Using the Diels−Alder (DA) “click chemistry” strategy between anthracene and maleimide functional groups, two series of well-defined polystyrene-g-poly(ethylene glycol) (PS-g-PEG) polystyrene-g-poly(methyl methacrylate) (PS-g-PMMA) copolymers were successfully prepared. The whole process was divided into stages: (i) preparation polymers (ii) use reaction these groups. First, random styrene (S) chloromethylstyrene (CMS) with various CMS contents prepared by nitroxide-mediated radical...

We report a one-pot synthesis of ABC triblock copolymers poly(ethylene glycol)− (PEG−) polystyrene− (PS−) poly(methyl methacrylate) (PMMA), and poly(ε-caprolactone)− (PCL−) PS−PMMA by combining in situ click [3 + 2] Diels−Alder [4 reactions. For this purpose, furan-protected maleimide end-functionalized PMMA, PS with α-anthracene ω-azide end-functionality, PEG or PCL an alkyne end-functional group were reacted N,N-dimehtylformamide (DMF) for 36 h at 120 °C order to give the corresponding...

Double click reaction strategies, which are a combination of different type reactions, allow the preparation polymers with various topologies and post-functionalization polymers, cannot be easily achieved by using only one reaction. The most studied combinations may listed as Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC)–Diels–Alder, CuAAC–nitroxide radical coupling reactions for polymer–polymer conjugation CuAAC–Diels–Alder, or CuAAC–thiol-ene post-modification polymers.

Abstract 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) (P t BA), 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 2‐bromo‐propionic 4 used as...

Abstract Diels–Alder click reaction was successfully applied for the preparation of 3‐arm star polymers (A 3 ) using furan protected maleimide end‐functionalized and trianthracene functional linking agent (2) at reflux temperature toluene 48 h. Well‐defined polymers, poly (ethylene glycol), poly(methyl methacrylate), poly( tert ‐butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained characterized via NMR GPC (refractive index triple detector...

Abstract 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. synthetic to various stages this work is outlined: (i) preparing random styrene (St) p ‐chloromethylstyrene (CMS) (which functionalizable monomer) via nitroxide mediated radical polymerization (NMP); (ii) attachment anthracene functionality preformed copolymer by o ‐etherification procedure then...

ABSTRACT Post‐polymerization modification (PPM) of polymers is extremely beneficial in terms designing brand new synthetic pathways toward functional complex polymers. Fortunately, the developments field organic chemistry along with controlled/living radical polymerization (CLRP) techniques have enabled scientists to readily design and synthesize functionalized‐polymers for wide range applications via PPM. In this regard, reactivity para ‐fluorine atom fluorinated aromatic structures...

A polyester scaffold possessing electron deficient triple bonds in the main chain was prepared and utilized as a precursor for aza- thiol-Michael addition reactions.

A straightforward, novel, and extremely rapid method is developed for the synthesis of polythioether based on reaction dimethyl acetylenedicarboxylate with electron-deficient triple bond 1,6-hexanedithiol in CHCl3 using an organobase 1,5,7-triazabicyclo[4.4.0]dec-5-ene at room temperature. The influence various parameters, such as concentration monomers, solvent, catalyst, time, polymerization was investigated through kinetic studies. Polythioether molecular weight up to ∼50 kDa...

Abstract The ABC type miktoarm star terpolymer was prepared utilizing “core‐in” and “core‐out” methods via combination of Diels–Alder reaction (DA), stable free radical polymerization (SFRP), atom transfer (ATRP). First, in DA reaction, poly(ethylene glycol)‐maleimide (PEG‐maleimide) precursor reacted with succinic acid anthracen‐9‐ylmethyl ester 3‐(2‐bromo‐2‐methyl‐propionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yloxy)‐ethoxy‐carbonyl]‐propyl ester, 8 , to give adduct,...

Abstract 3‐Arm star‐block copolymers, (polystyrene‐ b ‐poly(methyl methacrylate)) 3 , (PS‐ ‐PMMA) and ‐poly(ethylene glycol)) ‐PEG) are prepared using double‐click reactions: Huisgen Diels–Alder, with a one‐pot technique. PS PMMA blocks α‐anthracene‐ω‐azide‐ α‐maleimide‐end‐groups, respectively, achieved suitable initiators in ATRP of styrene MMA, respectively. However, PEG obtained from commercial source is reacted 3‐acetyl‐ N ‐(2‐hydroxyethyl)‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2‐carboxamide...

Abstract Well‐defined linear α‐anthracene‐ω‐maleimide functionalized polystyrene ( l ‐Anth‐PS‐MI) and α‐alkyne‐ω‐maleimide poly( tert ‐butyl acrylate) ‐alkyne‐P t BA‐MI) homopolymers, PS‐ b ‐P BA ‐Anth‐PS‐ ‐poly(ε‐caprolactone) (PCL) ‐PCL‐MI) block copolymers were obtained via combination of atom transfer radical polymerization (ATRP)/ring opening (ROP) azide‐alkyne click reaction strategy. Subsequently, these homo efficiently clicked Diels‐Alder to give their corresponding cyclic at reflux...

Compared to two-dimensional substrates, only a few methodologies exist for the spatially controlled decoration of three-dimensional objects, such as microparticles. Combining electrohydrodynamic co-jetting with synthetic polymer chemistry, we were able create two- and three-patch microparticles displaying chemically orthogonal anchor groups on three distinct surface patches same particle. This approach takes advantage combination novel polylactide-based polymers their processing by yield...

The synthesis of fluorinated polymers via efficient routes along with mild experimental conditions is always desirable in terms synthetic polymer chemistry. In this work, a straightforward method for polythioether was developed. A commercially available electron-deficient alkyne compound, namely 4,4,4-trifluoro-2-butynoate (1), linked to both trifluoromethyl (CF3) and ester units polymerized various dithiols by using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst at room temperature,...

Abstract Heteroarm H‐shaped terpolymers (PS)(P t BA)–PEO–(P BA)(PS) and BA)–PPO–(P [where PS is polystyrene, P BA poly( tert ‐butyl acrylate), PEO poly(ethylene oxide), PPO poly(propylene oxide)], containing or as a backbone side arms, were prepared via the combination of Diels–Alder reaction atom transfer radical nitroxide‐mediated polymerization routes. Commercially available bismaleimide end groups was reacted with compound having an anthracene functionality, succinic acid anthracen‐9‐yl...

Abstract Two types of multiarm star block copolymers: (polystyrene) m ‐poly(divinylbenzene)‐poly(methyl methacrylate) n , (PS) ‐polyDVB‐(PMMA) and ‐poly(divinylbenzene)‐poly( tert ‐butyl acrylate) k ‐polyDVB‐(P t BA) were successfully prepared via a combination cross‐linking Diels–Alder click reactions based on “arm‐first” methodology. For this purpose, polymer with anthracene functionality as reactive periphery groups was by reaction divinyl benzene using α‐anthracene end functionalized...

Abstract A combination of ring opening metathesis polymerization (ROMP) and click chemistry approach is first time utilized in the preparation 3‐miktoarm star terpolymer. The bromide end‐functionality monotelechelic poly( N ‐butyl oxanorbornene imide) (PNBONI‐Br) transformed to azide then reacted with polystyrene‐ b ‐poly(methyl methacrylate) copolymer alkyne at junction point (PS‐ ‐PMMA‐alkyne) via strategy, producing PS‐PMMA‐PNBONI PNBONI‐Br was prepared by ROMP imide (NBONI) 1 presence (...

Abstract We demonstrated the successful postfunctionalization of poly(oxanorbornene imide) (PONB) with two types double bonds using sequential orthogonal reactions, nucleophilic thiol‐ene coupling via Michael addition and radical click reactions. First, synthesis PONB side chain acrylate groups is carried out ring‐opening metathesis polymerization nitroxide reaction, respectively. Subsequently, resulting polymer having different functionalities, main vinyl acrylate, selectively modified...

A polyester containing electron deficient internal alkyne units derived from acetylene dicarboxylic acid in the main backbone was employed as a polymeric platform copper free cycloaddition reactions.

The quest for sustainable monomers and "green" synthetic pathways the design, fabrication, modification of various polymers is great importance attracts a deal attention. Here, highly versatile novel bio-based platform was developed by reacting castor oil with propiolic acid performing amino-yne click reactions. Owing to electron-deficient nature esters, reactions were conducted ease at room temperature, in absence any catalyst solvent (as long as amines low-viscosity liquids temperature),...