Maleimide Glycidyl Ether: A Bifunctional Monomer for Orthogonal Cationic and Radical Polymerizations

A novel bifunctional monomer, namely maleimide glycidyl ether (MalGE), prepared in a four‐step reaction sequence is introduced. This monomer allows for selective (co)polymerization of the epoxide group via cationic ring‐opening polymerization, preserving the maleimide functionality. On the other hand, the maleimide functionality can be copolymerized via radical techniques, preserving the epoxide moiety. Cationic ring‐opening multibranching copolymerization of MalGE with glycidol was performed, and a MalGE content of up to 24 mol% could be incorporated into the hyperbranched polymer backbone (M_n = 1000–3000 g mol⁻¹). Preservation of the maleimide functionality during cationic copolymerization was verified via NMR spectroscopy. Subsequently, the maleimide moiety was radically crosslinked to generate hydrogels and additionally employed to perform Diels‐Alder (DA) “click” reactions with (functional) dienes after the polymerization process. Radical copolymerization of MalGE with styrene (M_n = 5000–9000 g mol⁻¹) enabled the synthesis of a styrene copolymer with epoxide functionalities that are useful for versatile crosslinking and grafting reactions.

     

Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel,self-referencing fluorescence method

The effect of nanoscale confinement on the glass transition temperature, T_g, of freely standing polystyrene (PS) films was determined using the temperature dependence of a fluorescence intensity ratio associated with pyrene dye labeled to the polymer. The ratio of the intensity of the third fluorescence peak to that of the first fluorescence peak in 1-pyrenylmethyl methacrylate-labeled PS (MApyrene-labeled PS) decreased with decreasing temperature, and the intersection of the linear temperature dependences in the rubbery and glassy states yielded the measurement of T_g. The sensitivity of this method to T_g was also shown in bulk, supported PS and poly(isobutyl methacrylate) films. With free-standing PS films, a strong effect of confinement on T_g was evident at thicknesses less than 80–90 nm. For MApyrene-labeled PS with M_n = 701 kg mol⁻¹, a 41-nm-thick film exhibited a 47 K reduction in T_g relative to bulk PS. A strong molecular weight dependence of the T_g-confinement effect was also observed, with a 65-nm-thick free-standing film exhibiting a reduction in T_g relative to bulk PS of 19 K with M_n = 701 kg mol⁻¹ and 31 K with M_n = 1460 kg mol⁻¹. The data are in reasonable agreement with results of Forrest, Dalnoki-Veress, and Dutcher who performed the seminal studies on T_g-confinement effects in free-standing PS films. The utility of self-referencing fluorescence for novel studies of confinement effects in free-standing films is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2754–2764, 2008     

Free‐radical copolymerization of styrene and itaconic acid studied by 1H NMR kinetic experiments

The free‐radical copolymerization of itaconic acid (IA) and styrene in solutions of dimethylformamide and d₆‐dimethyl sulfoxide (50 wt %) has been studied by ¹H NMR kinetic experiments. Monomer conversion versus time data were used to estimate the ratio k_p · k_t^−0.5 for various comonomer mixture compositions. The ratio k_p · k_t^−0.5 varies from 5.2 · 10⁻² for pure styrene to 2.0 · 10⁻² mol^0.5 L^−0.5 s^−0.5 for pure IA, indicating a significant decrease in the rate of polymerization. Individual monomer conversion versus time traces were used to map out the comonomer mixture–composition drift up to overall monomer conversions of 60%. Within this conversion range, a slight but significant depletion of styrene in the monomer feed can be observed. This depletion becomes more pronounced at higher levels of IA in the initial comonomer mixture. The kinetic information is supplemented by molecular weight data for IA/styrene copolymers obtained by variation of the comonomer mixture composition. A significant decrease in molecular weight of a factor of 2 can be observed when increasing the mole fraction of IA in the initial reaction mixture from 0 to 0.5. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 656–664, 2001     

Hyperbranched polymers as scaffolds for multifunctional reversible addition–fragmentation chain‐transfer agents: A route to polystyrene‐core‐polyesters and polystyrene‐block‐poly(butyl acrylate)‐core‐polyesters

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain‐transfer (RAFT) agents. The polyester‐core‐based RAFT agents were subsequently employed to synthesize star polymers of n‐butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free‐radical process. Although the polyester‐core‐based RAFT agent mediated polymerization of n‐butyl acrylate displayed a linear evolution of the number‐average molecular weight (M_n) up to high monomer conversions (>70%) and molecular weights [M_n > 140,000 g mol^?1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene‐based system reached a maximum molecular weight at low conversions (≈30%, M_n = 45,500 g mol^?1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n‐butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene‐based star polymers were successfully cast into highly regular honeycomb‐structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003     

Stereoselective Copolymerization of Unprotected Polar and Nonpolar Styrenes by an Yttrium Precursor: Control of Polar‐Group Distribution and Mechanism

Styrene underwent unprecedented coordination–insertion copolymerization with naked polar monomers (ortho ‐/meta ‐/para ‐methoxystyrene) in the presence of a pyridyl methylene fluorenyl yttrium catalyst. High activity (1.26×10⁶ g mol_Y⁻¹ h⁻¹) and excellent syndioselectivity were observed, and high‐molecular‐weight copolymers (24.6×10⁴ g mol⁻¹) were obtained. The insertion rate of the polar monomers could be adjusted in the full range of 0–100 % simply by changing the loading of the polar styrene monomer. Strikingly, the copolymers had tapered, gradient, and even random sequence distributions, depending on the position of the polar methoxy group on the phenyl ring and thus on its mode of coordination to the active metal center, as shown by tracking the polymerization process and DFT calculations.     

Synthesis of end-functionalized (1 → 6)-2,5-anhydro-D-glucitols via anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol for preparing graft copolymers

End-functionalized (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitols ( 3a–c ) were synthesized by the anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol ( 1 ), followed by treatment with a terminating agent such as 4-vinylbenzyl ( 2a ), oxetanyl ( 2b ), and methacryloyl group ( 2c ). The end-functionalization proceeded in a high efficiency at 73–98%. The radical copolymerization of styrene with 3a yielded a polymer ( 5a ) whose GPC trace exhibited a unimodal peak. 5a was polystyrene with (1→6)-2,5-anhydro-3,4-di-O-methyl-D -glucitol as pendant groups whose structure was confirmed by the ¹H NMR spectrum.     

Gel permeation chromatographic determination of activation rate constants in nitroxide-controlled free radical polymerization, 1. Direct analysis by peak resolution

The dissociation rate constant k_d related to the homolytic cleavage of the C ON bond formed between a polystyrene (PS) and 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) is determined by adopting the gel permeation chromatography peak-resolution method to the styrene polymerization with a PS-TEMPO adduct as a probe and the radical initiator tert-butyl hydroperoxide. The result was given by the Arrhenius equation, k_d = A exp(−E/(RT)) with A = 3.0 × 10¹³ s⁻¹ and E = 124 kJ · mol⁻¹.     

Dendritic growth of poly(ε-caprolactone) crystals from compatible blends with poly(t-butyl acrylate) at the air/water interface

Thermodynamic analyses of surface pressure-area (Π-A) isotherms and Brewster angle microscopy (BAM) reveal that poly(ε-caprolactone) (PCL) with a weight average molar mass of M_w = 10 kg mol⁻¹ and polydispersity index of M_w/M_n = 1.25 and poly(t-butyl acrylate) (PtBA, M_w = 25.7 kg mol⁻¹; M_w/M_n = 1.07) form compatible blends as Langmuir films below the dynamic collapse transition for PCL at Π = 11 mN m⁻¹. For PCL-rich blends, in situ BAM studies reveal growth of PCL crystals for compression past the PCL collapse transition. PCL crystals grown in the plateau regime of the Π-A isotherm exhibit a dendritic morphology presumably resulting from the rejection of PtBA from the growing PCL crystals and hindered diffusion of PCL from the surrounding monolayer to the crystal growth fronts. The ability to transfer the PCL dendrites as Langmuir–Schaefer films onto silicon substrates spincoated with a polystyrene layer facilitates detailed morphological characterization by optical and atomic force microscopy (AFM). AFM reveals that the dendritic branching occurs along the {100} and {110} sector boundaries and is essentially independent of composition. AFM also reveals that the average thickness of PCL dendrites formed at room temperature (22.5 °C), ∼7–8 nm, is comparable with that of PCL crystals grown from single-component PCL Langmuir films and spincoated thin films. In contrast, for PtBA-rich blend films PCL crystallization is suppressed. These findings establish PCL blends as an ideal system for exploring the interplay between chain diffusion and crystal growth in a two-dimensional confined geometry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3300–3318, 2007     

Ultrathin self-assembled polymeric films on solid surfaces. I. Synthesis and characterization of acrylate copolymers containing alkyl disulfide side chains

Copolymers of 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate with variable compositions were synthesized, fractionated, and characterized by ¹H-NMR, IR, GPC, and viscometry. These copolymers were further modified via polymer analog esterification of copolymer hydroxy groups by a series of disulfide-containing carboxylic acids including lipoic acid and (n-pentyldithio) alkyl carboxylic acids (n-C₅H₁₁SS(CH₂)m? COOH, m = 10, 15, 22) in the presence of 1,3-dicyclohexylcarbodiimide (DCC). Esterification reactions were quantitative for copolymers possessing hydroxy monomer contents ≤ 40% when excess acid and DCC were present for sufficiently long reaction times (2–4 days) at room temperature. Copolymer DSC analysis demonstrates a systematic variation of T_g with copolymer composition in good agreement with ideal mixing theory. These disulfide-bearing copolymers spontaneously yield two-dimensional ultrathin polymer films with side chain-dependent layer thicknesses of 20–45 Å by solution adsorption onto freshly deposited gold surfaces. Such ultrathin polymer films are expected to have diverse applications as bound polymeric surface modification reagents. © 1993 John Wiley & Sons, Inc.     

Synthesis of a novel [60]fullerene pearl-necklace polymer,poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide)

A novel [60]fullerene pearl-necklace polymer, poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide), was synthesized by a direct polycondensation of trans-2-[60]fullerenobisacetic acid with 4,4′-diaminobenzophenone in the presence of large excesses of triphenyl phosphite and pyridine. In the present polymer, [60]fullerene pearls and diamine linkers were attached to each other by methano-carbonyl connectors. The molecular weight M_w of the polymer was determined to be 4.5 × 10⁴ on the basis of the TOF-MS, and a GPC analysis of the polymer using polystyrene standards showed a weight-average molecular weight of 5.3 × 10⁴. The UV-vis spectrum of the resultant polymer in N,N-dimethylacetamide (DMAc) exhibited a broad absorption (λ_max 310 nm, ε 2.1 × 10⁴ L · mol⁻¹ · cm⁻¹), tailing to longer wavelengths, and a fluorenscence peak centered at 550 nm was observed in DMAc. There was observed a large downfield-shift of the cyclopropane methyne proton in the ¹H-NMR spectra from 4.57 ppm of the ethyl ester to 5.78 ppm of the polyamide. These observations indicate that the present polyamide is a high-molecular-weight [60]fullerene pearl-necklace polymer and that the cyclopropane rings are efficient to make the [60]fullerene cages and the diamine components conjugatable. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3632–3637, 1999     

Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1-Vinylcyclohexene (VCH)

We report the first anionic polymerization of 1-vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2-disubstituted 1,3-diene proceeded quantitatively in cyclohexane at 25 °C with sec-butyllithium as an initiator. The obtained polymers have well-controlled molecular weights in the range of 5 to 142 kg mol⁻¹, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ ¹H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (r_Sty=2.55, r_VCH=0.39). P(VCH) obtained in cyclohexane with sec-BuLi as an initiator showed both 1,4- and 3,4-incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4-microstructure (up to 78 %) and elevated glass-transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well-defined polymer architectures and materials.     

Synthesis of poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

A series of new functional poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymers (EVAL‐g‐PS) with controlled molecular weight (M_n = 38,000–94,000 g mol^?1) and molecular weight distribution (M_w/M_n = 2.31–3.49) were synthesized via a grafting from methodology. The molecular structure and component of EVAL‐g‐PS graft copolymers were confirmed by the analysis of their ¹H NMR spectra and GPC curves. The porous films of such copolymers were fabricated via a static breath‐figure (BF) process. The influencing factors on the morphology of such porous films, such as solvent, temperature, polymer concentration, and molecular weight of polymer were investigated. Ordered porous film and better regularity was fabricated through a static BF process using EVAL‐g‐PS solution in CHCl₃. Scanning electron microscopy observation reveals that the EVAL‐g‐PS graft copolymer is an efficient compatibilizer for the blend system of low‐density polyethylene/polystyrene. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 516–524     

Linear Bio-Based Water Soluble Aromatic Polymers from Syringic Acid,S Type Degradation Fragment from Lignin

Degradation products of lignin, a widely available biopolymer, represent the most abundant feedstock for aromatics in nature. In this work, we focused on syringic acid, derived from lignin S-type monolignol, to synthesize different monomers for radical polymerization. The resulting polymers have molecular weight spanning over a wide range, which depends on the monomer, with up to M_n = 1,100,000 g.mol⁻¹ and Đ = 3.0. The novel polymers exhibit a thermal stability higher than 350°C and differentiated glass transition temperatures, ranging from 105 to 120°C. One of the monomers synthesized with a free carboxyl group was able to polymerize in water—instead of organic solvent—and resulted in a water soluble polymer. Monomers from syringic acid offer a unique bio-based alternative to oil-based polystyrene in industry for a wider range of application. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 540–547     

Propagation rate coefficients of isobornyl acrylate,tert‐butyl acrylate and 1‐ethoxyethyl acrylate: A high frequency PLP‐SEC study

Pulsed laser polymerization (PLP) coupled to size exclusion chromatography (SEC) is considered to be the most accurate and reliable technique for the determination of absolute propagation rate coefficients, k_p. Herein, k_p data as a function of temperature were determined via PLP‐SEC for three acrylate monomers that are of particular synthetic interest (e.g., for the generation of amphiphilic block copolymers). The high‐T_g monomer isobornyl acrylate (iBoA) as well as the precursor monomers for the synthesis of hydrophilic poly(acrylic acid), tert‐butyl acrylate (tBuA), and 1‐ethoxyethyl acrylate (EEA) were investigated with respect to their propagation rate coefficient in a wide temperature range. By application of a 500 Hz laser repetition rate, data could be obtained up to a temperature of 80 °C. To arrive at absolute values for k_p, the Mark‐Houwink parameters of the polymers have been determined via on‐line light scattering and viscosimetry measurements. These read: K = 5.00 × 10⁵ dL g⁻¹, a = 0.75 (piBoA), K = 19.7 × 10⁵ dL g⁻¹, a = 0.66 (ptBA) and K = 1.53 × 10⁵ dL g⁻¹, a = 0.85 (pEEA). The bulky iBoA monomer shows the lowest propagation rate coefficient among the three monomers, while EEA is the fastest. The activation energies and Arrhenius factors read: (iBoA): log(A/L mol⁻¹ s⁻¹) = 7.05 and E_A = 17.0 kJ mol⁻¹; (tBuA): log(A/L mol⁻¹ s⁻¹) = 7.28 and E_A = 17.5 kJ mol⁻¹ and (EEA): log(A/L mol⁻¹ s⁻¹) = 6.80 and E_A = 13.8 kJ mol⁻¹. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6641–6654, 2009     

Solution characterization of the novel organometallic polymer poly(ferrocenyldimethylsilane)

A series of four well‐defined poly(ferrocenyldimethylsilane) (PFS) samples spanning a molecular weight range of approximately 10,000–100,000 g mol⁻¹ was synthesized by the living anionic polymerization of dimethyl[1]silaferrocenophane initiated with n‐BuLi. The polymers possessed narrow polydispersities and were used to characterize the solution behavior of PFS in tetrahydrofuran (THF). The weight‐average molecular weights (M_w ) of the polymers were determined by low‐angle laser light scattering (LALLS), conventional gel permeation chromatography (GPC), and GPC equipped with a triple detector (refractive index, light scattering, and viscosity). The molecular weight calculated by conventional GPC, with polystyrene standards, underestimated the true value in comparison with LALLS and GPC with the triple detection system. The Mark–Houwink parameter a for PFS in THF was 0.62 (k = 2.5 × 10⁻⁴), which is indicative of fairly marginal polymer–solvent interactions. The scaling exponent between the radius of gyration and M_w was 0.54, also consistent with marginal polymer–solvent interactions for PFS in THF. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3032–3041, 2000     

Synthesis of comb polymers via grafting‐onto macromolecules bearing pendant diene groups via the hetero‐Diels‐Alder‐RAFT click concept

Comb polymers were synthesized by the “grafting‐onto” method via a combination of Reversible Addition‐Fragmentation Chain Transfer (RAFT) polymerization and the hetero‐Diels‐Alder (HDA) cycloaddition. The HDA reactive monomer trans, trans‐hexa‐2,4‐dienylacrylate (ttHA) was copolymerized with styrene via the RAFT process. Crosslinking was minimized by decreasing the monomer concentration—whilst keeping monomer to polymer conversions low—resulting in reactive backbones with on average one reactive pendant diene groups for 10 styrene units. The HDA cycloaddition was performed between the diene functions of the copolymer and a poly(n‐butyl acrylate) (PnBA) prepared via RAFT polymerization with pyridin‐2‐yldithioformate, which can act as a dienophile. The coupling reactions were performed within 24 h at 50 °C and the grafting yield varies from 75% to 100%, depending on the number average molecular weight of the PnBA (3500 g mol^?1 < M_n < 13,000 g mol^?1) grafted chain and the reaction stoichiometry. The molecular weights of the grafted block copolymers range from 19,000 g mol^?1 to 58,000 g mol^?1 with polydispersities close to 1.25. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1773–1781, 2010     

Synthesis of isotactic polystyrene with a rare-earth catalyst

Polymerization of styrene with the neodymium phosphonate Nd(P₅₀₇)/H₂O/Al(i-Bu)₃ catalytic system has been examined. The polymer obtained was separated into a soluble and an insoluble fraction by 2-butanone extraction. ¹³C-NMR spectra indicate that the insoluble fraction is isotactic polystyrene and the soluble one is syndiotactic-rich atactic polystyrene. The polymerization features are described and discussed. The optimum conditions for the polymerization are as follows: [Nd] = (3.5–5.0) × 10⁻² mol/L; [styrene] = 5 mol/L; [Al]/[Nd] = 6–8 mol/mol; [H₂O]/[Al] = 0.05–0.08 mol/mol; polymerization temperature around 70°C. The percent yield of isotactic polystyrene (IY) is markedly affected by catalyst aging temperature. With increase of the aging temperature from 40 to 70°C, IY increases from 9% to 48%. Using AlEt₃ and Al(i-Bu)₂H instead of Al(i-Bu)₃ decreases the yield of isotactic polystyrene. Different neodymium compounds give the following activity order: Nd(P₅₀₇)₃ > Nd(P₂₀₄)₃ > Nd(OPrⁱ)₃ > NdCl₃ + C₂H₅OH > Nd(naph)₃. With Nd(naph)₃ as catalyst, only atactic polystyrene is obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1773–1778, 1998     

Synthesis of central functionalized asymmetric triblock copolymers for surface modification and switchable surface properties

Well‐defined central functionalized asymmetric triblock copolymers (CFABC) were designed as a new type of polymer‐brush surface modifier with a short central functionalized block that could form chemical bonds with a suitable substrate surface. A combination of sequential living anionic polymerization and polymer modification reactions was used for the synthesis of two CFABCs: polystyrene‐b‐poly(4‐hydroxystyrene)‐b‐poly(methyl methacrylate) (3) and polystyrene‐b‐poly(4‐urethanopropyl triethoxysilylstyrene)‐b‐poly(methyl methacrylate) (4). The central block of 3, poly(4‐hydroxystyrene), was synthesized with a protected monomer, p‐[(tert‐butyldimethylsilyl)oxy]styrene, for the polymerization step, and this synthesis was followed by the hydrolysis of the silyl protecting group. To obtain polymer 4, the phenol functionality in 3 was converted to triethoxysilyl groups by a quantitative reaction with isocyanato propyl triethoxysilane. Gel permeation chromatography and NMR characterization indicated that the block copolymers possessed controlled molecular weights and narrow molecular weight distributions. Preliminary atomic force microscopy and X‐ray photoelectron spectroscopy analysis of the polymer brushes were reported. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3742–3750, 2000     

Emulsion copolymerization of styrene and methyl methacrylate

Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10^?5 for styrene polymerization and 0.4 × 10^?5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10^?5. Reactivity ratios measured in emulsion were r₁ (styrene) = 0.44, r₂ = 0.46. Those in bulk polymerizations were r₁ = 0.45, r₂ = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25–1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.     

Graft block copolymers of propargyl methacrylate and vinyl acetate via a combination of RAFT/MADIX and click chemistry: Reaction analysis

Propargyl methacrylate with its acetylene function protected with a silyl group is polymerized via the reversible addition fragmentation chain transfer (RAFT) process, using cyanoisopropyl dithiobenzoate (CPDB) as RAFT agent, and subsequently deprotected to afford a polymer backbone where each repeated unit is decorated with an acetylene functionality (1000 < M_n < 13,600 g mol⁻¹, 1.07 < PDI < 1.29). In parallel, an azide functionalized xanthate (ethoxythiocarbonylsulfanyl‐acetic acid 3‐azido‐propyl ester) was employed to prepare narrow polydisperse poly(vinyl acetate) (M_n = 850 g mol⁻¹, PDI = 1.20). The two polymers are conjugated by Huisgen 1,3‐dipolar cycloaddition to afford narrow polydisperse comb polymer (1.12 < PDI < 1.18, 3400 < M_n < 12,500 g mol⁻¹, based on linear polystyrene calibration, 4500 < M < 15,600 g mol⁻¹). The study places special emphasis on following the copper catalyzed 1,3‐dipolar cycloaddition via Fourier Transform Infrared Spectroscopy (FTIR) as well as via on‐line UV–Vis photospectrometry on several model compounds, i.e. the nonmonomer inserted azido‐xanthate RAFT/MADIX agent as well as a 2‐propargyl‐2‐bromopropionate and 3‐azidopropyl‐2‐bromopropionate model compounds. A suitable absorption band in the VIS at 666 nm (tentatively assigned to a charge transfer complex between copper(I) and the forming triazole moieties) is identified as a promising sensor for following the click reaction kinetics, thus allowing for the rapid assessment of reaction completion in an on‐line fashion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 155–173, 2008