Synthesis of polar block grafted syndiotactic polystyrenes via a combination of iridium‐catalyzed activation of aromatic C?H bonds and atom transfer radical polymerization

A combination of iridium‐catalyzed C H activation/borylation and atom transfer radical polymerization (ATRP) was used to generate polar graft copolymers of syndiotactic polystyrene (sPS). The borylation at aromatic C H bonds of sPS and subsequent oxidation of boronate ester proceeded without negatively affecting the molecular weight properties and the tacticity of sPS. A macroinitiator suitable for ATRP could be synthesized by the esterification of 2‐bromo‐2‐methylpropionyl bromide and hydroxy‐functionalized sPS. The graft polymerizations of methyl methacrylate and tert‐butyl acrylate from the macroinitiator using ATRP afforded polar block grafted sPS materials, syndiotactic polystyrene‐graft‐poly(methyl methacrylate) (sPS‐g‐PMMA) and syndiotactic polystyrene‐graft‐poly(tert‐butyl acrylate) (sPS‐g‐PtBA). The latter was hydrolyzed to yield an amphiphilic graft copolymer, syndiotactic polystyrene‐graft‐poly(acrylic acid) (sPS‐g‐PAA). The structures of the copolymers were characterized by NMR and FTIR spectroscopies. Size exclusion chromatography and ¹H NMR spectroscopy were used to study any changes in the molecular weight properties from the parent polymer. A decrease in the hydrophobicity of the graft copolymers was confirmed by water contact angle measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6655–6667, 2009     

Synthesis and characterization of syndiotactic polystyrene-graft-poly(glycidyl methacrylate) copolymer by atom transfer radical polymerization

Syndiotactic polystyrene-graft-poly(glycidyl methacrylate) (sPS-graft-PGMA) copolymer was synthesized by a heterogenous atom transfer radical polymerization (ATRP) using 2-bromo-2-methylpropanoyl bromide modified syndiotactic polystyrene (BMPsPS) as macroinitiator and copper bromide combined with 2,2′-bipyridine as catalyst in anisole at room temperature. The macroinitiator with 7.0 mol% bromine content was prepared from Friedel-Crafts acylation reaction of sPS with 2-bromo-2-methylpropanoyl bromide in a heterogeneous process. It was found that BMsPS macroinitiator was well swelled in the mixture of anisole and GMA, the equilibrium swelling degree could reach 370%. The resultant polymer was characterized by FTIR and NMR spectroscopies. In addition, the thermal properties of the graft copolymers were also investigated with differential scanning calorimetry (DSC).     

Grafting of poly(styrene‐co‐p‐chloromethyl styrene) with ethyl methacrylate via atom transfer radical polymerization catalyzed by CuCl/1,2‐dipiperidinoethane

Poly(styrene‐graft‐ethyl methacrylate) graft copolymer was prepared by atom transfer radical polymerization (ATRP) with poly(styrene‐co‐p‐chloromethyl styrene)s in various compositions as macroinitiator in the presence of CuCl/1,2‐dipiperidinoethane at 130 °C in N,N‐dimethylformamide. Both macroinitiators and graft copolymers were characterized by elemental analysis, IR, ¹H and ¹³C NMR, and differential scanning calorimetry. 1,2‐Dipiperidinoethane was an effective ligand of CuCl for ATRP in the graft copolymerization. The controlled growth of the side chain provided the graft copolymers with polydispersities of 1.60–2.05 in the case of poly(styrene‐co‐p‐chloromethyl styrene) (62:38) macroinitiator. Thermal stabilities of poly(styrene‐graft‐ethyl methacrylate) graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 668–673, 2003     

Cellulose-g-PDMAam copolymers by controlled radical polymerization in homogeneous medium and their aqueous solution properties

Water-soluble cellulose-graft-PDMAam copolymers were prepared by single-electron-transfer living radical polymerization (SET-LRP). Cellulose based macroinitiator for SET-LRP with a degree of substitution DS ≈ 2 was synthesized from softwood dissolving pulp in a homogeneous LiCl/DMAc solution. The macroinitiator was then grafted using N,N-dimethyl acrylamide (DMAam) in DMSO. Formation of cellulose-g-DMAam copolymers were confirmed by ATR–FTIR, ¹H and ¹³C NMR spectroscopy and SEC analyses. Light scattering and steady–shear viscosity measurements revealed that the studied chain length of grafts (DP_graft) had only minor effects on the solution properties of cellulose-g-PDMAam copolymers. SLS studies suggested a loose, solvent-draining architecture of the cellulose-g-PDMAam copolymer particles in H₂O.     

Synthesis of graft copolymers onto styrenic polymer backbone via “grafting from” raft process

A new synthetic methodology is developed for preparing graft copolymers via RAFT polymerization method by the “R group approach” onto styrenic polymers. In this approach, latent sites of the styrenic polymer was brominated first and then converted into macro‐RAFT agents with pyrazole and thio dodecyl as the Z groups. This was used to synthesize graft copolymer such as polystyrene‐graft‐polymethyl methacrylate (PS‐g‐PMMA), polystyrene‐graft‐poly(isobornyl acrylate), polystyrene‐graft‐poly[2‐(acetoacetoxy)ethyl methacrylate] (PS‐g‐PAEMA), and poly(para‐methoxystyrene)‐graft‐polystyrene (P(p‐MS)‐g‐PS). The polymers are characterized by gel permeation chromatography, ¹H NMR, IR, and atomic force microscopy (AFM). The morphology of PS‐g‐PMMA in THF was investigated using AFM and island‐like features were noticed. The AFM studies of the PS‐g‐PAEMA graft copolymers revealed the formation of globules and ribbon‐like morphological features. The PS‐g‐PAEMA graft copolymers form complex with Fe(III) in dimethylformamide and the AFM studies suggest the formation of globular superstructures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of graft copolymers by combination of radical photopolymerization and iniferter process

Various PS‐based graft copolymers including polystyrene‐graft‐poly(methyl methacrylate) and poly(styrene‐graft‐poly(ethylene glycol) methacrylate) are prepared via subsequent visible light radical photopolymerization and iniferter processes. Thus, poly(styrene‐co‐4‐chloromethylstyrene) P(S‐co‐VBC) is synthesized by light induced free‐radical polymerization. Then, chloride moieties are substituted with triphenylmethyl (trityl) groups to give trityl‐substituted PS (PS‐trityl) under visible light irradiation using dimanganese decacarbonyl (Mn₂(CO)₁₀) photochemistry. Side chains are then grafted from PS‐trityl backbone via iniferter process to give desired graft copolymers in a controlled manner. The precursor intermediates and the final graft copolymers are analyzed by ¹H NMR, FT‐IR, and GPC measurements. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1344–1348     

Effect of catalyst systems and reaction conditions on the synthesis of cellulose‐g‐PDMAam copolymers by controlled radical polymerization

Various copper‐based catalyst systems and reaction conditions were studied in the graft copolymerization of N,N‐dimethylacrylamide (DMAam) with a cellulose‐based macroinitiator by controlled radical polymerization. The cellulose macroinitiator with degree of substitution DS = 0.44 was synthesized from dissolving softwood pulp in a LiCl/DMAc solution. The graft copolymerizations of DMAam, using the cellulose macroinitiator and various copper‐based catalyst systems, were then carried out in DMSO solutions. The copolymerization kinetics was followed by ¹H NMR. Water‐soluble cellulose‐g‐PDMAam copolymers were comprehensively characterized by ATR‐FTIR and ¹H NMR spectroscopies and SEC analyses. DLS and steady‐shear viscosity measurements revealed that when the DP_graft of the cellulose‐g‐PDMAam copolymer is high enough, the copolymer forms a more compact structure in water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(N-isopropylacrylamide)/poly[(N-acetylimino)ethylene] thermosensitive block and graft copolymers

Block and graft copolymers with poly(N-isopropylacrylamide) and poly[(N-acetylimino)ethylene] (PNAI) sequences were synthesized via PNAI derivatives (macroinitiators or macromers). The polymerization yields for block copolymers synthesized in ethanol, using the PNAI macroinitiator, were low (<10%), except where photochemical polymerization was applied. By contrast, for the copolymerizations of N-isopropylacrylamide with the PNAI macromers, performed in alcoholic solution, quite high polymerization yields, around 80-90%, were reached. ¹H-NMR and IR spectral and differential scanning calorimeter thermal data confirmed the copolymer formation. Thermosensitivity of the copolymers was investigated by means of turbidimetric technique as a function of their nature, average molecular weight and composition. It was found that the length of the chain of the PNAI macromer and the content in hydrophilic PNAI units of the resulted copolymer affected this behavior.     

Comb copolymers of polystyrene-poly(tert-butyl (meth)acrylate) prepared by combination of nitroxide mediated polymerization and photoinduced iniferter technique

Comb copolymers consisting of polystyrene backbone and poly(tert-butyl (meth)acrylate) side chains were synthesized by combination of nitroxide (TEMPO)-mediated polymerization (NMP) and photoinduced grafting from macro-iniferters. First, poly(chloromethylstyrene), PCMS, with the degree of polymerization and two random poly(styrene-co-chloromethylstyrene) copolymers, P(S-co-CMS), with similar but different content (8 and 14 mol%) of CMS units, were synthesized by NMP. In the second step the CMS units both in the homopolymer and the copolymers were converted to N,N-diethyldithiocarbamyl groups (DC) yielding photosensitive multifunctional macro-iniferters. Finally, tert-butyl methacrylate tBuMA was grafted from the synthesized polymer backbones by iniferter technique under UV-irradiation yielding copolymers polystyrene-graft-poly(tert-butyl methacrylate) PS-g-P(tBuMA). Grafting initiated by the macro-iniferters containing ∼6-11 DC initiating sites per macromolecule proceeded by pseudo-living polymerization mechanism, i.e., the number-average molecular weight increased with conversion and the SEC traces were unimodal. In contrast, photo-polymerization initiated by highly functionalized polystyrene backbone was poorly controlled. Hydrolysis of loosely grafted copolymers PS-g-P(tBuMA) afforded amphiphilic copolymers polystyrene-graft-poly(methacrylic acid). Molecular parameters of the synthesized graft copolymers in dilute THF solutions were determined by scattering (DLS, SLS, SAXS) and viscometric measurements.     

Synthesis of aromatic polyethersulfone‐based graft copolyacrylates via ATRP catalyzed by FeCl2/isophthalic acid

The atom transfer radical polymerization (ATRP) catalyzed by the FeCl₂/isophthalic acid system was used for the preparation of novel aromatic polyethersulfone (PSF)‐based graft copolymers in N,N‐dimethylformamide (DMF), such as aromatic PSF‐graft‐poly(methyl methacrylate), aromatic PSF‐graft‐polymethylacrylate, and aromatic PSF‐graft‐poly(butyl acrylate). The route consisted of two steps. The first step included the chloromethylation of aromatic PSF, and the second step involved the ATRP of acrylate monomers using chloromethylated aromatic PSF as the macroinitiator and FeCl₂/isophthalic acid as the catalyst in DMF. Characterization data by gel permeation chromatography, DSC, IR, ¹H NMR, and thermogravimetric analysis confirmed that the graft copolymerization was successful. Only one glass‐transition temperature (T_g) was observed for aromatic PSF‐graft‐poly(methyl methacrylate), and two T_g's were detected for aromatic PSF‐graft‐methyl acrylate and aromatic PSF‐graft‐poly(butyl acrylate). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2943–2950, 2001     

Preparation of starch-<Emphasis Type="Italic">g</Emphasis>-PMMA,starch-<Emphasis Type="Italic">g</Emphasis>-P(MMA/BMA) and starch-<Emphasis Type="Italic">g</Emphasis>-P(MMA/MA) nanoparticles and their reinforcing effect on natural rubber by latex blending: a comparative study

Nanoparticles including starch-graft-methylmethacrylate, starch-graft-(methylmethacrylate/methyl acrylate), starch-graft-(methyl methacrylate/butyl methacrylate) were synthesized via emulsifier-free emulsion polymerization and were blended with natural rubber latex at various mass ratios. Chemical structure of graft copolymers was confirmed by Fourier transform infrared. Transmission electron microscopy demonstrated the core-shell structures of the nanoparticles distributed uniformly around the natural rubble particles. The tensile strength of blend films was significantly enhanced by addition of graft copolymers. Besides, scanning electron microscopy and atomic force microscopy showed the blend film had smooth surface.     

Synthesis of poly(β‐pinene)‐g‐poly(meth)acrylate by the combination of living cationic polymerization and atom transfer radical polymerization

New graft copolymers of β‐pinene with methyl methacrylate (MMA) or butyl acrylate (BA) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). β‐Pinene polymers with predetermined molecular weights and narrow molecular weight distributions (MWDs) were prepared by living cationic polymerization with the 1‐phenylethyl chloride/TiCl₄/Ti(OiPr)₄/nBu₄NCl initiating system, and the resultant polymers were brominated quantitatively by N‐bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(β‐pinene) macroinitiators with different bromine contents (Br/β‐pinene unit molar ratio = 1.0 and 0.5 for macroinitiators a and b , respectively). The macroinitiators, in conjunction with CuBr and 2,2′‐bipyridine, were used to initiate ATRP of BA or MMA. With macroinitiator a or b , the bulk polymerization of BA induced a linear first‐order kinetic plot and gave graft copolymers with controlled molecular weights and MWDs; this indicated the living nature of these polymerizations. The bulk polymerization of MMA initiated with macroinitiator a was completed instantaneously and induced insoluble gel products. However, the controlled polymerization of MMA was achieved with macroinitiator b in toluene and resulted in the desired graft copolymers with controlled molecular weights and MWDs. The structures of the obtained graft copolymers of β‐pinene with (methyl)methacrylate were confirmed by ¹H NMR spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1237–1242, 2003     

Pyrolysis of polyphenylenes with PCL or/and PSt side chains

Thermal degradation characteristic of polyphenylenes is an important issue for developing a rational technology of polymer processing and applications. In this study, we discussed thermal degradation of polyphenylenes (PP) with poly(ɛ-caprolactone) (PCL) and/or PCL/polystyrene copolymers (PSt) prepared by combined controlled polymerization and cross-coupling processes via direct pyrolysis mass spectrometry. When PP-graft-PCL/PSt copolymers were considered, thermally less stabile PCL side chains decomposed in the first step. In the second stage of pyrolysis, the decomposition of the polystyrene chains has taken place. A slight increase in thermal stability of PCL chains for PP-graft-PCL/PSt copolymers was noted compared to copolymer PP-graft-PCL due to the interaction between PSt and PCL chains. This interaction was stronger when PSt chains were linked to the 2-position of the 1,4-phenylene ring.     

“Living” radical graft polymerization of styrene to styrene butadiene rubber (SBR) with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)

Well‐defined graft copolymers with styrene butadiene rubber (SBR) backbones and polystyrene branches were synthesized by living free radical polymerization (LFRP) techniques. Thus 1‐ benzoyl‐2‐phenyl‐2‐(2′,2′,6′,6′‐tetramethyl‐piperidinyl‐1′‐oxy)ethane (BZ‐TEMPO) was synthesized and hydrolyzed to the corresponding 1‐hydroxyl derivative. This functional nitroxyl compound was coupled with brominated SBR (SBR‐Br). The resulting macroinitiator (SBR‐TEMPO) for “living” free radical polymerization was then heated in the presence of styrene for the formation of the controlled graft copolymer. ¹H‐NMR and IR spectroscopy were used to investigate the structure of the polymers. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and properties of electroactive polyaniline-graft-poly(2-hydroxy ethyl metacrylate) copolymers

In this paper we report on the synthesis of a polyaniline-graft-poly(2-hydroxy ethyl metacrylate), which was obtained by atom-transfer radical polymerization of 2-hydroxy ethyl metacrylate using polyaniline as a macroinitiator. The latter was prepared by chemical oxidation (interfacial method) and further modification. Macroinitiator and graft copolymer were characterized by FTIR and ¹H NMR spectroscopy. The scanning electron microscopy and atomic force microscopy images showed the growing of poly(2-hydroxy ethyl metacrylate) chains on polyaniline backbone. The solubility test revealed that the polyaniline-graft-poly(2-hydroxyethyl metacrylate) copolymer is water soluble and some organic solvents soluble. The cyclic voltammetry study confirmed the electroactivity of the copolymer.     

A Grafting Study on Partially Dehydrochlorinated Poly(vinyl chloride) by Atom Transfer Radical Polymerization

HCl elimination in low ratio was first carried out from poly(vinyl chloride) to increase allylic chlorines. Partially dehydrochlorinated poly(vinyl chloride), having a macroinitiator effect, was grafted with tert‐butyl methacrylate via atom transfer radical polymerization in the presence of CuBr/2,2′‐bipyridine at 64°C in tetrahydrofuran. Original poly(vinyl chloride) was also grafted with tert‐butyl methacrylate under the same conditions to compare with that of partially dehydrochlorinated poly(vinyl chloride). The graft copolymers were characterized by elemental analysis, FTIR, ¹H and ¹³C‐NMR, differential scanning calorimetry, and gel permeation chromatography (GPC). Thermal stabilities of the graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators.     

“One pot” homogeneous synthesis of thermoplastic cellulose acetate-graft-poly(l-lactide) copolymers from unmodified cellulose

Using native cellulose as the starting material, cellulose acetate-graft-ploy (l-lactide) (CA-g-PLA) copolymers were successfully synthesized by “one-pot” process in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). In this process, cellulose was first reacted with acetic anhydride, yielding cellulose acetate (CA), and then ring opening graft copolymerization of l-lactide was carried out from the residual hydroxyl groups of CA in the same solution using 4-dimethylaminopridine (DMAP) as the catalyst. Both acetyl and ploy (l-lactide) contents in CA-g-PLA copolymers could be well controlled by changing reaction conditions. The structures and thermal properties of CA-g-PLA copolymers were characterized. The glass transition temperature T_g of copolymers decreased with increasing PLA content. Compared to the pure PLA and cellulose-graft-PLA copolymers, the CA-g-PLA copolymers possessed better thermo mechanical properties in a temperature range of 60–130 °C. When the molar substitution of PLA (MS_PLA) was above 1.71, the CA-g-PLA copolymers exhibited thermoplastic behavior and could be processed by conventional thermal processing methods, such as injection molding and melt spinning.     

Synthesis of functional polyethylene graft copolymers by nitroxide‐mediated living radical polymerization

This paper describes a new method to prepare graft copolymers, such as polyethylene‐g‐polystyrene (PE‐g‐PS), with a relatively well‐controlled reaction mechanism. The chemistry involves a transformation process from the metallocene copolymerization of ethylene and m,p‐methylstyrene (m,p‐MS) to nitroxide‐mediated “living” free radical polymerization (LRFP) of styrene. The metallocene catalysis produces ethylene‐co‐m,p‐methylstyrene (EMS) random copolymers. Next, 1‐hydroxyl‐2,2,6,6‐tetramethylpiperidine (HO‐TEMPO) was synthesized by the reduction of TEMPO with sodium ascorbate. The macroinitiator (EMS‐TEMPO) was synthesized with the bromination reaction of EMS, and the following nucleofilic reaction with this functional nitroxyl compound. The resulting macroinitiator (EMS‐TEMPO) for LRFP was then heated in the presence of styrene to form graft copolymer. DSC, ¹H‐NMR, FTIR spectroscopy were employed to investigate the structure of the polymers. The results of Molau test showed that PE‐g‐PS could be a potential good compatilizer. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Mechanical Properties of Polypropylene-based Polymer Hybrids via Controlled Radical Polymerization

Isotactic polypropylene-based graft copolymers linking poly(methyl methacrylate), poly(n-butyl acrylate) and polystyrene were successfully synthesized by a controlled radical polymerization with isotactic polypropylene (iPP) macroinitiator. The hydroxylated iPP, prepared by propylene/10-undecen-1-ol copolymerization with a metallocene/methyl-aluminoxane/triisobutylaluminum catalyst system, was treated with 2-bromoisobutyryl bromide to produce a Br-group containing iPP (PP-g-Br). The resulting PP-g-Br could initiate controlled radical polymerization of methyl methacrylate, n-butyl acrylate and styrene by using a copper catalyst system, leading to a variety of iPP-based graft copolymers with a different content of the corresponding polar segment. These graft copolymers demonstrated unique mechanical properties dependent upon the kind and content of the grafted polar segment.     

Synthesis and Characterization of Sulfonated Polyphosphazene-graft-Polystyrene Copolymersfor Proton Exchange Membranes简

A novel series of polyphosphazene-grafl-polystyrene （PP-g-PS） copolymers were successfully prepared by atom transfer radical polymerization （ATRP） of styrene monomers and brominated poly（bis（4-methylphenoxy）phosphazene） macroinitiator. The graft density and the graft length could be regulated by changing the bromination degree of the macroinitiator and the ATRP reaction time, respectively. The PP-g-PS copolymers readily underwent a regioselective sulfonation reaction, which occurred preferentially at the polystyrene sites, producing the sulfonated PP-g-PS copolymers with a range of ion exchange capacities. The resulting sulfonated PP-g-PS membranes prepared by solution casting showed high water uptake, low water swelling and considerable proton conductivity. They also exhibited good oxidative stability and high resistance to methanol crossover. Morphological studies of the membranes by transmission electron microscopy showed clear nanophase-separated structures resulted from hydrophobic polyphosphazene backbone and hydrophilic polystyrene sulfonic acid segments, indicating the formation of proton transferring tunnels. Therefore, these sulfonated copolymers may be candidate materials for proton exchange membranes in direct methanol fuel cell （DMFC） applications.