Polymerization of acrylonitrile. Kinetics of the reaction initiated by the Ce(IV)/thioacetamide redox system

Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (R_p) and the rate of Ce(IV) disappearance (?R_Ce) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.     

Spectroscopic,electrochemical, and structural aspects of the Ce(IV)/Ce(III) DOTA redox couple chemistry in aqueous solutions

The redox potential of the Ce(IV)/Ce(III) DOTA is determined to be 0.65 V versus SCE, pointing out a stabilization of ~13 orders of magnitude for the Ce(IV)DOTA complex, as compared to Ce(IV)_aq. The Ce(III)DOTA after electrochemical oxidation yields a Ce(IV)DOTA complex with a t_1/2 ~3 h and which is suggested to retain the “in cage” geometry. Chemical oxidation of Ce(III)DOTA by diperoxosulfate renders a similar Ce(IV)DOTA complex with the same t_1/2. From the electrochemical measurements, one calculates logK (Ce(IV)DOTA^2?) ~ 35.9. Surprisingly, when Ce(IV)DOTA is obtained by mixing Ce(IV)_aq with DOTA, a different species is obtained with a 2 : 1(M : L) stoichiometry. This new complex, Ce(IV)DOTACe(IV), shows redox and spectroscopic features which are different from the electrochemically prepared Ce(IV)DOTA. When one uses thiosulfate as a reducing agent of Ce(IV)DOTACe(IV), one gets a prolonged lifetime of the latter. The reductant seems to serve primarily as a coordinating ligand with a geometry which does not facilitate inner sphere electron transfer. The reduction process rate in this case could be dictated by an outer sphere electron transfer or DOTA exchange by S₂O₃^2?. Both Ce(IV)DOTA and Ce(IV)DOTACe(IV) have similar kinetic stability and presumably decompose via decarboxylation of the polyaminocarboxylate ligand.     

Study on aqueous polymerizations of vinyl monomers initiated by metal oxidant–chelating agent redox initiators

In this study, a series of chelating type reductants containing redox pairs were tested as the initiator for aqueous polymerizations. The redox pairs consist of Ce(IV) or several first-row transition metals coupled with chelating agents of amino acids, dibasic acids, or diamine. The initial rates and limiting conversions of acrylamide polymerization initiated by those redox pairs were determined. The reductive reactivity of the chelating agents with Ce(IV) and the oxidative half-wave potential of Ce(III)-chelating agent/Ce(IV)-chelating agent were measured to evaluate the feasibility of these redox pairs as initiators. After the evaluation, the redox pairs other than Ce(IV)-amino acid type chelating agent were precluded to be promising initiators for aqueous polymerizations. Those Ce(IV)-amino acid type chelating agent redox pairs which could form at least two five- or six-membered rings were found to be potential initiators. The Ce(IV)-NTA pair was the most promising one. The mechanism of initiation of the redox pairs was proposed and further confirmed by the ¹³C- and ¹H-NMR spectra of NTA-terminated polyacrylamide. The complex formation constants (K) and disproportionation constants (k_d) of the Ce(IV)-amino acid type chelating agent redox initiators for acrylamide polymerization were evaluated. The factors governing the parameters of chelated complexes and the performance of polymerizations were discussed. These redox pairs were also used as the initiators for aqueous polymerizations of acrylic acid and acrylonitrile. © 1993 John Wiley & Sons, Inc.     

Aqueous polymerization of acrylamide initiated by cerium (IV)–ethylenediamine tetraacetic acid redox system

Ethylenediamine tetraacetic acid (EDTA) terminated polyacrylamide was obtained by using the EDTA–cerium(IV) ammonium nitrate [Ce(IV)] redox initiator in the aqueous polymerization of acrylamide. The polymerization behaviors as a function of the concentration of Ce(IV), EDTA, and acrylamide as well as temperature were studied. The consumption rate of cerium(IV) depends a first-order reaction on the ceric ion concentration ([Ce(IV)]). The complex formation constant (K) and disproportionation constant (k_d) of Ce(IV)–EDTA chelated complex are 1.67 × 10⁴ and 3.77 × 10^?3, respectively. The rate dependences of polymerization on monomer concentration and EDTA concentration both follow a second-order reaction in the run of initial monomer concentration ([M]_i) equal to 0.2 mol dm^?3. The number average molecular weight increases linearly with the ratio of [M]_i/[Ce(IV)]_i. The mechanism and kinetics for the polymerization was proposed. The kinetic parameters involved were determined. © 1992 John Wiley & Sons, Inc.     

Electrochemical Behavior of Ce(IV)/Ce(III) Couple in N,N-Di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-Di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-Di(2-ethylhexyl)-3,3-dimethyl Butanamide (DEHDMBA)

In this work we report on the electrochemical behavior of Ce(IV)/Ce(III) redox couple in pure N,N-dialkyl amides (N,N-DA), namely N,N-di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-di(2-ethylhexyl)-3,3-dimethyl butanamide (DEHDMBA) equilibrated with nitric aqueous solutions as an entry to the direct electrochemical characterization of plutonium in these extractants. Ce(IV)/Ce(III) redox process was used as a model. Its potential (E_1/2≅1.02 V/SCE) is not affected by the temperature and the nature of the N,N-DA and this clearly indicates that the functionalities of these extractants produce the same relative effect on both +IV and +III oxidation states of the cerium cation. Linear variations of the current intensity of the reduction peak of Ce(IV) with the concentration of Ce(IV)/N,N-DAs/HNO₃(5 M) solutions were obtained from cyclic voltammograms recorded at 25 °C and 40 °C. Due to the poor definition of the voltammograms in DEHiBA and DEHDMBA, such characterization allows only the evaluation of the performances of the chemical extraction of Ce(IV) from aqueous nitric acid solution by the undiluted DEHBA. To our knowledge, the electrochemical behavior of Ce(IV)/Ce(III) in N,N-DAs was not previously studied and our findings will for sure open the door for further investigations in this field.     

Effects of TEMED and EDTA on the structural and mechanical properties of NIPAAm/Na+MMT composite hydrogels

N‐isopropyl acrylamide (NIPAAm) hydrogels are known as thermosensitive crosslinked polymer networks. In this work, the network parameters of their composites, i.e., NIPAAm/sodium montmorillonite (NIPAAm/Na⁺MMT) hydrogels synthesized by free radical solution polymerization in the presence of two different types of accelerator (tetramethyl ethylenediamine (TEMED) and ethylenediamine tetraacetic acid (EDTA)) and initiator (potassium persulphate (K₂S₂O₈) and cerium ammonium nitrate ((NH₄)₂Ce(NO₃)₆), Ce(IV)) using five different clay content (in the range of 1.0–5.0 wt % of total monomer concentration) at 25 °C were presented and discussed. FTIR spectra, XRD patterns, SEM photographs, and network parameters of the samples indicated that the presence of COOH groups on EDTA molecules was resulted in the formation of exfoliated structures and the activity of EDTA/KPS redox pair was higher than those of TEMED/KPS and EDTA/Ce (IV) pairs. The compression moduli (G) of the hydrogels initiated with EDTA/Ce(IV) redox pair showed smooth and continual changings with increase in Na⁺MMT content (for swelling equilibrium at 25 °C) on the contrary of EDTA/KPS and TEMED/KPS pairs. It might be related to low initiator efficiency of cerium ammonium nitrate than KPS molecules, having higher effective crosslinking density with increasing clay content. On the other hand, the G moduli of NIPAAm/Na⁺MMT hydrogels (above their phase transition temperature) initiated with TEMED/KPS redox pair were higher than the others because of the more hydrophobic nature of TEMED molecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1256–1264, 2010     

A study on sorbitol-ceric ion initiated polymerization of acrylonitrile

The polymerization of acrylonitrile (M) initiated by the sorbitol (R)-Ce(IV) redox system has been studied in sulphuric acid in the range 30–40° under nitrogen. At moderately high concentrations of Ce(IV) (0.00015-0.02 M), the rate of polymerization (R_p) is proportional to $\text{[}\text{M}\text{]}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{[}\text{R}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and the rate of Ce(IV) disappearance is proportional to [R] and [Ce(IV)]. At lower concentration of Ce(IV) (0.00005–0.00015 M) R_p is proportional to [M], [R]^1/2 and [Ce(IV)]^1/2 and rate of Ce(IV) disappearance is proportional to [R] and [Ce(IV)]. The effects of certain salts, acid, solvent and temperature on both rates have been investigated. A kinetic scheme involving mutual termination has been proposed and various rate and energy parameters evaluated. At still higher concentration of Ce(IV) (0.02 M), a linear mode of termination seems to operate.     

Redox polymerization of methyl methacrylate with allyl alcohol 1,2-butoxylate-block-ethoxylate initiated by Ce(IV)/HNO3 redox system

Redox initiated free-radical polymerization of methyl methacrylate (MMA) with allyl alcohol 1,2-butoxylate-block-ethoxylate (AABE) was carried out using cerium(IV) ammonium nitrate/nitric acid (HNO₃) redox system to yield AABE-b-PMMA copolymers. The effects of MMA, AABE, Ce(IV) and HNO₃ concentrations on the polymerization rate and polymer yield were investigated. The effect of temperature on the rate of polymerization and polymer yield was also investigated in the temperature range of 25-70 °C. Copolymers were characterized using GPC, FT-IR, ¹H NMR and viscometry methods.     

Synthesis and applications of surface-grafted Th(IV)-imprinted polymers for selective solid-phase extraction of thorium(IV)

A new functional monomer N-(o-carboxyphenyl)maleamic acid (CPMA) was synthesized and chosen for the preparation of surface-grafted ion-imprinted polymers (IIPs) specific for thorium(IV). Polymerizable double bond was introduced to silica gel surface by amidation reaction between -NH₂ and maleic anhydride. In the ion-imprinting process, thorium(IV) was complexed with the carboxyl groups, then was imprinted in the polymers grafted to the silica gel surface. The imprinted Th(IV) was removed with 3 mol L⁻¹ HCl. The obtained imprinted particles exhibited excellent selectivity and rapid kinetics process for Th(IV). The relatively selective factor (α_r) values of Th(IV)/La(III), Th(IV)/Ce(III), Th(IV)/Nd(III), Th(IV)/U(VI), and Th(IV)/Zr(IV) were 85.7, 88.9, 26.6, 64.4, and 433.8, respectively, which were greater than 1. The precision (R.S.D.), the detection limit (3σ), and the quantification limit (10σ) of the method were 1.9%, 0.51 ng mL⁻¹ and 1.19 ng mL⁻¹, respectively. The prepared IIPs as solid-phase extractants were successfully applied for the preconcentration of trace thorium in natural and certified samples prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES) with satisfactory results.     

Aqueous polymerization of methyl methacrylate initiated by the redox system Ce(IV)–isopropyl alcohol. Kinetics and molecular weight

Polymerization of methyl methacrylate was carried out in aqueous nitric acid in the temperature range 26–40°C, with the redox initiator system ceric ammonium nitrate–isopropyl alcohol. A short induction period was observed, as well as the attainment of a limiting conversion, and the total ceric ion consumption with reaction time. The reaction orders were 1/2 and 3/2 with respect to the IPA and monomer concentration, respectively, within the range (3–5) × 10^?3M of Ce(IV). But at lower Ce(IV) concentration (≤ 1 × 10^?3M), the order with respect to monomer and Ce(IV) changed to 1 and 1/2, respectively. The rate of ceric ion disappearance was first order with respect to Ce(IV) concentration and (R_Ce)^?1 was proportional to [IPA]^?1. Both the rate of polymerization and the rate of ceric ion consumption increase with rise in temperature. The average-molecular weight can be controlled by variations in IPA, Ce(IV), and monomer concentrations, and in temperature. A kinetic scheme involving oxidation of IPA by Ce(IV) via complex formation, whose decomposition gives rise to a primary radical, initiation, propagation, and termination of the polymeric radicals by bimolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included.     

Aqueous polymerization of acrylamide initiated by cerium(IV)–amino acid chelating agent redox initiators

Amino acid-type chelating agents such as nitrilotriacetic acid (NTA), nitrilotripropionic acid (NPA), iminodiacetic acid (IDA), and ethylenediamine tetraacetic acid (EDTA) were used in combination with cerium(IV) ammonium nitrate [Ce(IV)] as the redox initiators for the aqueous polymerizations of acrylamide (AM). The polymerization behaviors and polymer qualities were studied as functions of the concentrations of Ce(IV), chelating agent, AM, as well as temperature. The performances of the chelating agent redox systems varied with the natures of the chelating agents. The NTA–Ce(IV) initiator showed the most promising polymerization rate and conversion. The blank tests for the reactions of cerium and chelating agents were also conducted for finding mechanism of formation of free radicals and determining their complex formation constants (K) and disproportionation constants (k_d). The mechanism for the polymerization was proposed and the kinetic parameters were evaluated. © 1993 John Wiley & Sons, Inc.     

Large electro‐optic activity and enhanced temporal stability of methacrylate‐based crosslinking hyperbranched nonlinear optical polymer

A methacrylate‐based crosslinking hyperbranced polymers have been synthesized through initiator‐fragment incorporation radical polymerization and used for the temperature stable electro‐optic (EO) polymer application. This polymer consists of methyl methacrylate, 2‐metacryloxyethyl isocyanate, and ethylene glycol dimethacrylate (EGDMA) monomers. The use of EGDMA as a bifunctional unit resulted in the solvent‐soluble crosslinking hyperbranched chain, so that the EO polymer enhanced glass transition temperatures. A phenyl vinylene thiophene vinylene bridge nonlinear optical chromophore was attached to the polymer backbone as the side‐chain by a post‐functionalization reaction. The loading concentration of the chromophore was varied between 30 and 50 wt % by simply changing the mixing ratio of the precursor polymer to the chromophore. The synthesized EO polymers produced optical quality films with a light propagation loss of 0.61 dB/cm in a slab waveguide at 1.31 μm. The electrically poled film had an EO coefficient (r₃₃) of 139 pm/V at 1.31 μm. The EO crosslinking hyperbranced polymer had a high‐glass transition temperature of 170 °C, and exhibited excellent temporal stability of the EO activity at 85 °C for 500 h. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Aqueous polymerization of ethyl acrylate initiated by ceric ion-reducing agent system in sulphuric acid medium

Kinetic study of aqueous polymerization of ethyl acrylate (EA) is carried out at 30 °C in dilute sulphuric acid medium by employing ammonium ceric sulphate–methyl ethyl ketone (MEK) as redox initiator system. The ceric ion consumption is found to be first order with respect to ceric ion and half order with respect to reducing agent concentrations. No complex formation between ceric ion and reducing agent is observed. The orders with respect to ceric ion, reducing agent and monomer concentrations are evaluated for the aqueous polymerization of EA by Ce(IV)–MEK redox initiator system, and are found to be 0.5, 0.5 and 1.4, respectively . The overall activation energy, E _overall, for aqueous polymerization of EA in the temperature region of 27–40°C is found to be 20.27 kJ/mol. A kinetic scheme for the aqueous polymerization of EA initiated by Ce(IV)–MEK redox initiator system is presented.This revised version was published online in June 2005 with corrections to figure legends as well as small corrections within text.     

Locating redox couples in the layered sulfides with application to Cu[Cr2]S4

Use of LiPF₆ in EC:DEC as electrolyte has allowed electrochemical extraction of Li from LiV_1−yM_yS₂ and LiTi_1−yM_yS₂ (M=Cr or Fe). The data show access not only to the Ti(IV)/Ti(III) and V(IV)/V(III) redox couples, but also to the V(V)/V(IV) and Fe(III)/Fe(II) couples in these layered sulfides. However, the Cr(IV)/Cr(III) couple could not be accessed. The concept of redox-couple pinning is outlined and applied to the V(V)/V(IV) and Fe(III)/Fe(II) couples, which are pinned at the top of the S-3p bands. Holes associated with the “pinned” couples occupy orbitals of dominant S-3p character, but they have sufficient cation-3d character to prevent condensation of the holes into p-p antibonding states of disulfide bonds. Strong covalent bonding in the pinned couples creates itinerant-electron states in the partially occupied couples. Application to the metallic, ferromagnetic thiospinel Cu[Cr₂]S₄ favors location of the itinerant holes in states of a pinned Cu(II)/Cu(I) couple having primarily S-3p character.     

Micelle Catalyzed Oxidation of D-Mannose by Cerium (IV) in Sulfuric Acid

Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40°C both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and cerium (IV), which decreased with increasing [H₂SO₄]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (IV) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was the reactive form of cerium (IV). From the kinetic data, micelle-cerium (IV) binding and rate constants in micellar medium were evaluated. The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: -d[Ce(IV)]=k1Kc1[D-mannose][Ce(IV)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.     

Hyperbranched copolymers made from A2, B2 and BB′2type monomers (iv)

The new approach for synthesis of hyperbranched polymers from commercially available A₂ and type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine) was prepared by copolymerization of divinyl sulfone (A₂) with 4,4′-trimethylenedipiperidine (B₂) and N-ethylethylenediamine (BB’₂). During the reaction, secondary-amino groups of B₂ and BB’₂ monomers react rapidly with vinyl groups of A₂ monomers within 35 s, generating a type of intermediate containing one vinyl group and two reactive hydrogen atoms. Now the intermediates can be regarded as a new type monomer, which further polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was investigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranched copolymers increased with decreasing the ratio of 4, 4′-trimethylenedipiperidine to N-ethylethylenediamine, so DB can be controlled. When the initial mole ratio of B₂ to BB′₂was equal to or higher than four,r≥4, resulted copolymers were semi-crystalline, while copolymers withr3 were amorphous.     

Vinyl Polymerization Initiated by Ceric Ion–Ethyl Cellosolve Redox System in Aqueous Nitric Acid

Abstract

Polymerizations of methyl methacrylate (MMA) and acrylonitrile (AN) were carried out in aqueous nitric acid at 30°C with the redox initiator system ammonium ceric nitrate-ethyl cellosolve (EC). A short induction period was observed as well as the attainment of a limiting conversion for polymerization reactions. The consumption of ceric ion was first order with respect to Ce(IV) concentration in the concentration range (0.2–0.4) × 10^?2 M, and the points at higher and lower concentrations show deviations from a linear fit. The plots of the inverse of pseudo-first-order rate constant for ceric ion consumption, (k ¹)^?1 vs [EC]^?1, gave straight lines for both the monomer systems with nonzero intercepts supporting complex formation between Ce(IV) and EC. The rate of polymerization increases regularly with [Ce(IV)] up to 0.003 M, yielding an order of 0.41, then falls to 0.0055 M and again shows a rise at 0.00645 M for MMA polymerization. For AN polymerization, R _p shows a steep rise with [Ce(IV)] up to 0.001 M, and beyond this concentration R _p shows a regular increase with [Ce(IV)], yielding an order of 0.48. In the presence of constant [NO^? ₃], MMA and AN polymerizations yield orders of 0.36 and 0.58 for [Ce(IV)] variation, respectively. The rates of polymerization increased with an increase in EC and monomer concentrations: only at a higher concentration of EC (0.5 M) was a steep fall in R _p observed for both monomer systems. The orders with respect to EC and monomer for MMA polymerization were 0.19 and 1.6, respectively. The orders with respect to EC and monomer for AN polymerization were 0.2 and 1.5, respectively. A kinetic scheme involving oxidation of EC by Ce(IV) via complex formation, whose decomposition gives rise to a primary radical, initiation, propagation, and termination of the polymeric radicals by biomolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included.     

Cerium/Ascorbic Acid/Iodine Active Species for Redox Flow Energy Storage Battery

In this study, we developed a novel cerium/ascorbic acid/iodine active species to design a redox flow battery (RFB), in which the cerium nitrate hexahydrate [Ce(NO₃)₃·6H₂O] was used as a positive Ce³⁺/Ce⁴⁺ ion pair, and the potassium iodate (KIO₃) containing ascorbic acid was used as a negative I₂/I⁻ ion pair. In order to improve the electrochemical activity and to avoid cross-contamination of the redox pair ions, the electroless plating and sol–gel method were applied to modify the carbon paper electrode and the Nafion 117 membrane. The electrocatalytic and electrochemical properties of the composite electrode using methanesulfonic acid as a supporting electrolyte were assessed using the cyclic voltammetry (CV) test. The results showed that the Ce (III)/Ce (IV) active species presented a symmetric oxidation/reduction current ratio (1.09) on the C–TiO₂–PdO composite electrode. Adding a constant amount of ascorbic acid to the iodine solution led to a good reversible oxidation/reduction reaction. Therefore, a novel Ce/ascorbic acid/I RFB was developed with C–TiO₂–PdO composite electrodes and modified Nafion 117–SiO₂–SO₃H membrane using the staggered-type flow channel, of which the energy efficiency (EE%) can reach about 72%. The Ce/ascorbic acid/I active species can greatly reduce the electrolyte cost compared to the all-vanadium redox flow battery system, and it therefore has greater development potential.     

Effect of Cu(II)/H2 Salen complex on the non-conventional initiated emulsion polymerization of acrylonitrile

Radical polymerization of acrylonitrile was carried out in an emulsifier-free condition initiated by KHSO₅ catalyzed with Cu(II)/bis-salicylidene ethylene diamine (H₂ Salen) complex. The Cu(II) salt alone, Cu(II)/salicylaldehyde and Cu(II)/ethylene diamine have a retarding effect on the polymerization reaction, while the chelate of Cu(II) with the tetradentate Schiff base ligand, H₂ Salen has a catalytic effect. Prior to this, the catalytic effect of various bivalent transition metal salts and their couple with the Schiff base, H₂ Salen on the polymerization reaction has been examined to be not significant. The in situ developed complex produces the stable emulsion leading to high conversion. In the polymerization, the variables studied were the concentration of monomer, initiator, Cu(II), H₂ Salen and temperature. The overall activation energy was computed to be 13.1 kcal/mol. From the kinetic and spectral analyses, the mechanism of the initiator decomposition and initiation of polymerization by Cu(II)/H₂ Salen complex were suggested. The rate of polymerization (R_p) was found to be dependent on the monomer, initiator, Cu(II) ion, H₂ Salen concentrations to the 1.4, 0.3, 1.6, 1.5 power respectively. The polymers are characterized by IR and molecular weight by viscosity and GPC methods.     

Chain‐Growth Click Polymerization of AB2 Monomers for the Formation of Hyperbranched Polymers with Low Polydispersities in a One‐Pot Process

Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB₂ monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed Cu^I, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83.