Synthesis of miktoarm star and miktoarm star block copolymers via a combination of atom transfer radical polymerization and stable free‐radical polymerization

A trifunctional initiator, 2‐phenyl‐2‐[(2,2,6,6‐tetramethyl)‐1‐piperidinyloxy] ethyl 2,2‐bis[methyl(2‐bromopropionato)] propionate, was synthesized and used for the synthesis of miktoarm star AB₂ and miktoarm star block AB₂C₂ copolymers via a combination of stable free‐radical polymerization (SFRP) and atom transfer radical polymerization (ATRP) in a two‐step or three‐step reaction sequence, respectively. In the first step, a polystyrene (PSt) macroinitiator with dual ω‐bromo functionality was obtained by SFRP of styrene (St) in bulk at 125 °C. Next, this PSt precursor was used as a macroinitiator for ATRP of tert‐butyl acrylate (tBA) in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 80 °C, affording miktoarm star (PSt)(PtBA)₂ [where PtBA is poly(tert‐butyl acrylate)]. In the third step, the obtained St(tBA)₂ macroinitiator with two terminal bromine groups was further polymerized with methyl methacrylate by ATRP, and this resulted in (PSt)(PtBA)₂(PMMA)₂‐type miktoarm star block copolymer [where PMMA is poly(methyl methacrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.38). All polymers were characterized by gel permeation chromatography and ¹H NMR. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2542–2548, 2003     

Photoresponsive poly(methyl methacrylate)2–(polystyrene)2 miktoarm star copolymer containing an azobenzene moiety at the core

We prepared a novel miktoarm star copolymer with an azobenzene unit at the core via combination of atom transfer radical polymerization (ATRP) and nitroxide‐mediated free radical polymerization (NMP) routes. For this purpose, first, mikto‐functional initiator, 3 , with tertiary bromide (for ATRP) and 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO) (for NMP) functionalities and an azobenzene moiety at the core was synthesized. The initiator 3 thus obtained was used in the subsequent living radical polymerization routes such as ATRP of MMA and NMP of St, respectively, to give A₂B₂ type miktoarm star copolymer, (PMMA)₂‐(PSt)₂ with an azobenzene unit at the core with controlled molecular weight and low polydispersity (M_w/M_n < 1.15). The photoresponsive properties of 3 and (PMMA)₂‐(PSt)₂ miktoarm star copolymer were investigated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1396–1403, 2006     

Synthesis of diblock copolymers by combining stable free radical polymerization and atom transfer radical polymerization

A stable nitroxyl radical functionalized with an initiating group for atom transfer radical polymerization (ATRP), 4‐(2‐bromo‐2‐methylpropionyloxy)‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (Br‐TEMPO), was synthesized by the reaction of 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy with 2‐bromo‐2‐methylpropionyl bromide. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br‐TEMPO. The obtained polystyrene had an active bromine atom for ATRP at the ω‐end of the chain and was used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare block copolymers. The molecular weights of the resulting block copolymers at different monomer conversions shifted to higher molecular weights and increased with monomer conversion. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2468–2475, 2006     

星形聚氧乙烯及星形杂臂氧化乙烯-苯乙烯共聚物的合成

以原子转移自由基偶联法合成了多臂星形聚合物S-PEO和星形杂臂共聚物PEO-PS。以傅立叶红外光谱(FT-IR)和核磁共振(1H NMR)分析方法确定了产物的结构。以GPC分析测试了产物的分子量和分子量分布。GPC分析结果表明所得聚合物分子量增大,分子量分布窄,偶联反应效率可高达99%以上。     

Novel miktofunctional initiator for the preparation of an ABC‐type miktoarm star polymer via a combination of controlled polymerization techniques

An ABC‐type miktoarm star polymer was prepared with a core‐out method via a combination of ring‐opening polymerization (ROP), stable free‐radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, ROP of ϵ‐caprolactone was carried out with a miktofunctional initiator, 2‐(2‐bromo‐2‐methyl‐propionyloxymethyl)‐3‐hydroxy‐2‐methyl‐propionic acid 2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yl oxy)‐ethyl ester, at 110 °C. Second, previously obtained poly(ϵ‐caprolactone) (PCL) was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PCL–polystyrene (PSt) precursor with a bromine functionality in the core was used as a macroinitiator for ATRP of tert‐butyl acrylate in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 100 °C. This produced an ABC‐type miktoarm star polymer [PCL–PSt–poly(tert‐butyl acrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.37). The obtained polymers were characterized with gel permeation chromatography and ¹H NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4228–4236, 2004     

Facile synthesis of AB2‐type miktoarm star polymers through the combination of atom transfer radical polymerization and ring‐opening polymerization

A novel miktofunctional initiator ( 1 ), 2‐hydroxyethyl 3‐[(2‐bromopropanoyl)oxy]‐2‐{[(2‐bromopropanoyl)oxy]methyl}‐2‐methyl‐propanoate, possessing one initiating site for ring‐opening polymerization (ROP) and two initiating sites for atom transfer radical polymerization (ATRP), was synthesized in a three‐step reaction sequence. This initiator was first used in the ROP of ?‐caprolactone, and this led to a corresponding polymer with secondary bromide end groups. The obtained poly(?‐caprolactone) (PCL) was then used as a macroinitiator for the ATRP of tert‐butyl acrylate or methyl methacrylate, and this resulted in AB₂‐type PCL–[poly(tert‐butyl acrylate)]₂ or PCL–[poly(methyl methacrylate)]₂ miktoarm star polymers with controlled molecular weights and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.23) via the ROP–ATRP sequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2313–2320, 2004     

Preparation of poly(ethylene oxide) star polymers and poly(ethylene oxide)–polystyrene heteroarm star polymers by atom transfer radical polymerization

Poly(ethylene oxide) (PEO) star polymer with a microgel core was prepared by atom transfer radical poylmerization (ATRP) of divinyl benzene (DVB) with mono‐2‐bromoisobutyryl PEO ester as a macroinitiator. Several factors, such as the feed ratio of DVB to the initiator, type of catalysts, and purity of DVB, play important roles during star formation. The crosslinked poly(divinyl benzene) (PDVB) core was further obtained by the hydrolysis of PEO star to remove PEO arms. Size exclusion chromatography (SEC) traces revealed the bare core has a broad molecular weight distribution. PEO–polystyrene (PS) heteroarm star polymer was synthesized through grafting PS from the core of PEO star by another ATRP of styrene (St) because of the presence of initiating groups in the core inherited from PEO star. Characterizations by SEC, ¹H NMR, and DSC revealed the successful preparation of the target star copolymers. Scanning electron microscopy images suggested that PEO–PS heteroarm star can form spherical micelles in water/tetrahydrofuran mixture solvents, which further demonstrated the amphiphilic nature of the star polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2263–2271, 2004     

Healable network polymers bearing flexible poly(lauryl methacrylate) chains via thermo‐reversible furan‐maleimide diels–alder reaction

A new ATRP initiator containing two furyl rings, namely, bis(furan‐2‐ylmethyl) 2‐bromopentanedioate was synthesized starting from commercially available l ‐glutamic acid as a precursor. Well‐defined bisfuryl‐terminated poly(lauryl methacrylate) macromonomers with molecular weight and dispersity in the range 5000–12,000 g mol^?1 and 1.30–1.37, respectively, were synthesized employing the initiator by atom transfer radical polymerization (ATRP). Independently, 1,1′,1″‐(nitrilotris(ethane‐2,1‐diyl))tris(1H‐pyrrole‐2,5‐dione) was synthesized as a tris‐maleimide counterpart for furan‐maleimide click reaction. Thermo‐reversible network polymer bearing flexible poly(lauryl methacrylate; (PLMA) chains was obtained by furan‐maleimide Diels–Alder click reaction of bisfuryl‐terminated PLMA with 1,1′,1″‐(nitrilotris(ethane‐2,1‐diyl))tris(1H‐pyrrole‐2,5‐dione). The prepared network polymer showed retro‐Diels–Alder reaction in the temperature range 110–170 °C as determined from DSC analysis. The presence of low Tg (–40 °C) PLMA chains induced chain mobility to the network structure which led to the complete scratch healing of the coating at 60 °C in five days due to furan‐maleimide adduct formation. The storage modulus of the network polymer was found to be 3.7 × 10⁴ Pa at the constant angular frequency of 5 rad/sec and strain of 0.5%. The regular reversal of storage (G ′) and loss modulus (G ″) was observed with repeated heating (40 to 110 °C) and cooling cycles (110 to 40 °C) at constant angular frequency and strain. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2700–2712     

Block and star block copolymers by mechanism transformation. VI. Synthesis and characterization of A4B4 miktoarm star copolymers consisting of polystyrene and polytetrahydrofuran prepared by cationic ring‐opening polymerization and atom transfer radical polymerization

The synthesis of A₄B₄ miktoarm star copolymers, where A is polytetrahydrofuran (PTHF) and B is polystyrene (PSt), was accomplished with orthogonal initiators and consecutive cationic ring‐opening polymerization (CROP) and atom transfer radical polymerization (ATRP). The compound formed in situ from the reaction of 3‐{2,2‐bis[2‐bromo‐2‐(chlorocarbonyl) ethoxy] methyl‐3‐(2‐chlorocarbonyl) ethoxy} propoxyl‐2‐bromopropanoyl chloride [C(CH₂OCH₂CHBrCOCl)₄] with silver perchlorate was used to initiate the CROP of tetrahydrofuran. The obtained polymer contained four secondary bromine groups at the α position to the original initiator sites and was used to initiate the ATRP of styrene with a CuBr/2,2′‐bipyridine catalyst to form a C(PTHF)₄(PSt)₄ miktoarm star copolymer. The miktoarm copolymer was characterized by gel permeation chromatography and ¹H NMR. The macroinitiator C(PTHF)₄Br₄ was hydrolyzed to afford PTHF arms. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2134–2142, 2001     

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Well‐defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol), poly(tert‐butyl methacrylate), and poly(N‐isopropylacrylamide) arms, PEG(‐b‐PtBMA)‐b‐PNIPAM, was synthesized via a combination of consecutive click reactions and atom transfer radical polymerization (ATRP). Click reaction of monoalkynyl‐terminated PEG with a trifunctional core molecule bis(2‐azidoethyl)amine, (N₃)₂? NH, afforded difunctional PEG possessing an azido and a secondary amine moiety at the chain end, PEG‐NH? N₃. Next, the amidation of PEG‐NH? N₃ with 2‐chloropropionyl chloride led to PEG‐based ATRP macroinitiator, PEG(? N₃)? Cl. The subsequent ATRP of N‐isopropylacrylamide (NIPAM) using PEG(? N₃)? Cl as the macroinitiator led to PEG(? N₃)‐b‐PNIPAM bearing an azido moiety at the diblock junction point. Finally, well‐defined ABC miktoarm star terpolymer, PEG(‐b‐PtBMA)‐b‐PNIPAM, was prepared via the click reaction of PEG(? N₃)‐b‐PNIPAM with monoalkynyl‐terminated PtBMA. In aqueous solution, the obtained ABC miktoarm star terpolymer self‐assembles into micelles consisting of PtBMA cores and hybrid PEG/PNIPAM coronas, which are characterized by dynamic and static laser light scattering, and transmission electron microscopy. On heating above the phase transition temperature of PNIPAM in the hybrid corona, micelles initially formed at lower temperatures undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4001–4013, 2009     

Synthesis of AB2 miktoarm star-shaped copolymers by combining stable free radical polymerization and atom transfer radical polymerization

A stable nitroxyl radical functionalized with two initiating groups for atom transfer radical polymerization (ATRP), 4-(2,2-bis-(methyl 2-bromo isobutyrate)-propionyloxy)-2,2,6,6-tetramethyl-1-piperidinyloxy (Br₂-TEMPO), was synthesized by reacting 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy with 2,2-bis-(methyl 2-bromo isobutyrate) propanoic acid. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br₂-TEMPO. The obtained polystyrene had two active bromine atoms for ATRP at the ω-end of the chain and was further used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare AB₂-type miktoarm star-shaped copolymers. The molecular weights of the resulting miktoarm star-shaped copolymers at different monomer conversions shifted to higher molecular weights without any trace of the macroinitiator, and increased with monomer conversion.     

Preparation of block copolymers via Diels Alder reaction of maleimide‐ and anthracene‐end functionalized polymers

A number of diblock copolymers were successfully prepared by Diels–Alder reaction, between maleimide‐ and anthracene‐end functionalized poly (methyl methacrylate) (PMMA), polystyrene (PS), poly(tert‐butyl acrylate) (PtBA), and poly(ethylene glycol) (PEG) in toluene, at 110 °C. For this purpose, 2‐bromo‐2‐methyl‐propionic acid 2‐(3,5‐dioxo‐10‐oxa‐4‐azatricyclo[5.2.1.02,6]dec‐8‐en‐4‐yl)‐ethyl ester, 2 , 9‐anthyrylmethyl 2‐bromo‐2‐methyl propanoate, 3 , and 2‐bromo‐propionic acid 2‐(3,5‐dioxo‐10‐oxa‐4‐azatricyclo[5.2.1.02,6]dec‐8‐en‐4‐yl)‐ethyl ester, 4 , were used as initiators in atom transfer radical polymerization, in the presence of Cu(I) salt and pentamethyldiethylenetriamine (PMDETA), at various temperatures. On the other hand, PEG with maleimide‐ or anthracene‐end functionality was achieved by esterification between monohydroxy PEG and succinic acid monoathracen‐9‐ylmethyl ester, 1 , or 4‐maleimido‐benzoyl chloride. Thus‐obtained PMMA‐b‐PS, PEG‐b‐PS, PtBA‐b‐PS, and PMMA‐b‐PEG block copolymers were characterized by ¹H NMR, UV, and GPC. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1667–1675, 2006     

Three‐arm star block copolymers of aromatic polyether and polystyrene from chain‐growth condensation polymerization,atom transfer radical polymerization,and click reaction

Well‐defined (AB)₃ type star block copolymer consisting of aromatic polyether arms as the A segment and polystyrene (PSt) arms as the B segment was prepared using atom transfer radical polymerization (ATRP), chain‐growth condensation polymerization (CGCP), and click reaction. ATRP of styrene was carried out in the presence of 2,4,6‐tris(bromomethyl)mesitylene as a trifunctional initiator, and then the terminal bromines of the polymer were transformed to azide groups with NaN₃. The azide groups were converted to 4‐fluorobenzophenone moieties as CGCP initiator units by click reaction. However, when CGCP was attempted, a small amount of unreacted initiator units remained. Therefore, the azide‐terminated PSt was then used for click reaction with alkyne‐terminated aromatic polyether, obtained by CGCP with an initiator bearing an acetylene unit. Excess alkyne‐terminated aromatic polyether was removed from the crude product by means of preparative high performance liquid chromatography (HPLC) to yield the (AB)₃ type star block copolymer (M_n = 9910, M_w/M_n = 1.10). This star block copolymer, which contains aromatic polyether segments with low solubility in the shell unit, exhibited lower solubility than A₂B or AB₂ type miktoarm star copolymers. In addition, the obtained star block copolymer self‐assembled to form spherical aggregates in solution and plate‐like structures in film. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of poly(methyl methacrylate)‐b‐polystyrene containing a crown ether unit at the junction point via combination of atom transfer radical polymerization and nitroxide mediated radical polymerization routes

Poly(methyl methacrylate)‐b‐polystyrene (PMMA‐b‐PS) containing a benzo‐15‐crown‐5 unit at the junction point was prepared by combining atom transfer radical polymerization and nitroxide‐mediated radical polymerization. For this purpose, 6,7,9,10,12,13,15,16‐octahydro‐5,8,11,14,17‐pentaoxa‐benzocyclopentadecene‐2‐carboxylic acid 3‐(2‐bromo‐2‐methyl‐propionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yloxy)‐ethoxycarbonyl]‐propyl ester ( 3 ) was synthesized and used as an initiator in atom transfer radical polymerization of methyl methacrylate in the presence of CuCl and pentamethyldiethylenetriamine at 60°C. A linear behavior was observed in both plots of ln([M]₀/[M]) versus time and M_n,_GPC versus conversion indicating that the polymerization proceeded in a controlled/living manner. Thus obtained PMMA precursor was used as a macroinitiator in nitroxide‐mediated radical polymerization of styrene (St) at 125°C to give well‐defined PMMA‐b‐PS with crown ether per chain. Kinetic data were also obtained for copolymerization. Moreover, potassium picrate (K⁺ picrate) complexation of 3 and PMMA‐b‐PS copolymer was studied. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3242–3249, 2006     

Synthesis of polystyrene–poly(tert‐butyl methacrylate)–poly(ethylene oxide) triarm star block copolymers

Three alternative routes, using the heterobifunctional macroinitiator technique, have been developed to obtain polystyrene–poly(tert‐butyl methacrylate)–poly(ethylene oxide) triarm star block copolymers. Only the route showing the reverse initiation of tert‐butyl methacrylate on potassium alkoxide leads to the pure star, whereas the other strategies lead to incomplete initiation because of either an increase in the side reactions, such as transesterification, or a decrease in the accessibility toward bulky catalysts. These limits are linked to the particular location of the initiating group at the junction of the two blocks of the copolymer precursor. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1745–1751, 2004     

Multiarm star polymers with a thermally cleavable core: A “grafting‐from” approach paves the way

Thermally cleavable multiarm star polymers containing thermo‐reversible furan–maleimide cycloadduct‐based core were synthesized using dendritic macroinitiators. Peripheries of dendritic macroinitiators were modified with bromine containing free radical initiators to obtain multiarm polymers by utilizing atom transfer radical polymerization (ATRP). Cleavage of thus obtained multiarm polymers was achieved via the retro Diels–Alder cycloreversion reaction of the furan–maleimide core at elevated temperatures. As an alternative approach, combination of multiarm polymers containing a furan and maleimide functional group at their core was attempted to realize that the steric bulk does not allow their formation. Hence the “grafting‐from” route using a thermally fragmentable trigger containing multiarm initiators provides a plausible methodology for fabrication of such thermally cleavable multiarm polymeric materials. Syntheses of dendritic initiators, formation of star polymers as well as their fragmentation were followed by proton nuclear magnetic resonance spectroscopy and size exclusion chromatography. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 885–893     

Maleimide‐based thiol reactive multiarm star polymers via Diels‐Alder/retro Diels‐Alder strategy

Multiarm star polymers containing thiol‐reactive maleimide groups at their core have been synthesized by utilization of atom transfer radical polymerization (ATRP) of various methacrylates using a masked maleimide containing multiarm initiator. One end of the initiator contains multiple halogen groups that produce the star architecture upon polymerization and the other end contains a masked maleimide functional group. Unmasking of the maleimide group after the polymerization provides the thiol reactive maleimide core that is widely used in bioconjugation. Functionalization of the core maleimide group with a thiol containing tripeptide was used to demonstrate facile reactivity of the core of these multiarm polymers under reagent‐free conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2546–2556, 2010     

Synthesis and characterization of fluorene end‐labeled polystyrene with atom transfer radical polymerization

Fluorene end‐labeled polystyrene was prepared by atom transfer radical polymerization with 9‐bromofluorene as the initiator. Reactions were carried out in bulk or tetrahydrofuran solutions at temperatures of 80 °C or above. Analysis by gel permeation chromatography indicated that the polymers formed had low polydispersities with molecular weights consistently 2–5 times higher than calculated based on monomer‐to‐initiator ratios. Coupling of two fluorenyl radicals, formed by activation of the 9‐bromofluorene, was found to compete with initiation, leading to the higher‐than‐expected molecular weight values while giving rise to a fluorene dimer. UV–vis spectrometry indicated near‐quantitative fluorene labeling of the polystyrene. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2657–2665, 2005     

Poly(ethylene glycol)‐thioxanthone prepared by Diels–Alder click chemistry as one‐component polymeric photoinitiator for aqueous free‐radical polymerization

Novel water‐borne macrophotoinitiator containing thioxanthone (TX) end group was successfully synthesized by using Diels–Alder (DA) [4 + 2] click chemistry strategy. For this purpose, thioxanthone‐anthracene (TX‐A) and maleimide end‐functionalized poly(ethylene glycol) (PEG‐MI) were reacted in toluene at reflux temperature for 48 h. The final polymer (PEG‐TX) and the intermediates were characterized in detail by spectral analysis. PEG‐TX possesses absorption characteristics similar to the parent TX. The one‐component photoinitiating nature of the photointiator was demonstrated by photopolymeization of several hydrophilic vinyl monomers, such as acrylic acid, acrylamide, 2‐hydroxyethyl acrylate, and 1‐vinyl‐2‐pyrrolidone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2109–2114, 2010