Block‐brush copolymers via ROMP and sequential double click reaction strategy

We report an efficient way, sequential double click reactions, for the preparation of brush copolymers with AB block‐brush architectures containing polyoxanorbornene (poly (ONB)) backbone and poly(ε‐caprolactone) (PCL), poly(methyl methacrylate) (PMMA) or poly(tert‐butyl acrylate) (PtBA) side chains: poly(ONB‐g‐PMMA)‐b‐poly(ONB‐g‐PCL) and poly(ONB‐g‐PtBA)‐b‐poly(ONB‐g‐PCL). The living ROMP of ONB affords the synthesis of well‐defined poly(ONB‐anthracene)₂₀‐b‐poly (ONB‐azide)₅ block copolymer with anthryl and azide pendant groups. Subsequently, well‐defined linear alkyne end‐functionalized PCL (PCL‐alkyne), maleimide end‐functionalized PMMA (PMMA‐MI) and PtBA‐MI were introduced onto the block copolymer via sequential azide‐alkyne and Diels‐Alder click reactions, thus yielding block‐brush copolymers. The molecular weight of block‐brush copolymers was measured via triple detection GPC (TD‐GPC) introducing the experimentally calculated dn/dc values to the software. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Multiarm star triblock terpolymers via sequential double click reactions

Multiarm star triblock terpolymers were obtained by using two different click reactions sequentially: Cu(I) catalyzed azide–alkyne and Diels–Alder. The synthetic strategy is described as follows: (poly(methyl methacrylate))_n‐(polystyrene)_m‐poly(divinyl benzene)) ((PMMA)_n‐(PS)_m‐polyDVB) multiarm star diblock copolymer was first obtained from an azide–alkyne click reaction of (alkyne‐PS)_m‐polyDVB multiarm star polymer with α‐anthracene‐ω‐azide PMMA (anth‐PMMA‐N₃), followed by a Diels–Alder click reaction of the anthracene groups at the star periphery with α‐maleimide poly (tert‐butyl acrylate) (PtBA‐MI) or α‐maleimide poly(ethylene glycol) (PEG‐MI) leading to target (PtBA)_k‐(PMMA)_n‐(PS)_m‐polyDVB and (PEG)_p‐(PMMA)_n‐(PS)_m‐polyDVB multiarm star triblock terpolymers. The hydrodynamic diameter of individual multiarm star triblock terpolymers were measured by dynamic light scattering (DLS) to be ～24–27 nm in consistent with the atomic force microscopy (AFM) images on silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1557–1564, 2010     

Multiarm star block and multiarm star mixed‐block copolymers via azide‐alkyne click reaction

The synthesis of multiarm star block (and mixed‐block) copolymers are efficiently prepared by using Cu(I) catalyzed azide‐alkyne click reaction and the arm‐first approach. α‐Silyl protected alkyne polystyrene (α‐silyl‐alkyne‐PS) was prepared by ATRP of styrene (St) and used as macroinitiator in a crosslinking reaction with divinyl benzene to successfully give multiarm star homopolymer with alkyne periphery. Linear azide end‐functionalized poly(ethylene glycol) (PEG‐N₃) and poly (tert‐butyl acrylate) (PtBA‐N₃) were simply clicked with the multiarm star polymer described earlier to form star block or mixed‐block copolymers in N,N‐dimethyl formamide at room temperature for 24 h. Obtained multiarm star block and mixed‐block copolymers were identified by using ¹H NMR, GPC, triple detection‐GPC, atomic force microscopy, and dynamic light scattering measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 99–108, 2010     

Sequential double polymer click reactions for the preparation of regular graft copolymers

In this study, graft copolymers with regular graft points containing polystyrene (PS) backbone and poly(methyl methacrylate) (PMMA), poly(tert‐butyl acrylate) (PtBA), or poly (ethylene glycol) (PEG) side chains were simply achieved by a sequential double polymer click reactions. The linear α‐alkyne‐ω‐azide PS with an anthracene pendant unit per chain was produced via atom transfer radical polymerization of styrene initiated by anthracen‐9‐ylmethyl 2‐((2‐bromo‐2‐methylpropanoyloxy)methyl)‐2‐methyl‐3‐oxo‐3‐(prop‐2‐ynyloxy) propyl succinate. Subsequently, the azide–alkyne click coupling of this PS to create the linear multiblock PS chain with pendant anthracene sites per PS block, followed by Diels–Alder click reaction with maleimide end‐functionalized PMMA, PtBA, or PEG yielded final PS‐g‐PMMA, PS‐g‐PtBA or PS‐g‐PEG copolymers with regular grafts, respectively. Well‐defined polymers were characterized by ¹H NMR, gel permeation chromatography (GPC) and triple detection GPC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

One‐pot double click reactions for the preparation of H‐shaped ABCDE‐type quintopolymer

We employed for the first time double click reactions: Cu(I) catalyzed azide‐alkyne 1,3‐dipolar cycloaddition and Diels–Alder (4 + 2) reactions for the preparation of H‐shaped polymer possessing pentablocks with different chemical nature (H‐shaped quintopolymer) using one‐pot technique. H‐shaped quintopolymer consists of poly(ethylene glycol) (PEG)‐poly(methylmethacrylate) (PMMA) and poly(ε‐caprolactone) (PCL)‐polystyrene (PS) blocks as side chains and poly (tert‐butylacrylate) (PtBA) as a main chain. For the preparation of H‐shaped quintopolymer, PEG‐b‐PMMA and PCL‐b‐PS copolymers with maleimide and alkyne functional groups at their centers, respectively, were synthesized and simply reacted in one‐pot with PtBA with α‐anthracene‐ω‐azide end functionalities in N,N‐dimethylformamide (DMF) using CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst at 120 °C for 48 h. The precursors and the target H‐shaped quintopolymer were characterized comprehensively by ¹H NMR, UV, FTIR, GPC, and triple detection GPC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3409–3418, 2009     

One‐pot synthesis of star‐block copolymers using double click reactions

3‐Arm star‐block copolymers, (polystyrene‐b‐poly(methyl methacrylate))₃, (PS‐b‐PMMA)₃, and (polystyrene‐b‐poly(ethylene glycol))₃, (PS‐b‐PEG)₃, are prepared using double‐click reactions: Huisgen and Diels–Alder, with a one‐pot technique. PS and PMMA blocks with α‐anthracene‐ω‐azide‐ and α‐maleimide‐end‐groups, respectively, are achieved using suitable initiators in ATRP of styrene and MMA, respectively. However, PEG obtained from a commercial source is reacted with 3‐acetyl‐N‐(2‐hydroxyethyl)‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2‐carboxamide (7) to give furan‐protected maleimide‐end‐functionalized PEG. Finally, PS/PMMA and PS/PEG blocks are linked efficiently with trialkyne functional linking agent 1,1,1‐tris[4‐(2‐propynyloxy)phenyl]‐ethane 2 in the presence of CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) at 120 °C for 48 h to give two samples of 3‐arm star‐block copolymers. The results of the peak splitting using a Gaussian deconvolution of the obtained GPC traces for (PS‐b‐PMMA)₃ and (PS‐b‐PEG)₃ displayed that the yields of target 3‐arm star‐block copolymers were found to be 88 and 82%, respectively. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7091–7100, 2008     

Multiarm star block copolymers via Diels‐Alder click reaction

Two types of multiarm star block copolymers: (polystyrene)_m‐poly(divinylbenzene)‐poly(methyl methacrylate)_n, (PS)_m‐polyDVB‐(PMMA)_n and (polystyrene)_m‐poly(divinylbenzene)‐poly(tert‐butyl acrylate)_k, (PS)_m‐polyDVB‐(PtBA)_k were successfully prepared via a combination of cross‐linking and Diels–Alder click reactions based on “arm‐first” methodology. For this purpose, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross‐linking reaction of divinyl benzene using α‐anthracene end functionalized polystyrene (PS‐Anth) as a macroinitiator. Thus, obtained multiarm star polymer was then reacted with furan protected maleimide‐end functionalized polymers: PMMA‐MI or PtBA‐MI at reflux temperature of toluene for 48 h resulting in the corresponding multiarm star block copolymers via Diels–Alder click reaction. The multiarm star and multiarm star block copolymers were characterized by using ¹H NMR, SEC, Viscotek triple detection SEC (TD‐SEC) and UV. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 178–187, 2009     

Graft copolymers via ROMP and Diels–Alder click reaction strategy

Anthracene‐functionalized oxanorbornene monomer and oxanorbornenyl polystyrene (PS) with ω‐anthracene end‐functionalized macromonomer were first polymerized via ring‐opening metathesis polymerization using the first‐generation Grubbs' catalyst in dichloromethane at room temperature and then clicked with maleimide end‐functionalized polymers, poly(ethylene glycol) (PEG)‐MI, poly(methyl methacrylate) (PMMA)‐MI, and poly(tert‐butyl acrylate) (PtBA)‐MI in a Diels–Alder reaction in toluene at 120 °C to create corresponding graft copolymers, poly(oxanorbornene)‐g‐PEG, poly(oxanorbornene)‐g‐PMMA, and graft block copolymers, poly(oxanorbornene)‐g‐(PS‐b‐PEG), poly(oxanorbornene)‐g‐(PS‐b‐PMMA), and poly(oxanorbornene)‐g‐(PS‐b‐PtBA), respectively. Diels–Alder click reaction efficiency for graft copolymerization was monitored by UV–vis spectroscopy. The dn/dc values of graft copolymers and graft block copolymers were experimentally obtained using a triple detection gel permeation chromatography and subsequently introduced to the software so as to give molecular weights, intrinsic viscosity ([η]) and hydrodynamic radius (R_h) values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Heterograft copolymers via double click reactions using one‐pot technique

The double click reactions (Cu catalyzed Huisgen and Diels–Alder reactions) were used as a new strategy for the preparation of well‐defined heterograft copolymers in one‐pot technique. The synthetic strategy to the various stages of this work is outlined: (i) preparing random copolymers of styrene (St) and p‐chloromethylstyrene (CMS) (which is a functionalizable monomer) via nitroxide mediated radical polymerization (NMP); (ii) attachment of anthracene functionality to the preformed copolymer by the o‐etherification procedure and then conversion of the remaining ? CH₂Cl into azide functionality; (iii) by using double click reactions in one‐pot technique, maleimide end‐functionalized poly(methyl methacrylate) (PMMA‐MI) via atom transfer radical polymerization (ATRP) of MMA and alkyne end‐functionalized poly (ethylene glycol) (PEG‐alkyne) were introduced onto the copolymer bearing pendant anthryl and azide moieties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6969–6977, 2008     

Diels‐alder click reaction for the preparation of polycarbonate block copolymers

The Diels‐Alder reaction as a click reaction strategy is applied to the preparation of well‐defined polycarbonate (PC)‐block copolymers. A well‐defined α‐anthracene‐terminated polycarbonate (PC‐anthracene) is prepared using 9‐anthracene methanol as an initiator in the ring opening polymerization of benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate in CH₂Cl₂ at room temperature for 5 h. Next, a well‐defined α‐furan protected maleimide‐terminated‐poly(ethylene glycol) (PEG₁₁‐MI or PEG₃₇‐MI), ‐poly(methyl methacrylate) (PMMA₂₆‐MI), and ‐poly(ε‐caprolactone) (PCL₂₇‐MI) were clicked with the PC‐anthracene at reflux temperature of toluene to yield their corresponding PC‐based block copolymers (PC‐b‐PEG, PC‐b‐PMMA, and PC‐b‐PCL). The homopolymer precursors and their block copolymers were characterized by using the GPC, NMR and UV analysis. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

ABC type miktoarm star copolymers through combination of controlled polymerization techniques with thiol‐ene and azide‐alkyne click reactions

ABC type miktoarm star copolymer with polystyrene (PS), poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) arms was synthesized using controlled polymerization techniques in combination with thiol‐ene and copper catalyzed azide‐alyne “click” reactions (CuAAC) and characterized. For this purpose, 1‐(allyloxy)‐3‐azidopropan‐2‐ol was synthesized as the core component in a one‐step reaction with high yields (96%). Independently, ω‐thiol functionalized polystyrene (PS‐SH) was synthesized in a two‐step protocol with a very narrow molecular weight distribution. The bromo end function of PS obtained by atom transfer radical polymerization was first converted to xanthate function and then reacted with 1, 2‐ethandithiol to yield desired thiol functional polymer (PS‐SH). The obtained polymer was grafted onto the core by thiol‐ene click chemistry. In the following stage, ε‐caprolactone monomer was polymerized from the core by ring opening polymerization (ROP) using tin octoate as catalyst through hydroxyl groups to form the second arm. Finally, PEG‐acetylene, which was simply synthesized by the esterification of Me‐PEG and 5‐pentynoic acid, was clicked onto the core through azide groups present in the structure. The intermediates at various stages and the final miktoarm star copolymer were characterized by ¹H NMR, FTIR, and GPC measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Postfunctionalization of polyoxanorbornene via sequential Michael addition and radical thiol‐ene click reactions

We demonstrated the successful postfunctionalization of poly(oxanorbornene imide) (PONB) with two types of double bonds using sequential orthogonal reactions, nucleophilic thiol‐ene coupling via Michael addition and radical thiol‐ene click reactions. First, the synthesis of PONB with side chain acrylate groups is carried out via ring‐opening metathesis polymerization and nitroxide radical coupling reaction, respectively. Subsequently, the resulting polymer having two different orthogonal functionalities, main chain vinyl and side chain acrylate, is selectively modified via two sequential thiol‐ene click reactions, nucleophilic thiol‐ene coupling via Michael addition and photoinduced radical thiol‐ene. The orthogonal reactivity of two diverse double bonds, vinyl and acrylate functionalities, for the abovementioned consecutive thiol‐ene click reactions was first demonstrated on the model compound. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Heterograft brush copolymers via romp and triple click reaction strategies involving CuAAC,diels–alder,and nitroxide radical coupling reactions

In this study, an equimolar mixture of oxanorbornenyl‐anthracene (ONB‐anthracene), oxanorbornenyl‐bromide (ONB‐Br), and oxanorbornenyl tosylate (ONB‐OTs) was polymerized via ring opening metathesis polymerization using the first generation Grubbs' catalyst in CH₂Cl₂ at room temperature to form poly(ONB‐anthracene‐co‐ONB‐Br‐co‐ONB‐OTs)₁₀ copolymer as a main backbone. Next, this main backbone was sequentially clicked with a furan protected maleimide‐terminated poly(methyl methacrylate), 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐terminated poly(ethylene glycol), and alkyne‐terminated poly(ε‐caprolactone) (PCL₂₀‐alkyne) via Diels–Alder, nitroxide radical coupling, and copper‐catalyzed azide‐alkyne cycloaddition, respectively, to yield a poly(ONB‐g‐PMMA‐co‐ONB‐g‐PEG‐co‐ONB‐g‐PCL)₁₀ heterograft brush copolymer © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of tadpole polymers via triple click reactions: Copper‐catalyzed azide–alkyne cycloaddition,diels–alder,and nitroxide radical coupling reactions

We designed a trifunctional initiator ( 3 ) containing anthracene, bromide, and OH functionalities and subsequently used as an initiator in atom transfer radical Polymerization (ATRP) of styrene to yield linear polystyrene (PS) with α‐anthracene, OH, and ω‐bromide terminal groups, of which bromide is later transformed into azide to result in the linear anthracene‐, OH‐, and azide‐terminated PS (l‐α‐anthracene‐OH‐ω‐azide‐PS). The copper‐catalyzed azide–alkyne cycloaddition reaction between l‐α‐anthracene‐OH‐ω‐azide‐PS and α‐furan‐protected‐maleimide‐ω‐alkyne linkage, 4 afforded the linear anthracene‐, OH‐, and maleimide‐terminated PS. The cyclization via intramolecular Diels–Alder click reaction of this linear PS and the subsequent conversion of the hydroxyl into bromide resulted in the cyclic PS with one bromide located on the ring, (c‐PS)‐Br. Finally, the c‐PS‐Br was clicked with either well‐defined tetramethylpiperidine‐1‐oxyl‐terminated poly(ethylene glycol) (PEG) or poly(ε‐caprolactone) (PCL) yielding the tadpole polymer, (c‐PS)‐b‐PEG or (c‐PS)‐b‐PCL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Orthogonal multiple click reactions in synthetic polymer chemistry

This review highlights the concept of multiple click reaction strategy which is utilized for design and synthesis of well‐defined complex macromolecular structures as well as multifunctionalization of well‐defined polymers. This review examines the click combinations mainly from double to quadruple and additionally from the most frequently used to the least. The present review may also be regarded as an update for recent reviews dealing with specifically double and triple click reaction combinations in synthetic polymer chemistry. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3147–3165     

Various polycarbonate graft copolymers via diels–alder click reaction

In this work, we used Diels–Alder click reaction for the preparation of various types of aliphatic polycarbonates (PCs). We first prepared a novel anthracene‐functionalized cyclic carbonate monomer, anthracen‐9‐ylmethyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate (2), followed by ring‐opening polymerization of this monomer to prepare PC with pendant anthracene groups (PC‐anthracene) using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU)/1‐(3,5‐bis(trifloromethyl)phenyl)‐3‐cyclohexylthiourea (TU) as the catalyst and benzyl alcohol as the initiator in CH₂Cl₂ at room temperature. Subsequently, the resulting PC‐anthracene (M_n,TDGPC = 6000 g/mol, M_w/M_n = 1.22) was grafted with a linear α‐furan protected‐maleimide terminated‐poly(methyl methacrylate) (PMMA‐MI) (M_n,GPC = 3100 g/mol, M_w/M_n = 1.31), or poly(ethylene glycol) (PEG‐MI) (M_n,GPC = 550 g/mol, M_w/M_n = 1.09), or a mixture of PMMA‐MI and PEG‐MI to yield well‐defined PC graft or hetero graft copolymers, PC‐g‐PMMA (M_n,TDGPC = 59000 g/mol, M_w/M_n = 1.22) or PC‐g‐PEG, or PC‐g‐(PMMA)‐co‐PC‐g‐(PEG) (M_n,TDGPC = 39900 g/mol, M_w/M_n = 1.16), respectively, using Diels–Alder click reaction in toluene at 110°C. The Diels–Alder grafting efficiencies were found to be over 97% using UV spectroscopy. Moreover, the structural analyses and the molecular weights of resulting graft copolymers were determined via ¹H NMR and triple detection GPC (TD‐GPC), respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Multiarm star polymers with peripheral dendritic PMMA arms through Diels–Alder click reaction

Dendritic 2‐ and 4‐arm PMMA‐based star polymers with furan‐protected maleimide at their focal point, (PMMA)_2n‐MI and (PMMA)_4n‐MI were efficiently clicked with the peripheral anthracene functionalized multiarm star polymer, (α‐anthryl functionalized‐polystyrene)_m‐poly(divinyl benzene) ((α‐anthryl‐PS)_m‐polyDVB) through the Diels–Alder reaction resulting in corresponding multiarm star block copolymers: (PMMA)_2n‐(PS)_m‐polyDVB and (PMMA)_4n‐(PS)_m‐polyDVB, respectively. Molecular weights (M_w,TDGPC), hydrodynamic radius (R_h), and intrinsic viscosity (η) of the multiarm star polymers were determined using three‐detection GPC (TD‐GPC). The high efficiency of this methodology to obtain such sterically demanding macromolecular constructs was deduced using ¹H‐NMR and UV–vis spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Conjugated block copolymers via functionalized initiators and click chemistry

Conjugated block copolymers are potentially useful for organic electronic applications and the study of interfacial charge and energy transfer processes; yet few synthetic methods are available to prepare polymers with well‐defined conjugated blocks. Here, we report the synthesis and thin film morphology of a series of conjugated poly(3‐hexylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3HT‐b‐PF) and poly(3‐dodecylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3DDT‐b‐PF) block copolymers prepared by functional external initiators and click chemistry. Functional group control is quantified by proton nuclear magnetic resonance spectroscopy, size‐exclusion chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The thin film morphology of the resulting all‐conjugated block copolymers is analyzed by a combination of grazing‐incidence X‐ray scattering, atomic force microscopy, and transmission electron microscopy. Crystallization of the P3HT or P3DDT blocks is present in thin films for all materials studied, and P3DDT‐b‐PF films exhibit significant PF/P3DDT co‐crystallization. Processing conditions are found to impact thin film crystallinity and orientation of the π–π stacking direction of polymer crystallites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 154–163     

Functionalized random copolymers from versatile one‐pot click chemistry/ATRP tandems approaches

Two complementary tandem strategies based on the one‐pot combination of click chemistry and atom transfer radical polymerization (ATRP) are studied. Initially, functionalized random copolymers are obtained by copolymerization of methyl methacrylate and propargyl methacrylate simultaneously to the click chemistry coupling of a monofunctional azide. Then, an approach based on the copolymerization of methyl methacrylate and 11‐azido‐undecanoyl methacrylate simultaneously to the click chemistry coupling of a monofunctional alkyne is also investigated. For both the approach, polymerization and click chemistry coupling are catalyzed by CuBr and bipyridine (Bipy) in diphenylether at 90 °C. The [Bipy]/[CuBr] ratio is varied from 2 to 25 and the ratio of functionalized comonomer from 20 to 70 mol %. Both the tandem strategies proceed with good yields (50–80%) and allow a good control over the characteristics of the resulting random copolymers and macromolecular brushes (M_n ～ 15,000–40,000 g/mol and PDI ～ 1.3–2.0) as well as quantitative click functionalization as characterized by ¹H NMR and size exclusion chromatography analyses. Although the click process is generally completed at the early stage of the process, the rate of polymerization depends on the amount of bipyridine involved. It was found that extending most of the polymerization process out of the click reaction regime results in a better control of the polymerization, preventing the significant occurrence of side reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3803–3813, 2009     

Thermal stability of ester linkage in the presence of 1,2,3‐Triazole moiety generated by click reaction

The copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC), so‐called “click” reaction, is one of most useful synthetic strategies to connect two polymer chains. 1,2,3‐Triazole ring (TA) produced by the click reaction has good thermal and chemical stability. However, we observed that block copolymers synthesized by the click reaction showed thermal degradation to give homopolymers when they are thermally annealed at high temperature, which is required for obtaining equilibrium microdomain structure. To investigate the origin of thermal instability of block copolymers, we synthesized model polystyrenes (PSs) using systematically designed bi‐functional atom transfer radical polymerization (ATRP) initiators containing TA. PS including both ester and TA groups showed thermal decomposition at relatively low temperature (e.g., 140 °C). MALDI‐TOF analysis clearly demonstrated that the cleavage site is the ester group adjacent to TA. We also found that the bromine group located at the polymer chain end plays an important role in pyrolysis of ester groups at low temperature. The pyrolysis occurs by syn‐elimination of the ester group. This result implies that the phase behavior of block copolymer synthesized by click reaction should be carefully investigated when high temperature thermal annealing is required. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 427–436