrylate by ATRP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1259–1265, 2009     

Plasma brominated polymer particles as grafting substrate for thiol‐terminated telomers

A combined surface activation and “grafting to” strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom‐%, as determined by X‐ray photoelectron spectroscopy. Grafting of thiol‐terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur‐carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two‐step procedure involving hydrolysis to 2,3‐hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent.     

结构规整的高密度两亲性接枝聚合物刷的合成及其自组装研究

大分子单体通过两种可控聚合方法, 即开环易位聚合(ROMP)和原子转移自由基聚合(ATRP)的联用, 合成一种新型两亲性接枝聚合物刷. 具有高环张力的降冰片烯单侧链大分子单体norbornene-graft-poly(ε-caprolactone)/Br (PCL- NBE-Br)首先进行ROMP反应, 生成聚合物主链, 每个单体单元上含有一条PCL链和一个溴官能团; 然后用含溴的ROMP聚合物poly(norbornene)-graft-poly(ε-caprolactone)/Br (PCL-PNBE-Br)作为大分子引发剂引发单体2-(dimethyl- amino)ethyl methacrylate)的ATRP反应, 生成结构明确的高密度两亲性接枝聚合物刷poly(norbornene)-graft-poly(ε- caprolactone)/poly(2-(dimethylamino)ethyl methacrylate) (PCL-PNBE-PDMAEMA), 其主链每个单体单元上均含有一条疏水性PCL接枝链和一条亲水性PDMAEMA接枝链. 最后, 研究此类高密度两亲性接枝聚合物刷的自组装行为, 用动态激光光散射(DLS)研究其在混合溶剂(THF/H2O)中的胶束行为, 考察胶束溶液的浓度以及不同长度的亲水性接枝链对胶束尺寸的影响; 利用透射电镜(TEM)观察胶束为球形, 具有类似线团或草莓状的形态.     

“Surface-photografting”: new applications to synthetic fibers

“Surface-photografting” with UV-irradiation of polypropylene (PP) fiber and film and high-strength polyethylene (HSPE) yarn has been made with acrylic acid (AA) and acrylamide (AM) as monomers and benzophenone (BP), 4-chlorobenzophenone (4-BCP) and hydroxylcyclohexylacetophenone (HHA) as photoinitiators using a new continuous method. The grafting reaction occurs in a thin liquid layer on the fiber or film substrate, which is presoaked in a solution containing initiator and monomer. After irradiation with a highpressure mercury lamp, HPM 15 (2 kW) from Philips, for 5–20 sec at about 50°C the fiber and film surface is completely covered with a 2–8 nm thick layer of grafted polymer, analyzed by electron spectroscopy for chemical analysis. The grafting efficiency is 70–80%, i.e. only 20–30% of the polymer is homopolymer which can be removed by extraction. The grafted layers are so thin that they cannot be analyzed as weight increase (<0.1% of fiber weight). Absolute values for the amount of grafted AA polymer is analyzed by microtitration of the COOH groups at the fiber surface. The results agree well with the relative ESCA values. Grafting of commercial PP yarn with AA increases the adsorption of Crystal Violet dye with a factor of about 6. Grafting the same yarn with AM increases the adhesion to epoxy resin by a factor of 3–4 without affecting the mechanical properties of the fiber more than a few percent. For comparison, strips of blown PP film (5 mm wide) are modified by “surface-photografting” with AM. With increasing grafting, the contact angle for drops of distilled water decreases from 90° to 20°, indicating extensive wetting. The adhesion to epoxy resin increases from about 0.35 to 1.7 N/mm², i.e. with a factor of about 5 when the film surface is completely covered. Other comparisons are made with grafting of commercial HSPE yarn. Grafting with AA increases the adsorption of Crystal Violet dye by a factor of about 6. Grafting with AM increases the adhesion to epoxy resin from 0.25 to 1.3 N/nm², i.e. with a factor of 5. The bulk mechanical properties of the HSPE filaments are not affected by the grafting measured as tensile strength 2.7±0.1 GPa, elongation at break 4.8±0.3%, and Young's modulus 55±3 GPa, both before and after “surface-photografting”.     

Efficient synthesis of monodisperse,highly crosslinked,and “living” functional polymer microspheres by the ambient temperature iniferter‐induced “living” radical precipitation polymerization

The facile and efficient one‐pot synthesis of monodisperse, highly crosslinked, and “living” functional copolymer microspheres by the ambient temperature iniferter‐induced “living” radical precipitation polymerization (ILRPP) is described for the first time. The simple introduction of iniferter‐induced “living” radical polymerization (ILRP) mechanism into precipitation polymerization system, together with the use of ethanol solvent, allows the direct generation of such uniform functional copolymer microspheres. The polymerization parameters (including monomer loading, iniferter concentration, molar ratio of crosslinker to monovinyl comonomer, and polymerization time and scale) showed much influence on the morphologies of the resulting copolymer microspheres, thus permitting the convenient tailoring of the particle sizes by easily tuning the reaction conditions. In particular, monodisperse poly(4‐vinylpyridine‐co‐ethylene glycol dimethacrylate) microspheres were prepared by the ambient temperature ILRPP even at a high monomer loading of 18 vol %. The general applicability of the ambient temperature ILRPP was confirmed by the preparation of uniform copolymer microspheres with incorporated glycidyl methacrylate. Moreover, the “livingness” of the resulting polymer microspheres was verified by their direct grafting of hydrophilic polymer brushes via surface‐initiated ILRP. Furthermore, a “grafting from” particle growth mechanism was proposed for ILRPP, which is considerably different from the “grafting to” particle growth mechanism in the traditional precipitation polymerization. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Grafting of polymers onto and/or from silica surface during the polymerization of vinyl monomers in the presence of γ‐ray‐irradiated silica

The effects of radicals on silica surface, which were formed by γ‐ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of γ‐ray‐irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of γ‐ray‐irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of γ‐ray‐irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC‐MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical (“grafting from” mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals (“grafting onto” mechanism) proceeded to give relatively higher molecular weight polymer‐grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972–2979, 2006