Reversible addition‐fragmentation chain transfer polymerization of methacrylates containing hole‐ or electron‐transporting groups

The controlled/living radical polymerization of 2‐(N‐carbazolyl)ethyl methacrylate (CzEMA) and 4‐(5‐(4‐tert‐butylphenyl‐1,3,4‐oxadiazol‐2‐yl)phenyl) methacrylate (t‐Bu‐OxaMA) via reversible addition‐fragmentation chain transfer polymerization has been studied. Functional polymers with hole‐ or electron‐transfer ability were synthesized with cumyl dithiobenzoate as a chain transfer agent (CTA) and AIBN as an initiator in a benzene solution. Good control of the polymerization was confirmed by the linear increase in the molecular weight (MW) with the conversion. The dependence of MW and polydispersity index (PDI) of the resulting polymers on the molar ratio of monomer to CTA, monomer concentration, and molar ratio of CTA to initiator has also been investigated. The MW and PDI of the resulting polymers were well controlled as being revealed by GPC measurements. The resulting polymers were further characterized by NMR, UV‐vis spectroscopy, and cyclic voltammetry. The polymers functionalized with carbazole group or 1,3,4‐oxadiazole group exhibited good thermal stability, with an onset decomposition temperature of about 305 and 323 °C, respectively, as determined by thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 242–252, 2007     

Living free‐radical polymerization of sterically hindered monomers: Improving the understanding of 1,1‐disubstituted monomer systems

The sterically hindered, 1,1‐disubstituted monomers di‐n‐butyl itaconate (DBI), dicyclohexyl itaconate (DCHI), and dimethyl itaconate (DMI) were polymerized with reversible addition–fragmentation chain transfer (RAFT) free‐radical polymerization and atom transfer radical polymerization (ATRP). Cumyl dithiobenzoate, cumyl phenyl dithioacetate, 2‐cyanoprop‐2‐yl dithiobenzoate, 4‐cyanopentanoic acid dithiobenzoate, and S‐methoxycarbonylphenylmethyl dithiobenzoate were employed as RAFT agents to mediate a series of polymerizations at 60 °C yielding polymers ranging in their number‐average molecular weight from 4500 to 60,000 g mol^?1. The RAFT polymerizations of these hindered monomers displayed hybrid living behavior (between conventional and living free‐radical polymerization) of various degrees depending on the molecular structure of the initial RAFT agent. In addition, DCHI was polymerized via ATRP with a CuCl/methyl benzoate/N,N,N′,N″,N″‐pentamethyldiethylenetriamine/cyclohexanone system at 60 °C. Both the ATRP and RAFT polymerization of the hindered monomers displayed living characteristics; however, broader than expected molecular weight distributions were observed for the RAFT systems (polydispersity index = 1.15–3.35). To assess the cause of this broadness, chain‐transfer‐to‐monomer constants for DMI, DBI, and DCHI were determined (1.4 × 10^?3, 1.3 × 10^?3, and 1.0 × 10^?3, respectively) at 60 °C. Simulations carried out with the PREDICI program package suggested that chain transfer to monomer contributed to the broadening process. In addition, the experimental results indicated that viscosity had a pronounced effect on the broadness of the molecular weight distributions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3692–3710, 2006     

Tetraalkylammonium salt as photoinitiator of vinyl polymerization in organic and aqueous media: A mechanistic and laser flash photolysis study

N‐Dimethyl‐N‐[2‐(N,N‐dimethylamino)ethyl]‐N‐(1‐methylnaphthyl)ammonium tetrafluoroborate ( I ) was synthesized with the aim of obtaining a versatile photoinitiator for vinyl polymerization in organic solvents and water. Salt I was able to trigger the polymerization of acrylamide, 2‐hydroxyethylmethacrylate and styrene even at very low concentrations of the salt (～1.0 × 10^?5 M). Using laser flash photolysis and fluorescence techniques and analyzing the photoproduct distribution, we were able to postulate a mechanism for the photodecomposition of the salt. With irradiation, I undergoes an intramolecular electron‐transfer reaction to form a radical ion pair (RIP). The RIP intermediate decomposes into free radicals. The RIP and the free radicals are active species for initiating the polymerization. Depending on the concentration of the vinyl monomers studied, the initiation mechanism of the polymerization reaction changes. At large monomer concentrations, the RIP state is postulated to trigger the reaction by generating the anion radical of the olefin substrate. At a low monomer concentration, the free radicals produced by the decomposition of I are believed to start the chain reaction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 901–913, 2002; DOI 10.1002/pola.10166     

Spontaneous Single‐Crystal‐to‐Single‐Crystal Evolution of Two Cross‐Laminated Polymers

Two cases of spontaneous evolution of monomers to linear polymers having novel cross‐laminated topology are reported. We synthesized two peptide monomers N₃‐Gly‐Gly‐NH‐CH₂‐CCH and N₃‐Gly‐Gly‐Gly‐CH₂‐CCH and solved their crystal structures by single‐crystal X‐ray diffraction. They adopt H‐bonded crisscrossed layered packing in their crystals such that: (a) the monomers are aligned head‐to‐tail in 1D‐chain‐like arrays and parallel arrangement of such arrays forms a layer; (b) the proximally placed azide and alkyne motifs are in an orientation apt for their regiospecific cycloaddition; (c) each monomer having x peptide bonds is H‐bonded with 2x monomers disposed in intersecting arrangement, which pre‐organize 1D‐chain‐like arrays in adjacent layers in perpendicular orientation. These crystals underwent spontaneous single‐crystal‐to‐single‐crystal (SCSC) polymerization via azide–alkyne cycloaddition reaction to form triazolyl‐polyglycines, at room temperature. The crisscrossed arrangement of monomers in adjacent layers ensured the formation of cross‐laminated polymers.     

Are o‐nitrobenzyl (meth)acrylate monomers polymerizable by controlled‐radical polymerization?

We report on the controlled‐radical polymerization of the photocleavable o‐nitrobenzyl methacrylate (NBMA) and o‐nitrobenzyl acrylate (NBA) monomers. Atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer polymerization (RAFT), and nitroxide‐mediated polymerization (NMP) have been evaluated. For all methods used, the acrylate‐type monomer does not polymerize, or polymerizes very slowly in a noncontrolled manner. The methacrylate‐type monomer can be polymerized by RAFT with some degree of control (PDI ∼ 1.5) but leading to molar masses up to 11,000 g/mol only. ATRP proved to be the best method since a controlled‐polymerization was achieved when conversions are limited to 30%. In this case, polymers with molar masses up to 17,000 g/mol and polydispersity index as low as 1.13 have been obtained. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6504–6513, 2009     

The influence of vinyl activating groups on β‐allyl sulfone‐based chain transfer agents for tough methacrylate networks

In radical polymerization of monofunctional monomers, addition fragmentation chain transfer (AFCT) agents are well known to regulate polymerization and yield polymers with lower molecular weights and narrower molecular weight distributions. Papers concerning bulk photopolymerization of monomer mixtures with AFCT agents are rarely found in literature. In this article, AFCT reagents based on β‐allyl sulfones with different vinyl activating groups were synthesized and compared. The compounds were tested in mono‐ and difunctional monomer systems providing information about the influence on photoreactivity, molecular weight, as well as thermal and mechanical properties of the resultant polymers. Where more potent activating groups (‐Ph, ‐CN) markedly influenced polymerization at lower concentrations, the AFCT reagent with an ester activating group reacted at a similar rate to the methacrylate monomer (C_T ≈ 1) and provided the best overall performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1417‐1427     

Polar,functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

2‐[(N‐Benzyl‐N‐methylamino)methyl]‐1,3‐butadiene (BMAMBD), the first asymmetric tertiary amino‐containing diene‐based monomer, was synthesized by sulfone chemistry and a nickel‐catalyzed Grignard coupling reaction in high purity and good yield. The bulk and solution free‐radical polymerizations of this monomer were studied. Traditional bulk free‐radical polymerization kinetics were observed, giving polymers with 〈M_n〉 values of 21 × 10³ to 48 × 10³ g/mol (where M_n is the number‐average molecular weight) and polydispersity indices near 1.5. In solution polymerization, polymers with higher molecular weights were obtained in cyclohexane than in tetrahydrofuran (THF) because of the higher chain transfer to the solvent. The chain‐transfer constants calculated for cyclohexane and THF were 1.97 × 10^?3 and 5.77 × 10^?3, respectively. To further tailor polymer properties, we also completed copolymerization studies with styrene. Kinetic studies showed that BMAMBD incorporated into the polymer chain at a faster rate than styrene. With the Mayo–Lewis equation, the monomer reactivity ratios of BMAMBD and styrene at 75 °C were determined to be 2.6 ± 0.3 and 0.28 ± 0.02, respectively. Altering the composition of BMAMBD in the copolymer from 17 to 93% caused the glass‐transition temperature of the resulting copolymer to decrease from 64 to ?7 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3227–3238, 2001     

R‐RAFT approach for the polymerization of N‐isopropylacrylamide with a star poly(ε‐caprolactone) core

Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a more robust and versatile approach than other living free radical polymerization methods, providing a reactive thiocarbonylthio end group. A series of well‐defined star diblock [poly(ε‐caprolactone)‐b‐poly(N‐isopropylacrylamide)]₄ (SPCLNIP) copolymers were synthesized by R‐RAFT polymerization of N‐isopropylacrylamide (NIPAAm) using [PCL‐DDAT]₄ (SPCL‐DDAT) as a star macro‐RAFT agent (DDAT: S‐1‐dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate). The R‐RAFT polymerization showed a controlled/“living” character, proceeding with pseudo‐first‐order kinetics. All these star polymers with different molecular weights exhibited narrow molecular weight distributions of less than 1.2. The effect of polymerization temperature and molecular weight of the star macro‐RAFT agent on the polymerization kinetics of NIPAAm monomers was also addressed. Hardly any radical–radical coupling by‐products were detected, while linear side products were kept to a minimum by careful control over polymerization conditions. The trithiocarbonate groups were transferred to polymer chain ends by R‐RAFT polymerization, providing potential possibility of further modification by thiocarbonylthio chemistry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Pursuit of reinitiation efficiency of resonance‐stabilized monomeric allyl radical generated via “degradative monomer chain transfer” in allyl polymerization

For a deeper understanding of allyl polymerization mechanism, the reinitiation efficiency of resonance‐stabilized monomeric allyl radical was pursued because in allyl polymerization it is commonly conceived that the monomeric allyl radical generated via the allylic hydrogen abstraction of growing polymer radical from monomer, i.e., “degradative monomer chain transfer,” has much less tendency to initiate a new polymer chain and, therefore, this monomer chain transfer is essentially a termination reaction. Based on the renewed allyl polymerization mechanism in our preceding article, the monomer chain transfer constant in the polymerization of allyl benzoate was estimated to be 2.7 × 10^?2 at 80 °C under the polymerization condition, where the coupling termination reaction of growing polymer radical with allyl radical was negligible and, concurrently, the reinitiation reaction of allyl radical was enhanced significantly. The reinitiation efficiencies of monomeric allyl radical were pursued by the dead‐end polymerizations of allyl benzoate at 80, 105, and 130 °C using a small amount of initiators; they increased remarkably with raised temperature. Thus, the enhanced reinitiation reactivity of allyl radical at an elevated temperature could bias the well‐known degradative monomer chain transfer characteristic of allyl polymerization toward the chain transfer in common vinyl polymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

End‐group fidelity of copper(0)‐meditated radical polymerization at high monomer conversion: an ESI‐MS investigation

Copper(0)‐mediated radical polymerization (single electron transfer‐living radical polymerization) is an efficient polymerization technique that allows control over the polymerization of acrylates, vinyl chloride and other monomers, yielding bromide terminated polymer. In this contribution, we investigate the evolution of the end‐group fidelity at very high conversion both in the presence and in the absence of initially added copper (II) bromide (CuBr₂). High resolution electrospray‐ionization mass spectroscopy (ESI‐MS) allows determination of the precise chemical structure of the dead polymers formed during the polymerization to very high monomer conversion, including post polymerization conditions. Two different regimes can be identified via ESI‐MS analysis. During the polymerization, dead polymer results mainly from termination via disproportionation, whereas at very high conversion (or in the absence of monomer, that is, post‐polymerization), dead polymers are predominantly generated by chain transfer reactions (presumably to ligand). The addition of CuBr₂ significantly reduces the extent of termination by both chain transfer and disproportionation, at very high monomer conversion and under post‐polymerization conditions, offering a convenient approach to maintaining high end‐group fidelity in Cu(0)‐mediated radical polymerization. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of thiophene‐substituted N‐phenyl maleimide polymers by photoinduced radical polymerization

Two types of novel functionalized N‐[4‐(4′‐hydroxyphenyloxycarbonyl)phenyl]maleimide and N‐(4‐{[2‐(3‐thienyl)acetyl]oxyphenyl}oxycarbonylphenyl)maleimide (MIThi) were synthesized starting from 4‐maleimido benzoic acid. Photoinduced radical homopolymerization of MIThi and its copolymerization with styrene were performed at room temperature to give linear polymers containing pendant thienyl moieties using ω,ω‐dimethoxy‐ω‐phenylacetophenone as an initiator. Copolymers' compositions and the equilibrium constant (K) for electron donor–acceptor complex formation suggest an alternating nature of the copolymerization. The monomer reactivity ratios and Alfrey–Price Q,e values were also determined. The thermal behavior of the new synthesized monomers and polymers was investigated by differential scanning calorimetry and thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 995–1004, 2002     

Synthesis of Structurally Well‐Defined Telechelic Polymers by Organostibine‐Mediated Living Radical Polymerization: In Situ Generation of Functionalized Chain‐Transfer Agents and Selective ω‐End‐Group Transformations

Several organostibine chain‐transfer agents possessing polar functional groups have been prepared by the reactions of azo initiators and tetramethyldistibine ( 1 ). Carbon‐centered radicals thermally generated from the azo initiators were trapped by 1 to yield the corresponding organostibine chain‐transfer agents. The high yields observed in the synthesis of the chain‐transfer agents strongly suggest that distibines have excellent radicophilic reactivity. As the reactions proceeded under neutral conditions, functional groups that are incompatible with ionic conditions were incorporated into the chain‐transfer agents. The chain‐transfer agents were used in living radical polymerization to synthesize the corresponding α‐functionalized polymers. As the functional groups in the chain‐transfer agents did not interfere with the polymerization reaction, well‐controlled polymers possessing number‐average molecular weights (M_ns) predetermined by the monomer/transfer agent ratios were synthesized with low polydispersity indices (PDIs). The organostibanyl ω‐polymer ends were transformed into a number of different functional groups by radical‐coupling, radical‐addition, and oxidation reactions. Therefore, it was possible to synthesize well‐controlled telechelic polymers with the same and also with different functional groups at their α‐ and ω‐polymer ends. Distibine 1 was also found to increase PDI control in the living radical polymerization of styrene and methyl methacrylate (MMA) using a purified organostibine chain‐transfer agent. Well‐controlled poly(methyl methacrylate)s with M_n values ranging from 10 000 to 120 000 with low PDIs (1.05–1.15) were synthesized by the addition of a catalytic amount of 1 . The results have been attributed to the high reactivity of distibine 1 towards polymer‐end radicals, which are spontaneously deactivated to yield organostibine dormant species.     

Functionalization of polymers prepared by ATRP using radical addition reactions

Low molecular weight linear poly(methyl acrylate), star and hyperbranched polymers were synthesized using atom transfer radical polymerization (ATRP) and end‐functionalized using radical addition reactions. By adding allyltri‐n‐butylstannane at the end of the polymerization of poly(methyl acrylate), the polymer was terminated by allyl groups. When at high conversions of the acrylate monomer, allyl alcohol or 1,2‐epoxy‐5‐hexene, monomers which are not polymerizable by ATRP, were added, alcohol and epoxy functionalities respectively were incorporated at the polymer chain end. Functionalization by radical addition reactions was demonstrated to be applicable to multi‐functional polymers such as hyperbranched and star polymers.     

Synthesis of Multivalent Organotellurium Chain‐Transfer Agents by Post‐modification and Their Applications in Living Radical Polymerization

Functionalized or multivalent organotellurium chain‐transfer agents (CTAs) for living radical polymerization were synthesized by post‐modification, which involved the condensation between a carboxylic‐acid‐functionalized CTA and various amines in excellent yields without affecting the reactive tellurium moiety. The CTAs exhibited high synthetic versatility for radical polymerization and gave structurally well‐controlled polymers, such as multiarmed polymers, from various monomers. Because all new CTAs are easily available on a large scale by simple purification, the current method significantly facilitates macromolecular engineering based on organotellurium‐mediated radical polymerization (TERP).     

Synthesis and characterization of tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers via RAFT polymerization

A new bipyridine‐functionalized dithioester was synthesized and further used as a RAFT agent in RAFT polymerization of styrene and N‐isopropylacrylamide. Kinetics analysis indicates that it is an efficient chain transfer agent for RAFT polymerization of the two monomers which produce polystyrene and poly(N‐isopropylacrylamide) polymers with predetermined molecular weights and low polydispersities in addition to the end functionality of bipyridine. The bipyridine end‐functionalized polymers were further used as macroligands for the preparation of star‐shaped metallopolymers. Hydrophobic polystyrene macroligand combined with hydrophiphilic poly(N‐isopropylacrylamide) was complexed with ruthenium ions to produce amphiphilic ruthenium‐cored star‐shaped metallopolymers. The structures of these synthesized metallopolymers were further elucidated by UV–vis, fluorescence, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) as well as NMR techniques. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4225–4239, 2007     

Modeling the cyclopolymerization of diallyl ether and methyl α‐[(allyloxy)methyl]acrylate

The free‐radical cyclopolymerization of diallyl ether (1) and methyl α‐(allyloxymethyl)acrylate (2) has been modeled with the B3LYP/6‐31G* methodology, by making use of model compounds for the growing radicals. The cyclization of both monomers is exo, with activation barriers of 5.33 and 9.82 kcal/mol, respectively. To account for the polymerizabilities of these monomers, competing reactions have also been modeled. Although both monomers have a lower barrier for homopolymerization than for cyclization, cyclization dominates due to entropy. This explains the high cyclopolymerization vs. homopolymerization of monomer 2, although its monofunctional counterpart has been reported to homopolymerize well. It has also been shown that the degradative chain transfer by H‐abstraction from the allylic carbon is not effective with this monomer. Poor cyclopolymerization of the monomer 1 has been demonstrated by modeling the degradative chain transfer by H‐abstraction from the allylic carbon, which has been shown to compete very efficiently with polymerization reactions. Additionally, intermolecular propagation reaction has been shown to be facile due to cyclization, since the attacking monomer adopts a cyclic structure. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Charge‐transfer piperazine‐containing polymeric systems via ring‐opening metathesis polymerization

This article describes the synthesis of piperazine‐containing homopolymer systems via ring‐opening metathesis polymerization (ROMP). These systems were subsequently used as electron donors in the formation of charge‐transfer (CT) complexes. Using exo‐N‐(6‐bromohexyl)‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxamide as a starting material, monomers were synthesized to act as electron donors. The amine group at the “open” end of the piperazine was either left open or alkylated with various alkyl groups. The monomers' ability to act as electron donors and their polymerization rates were studied. After initial photometric titration studies using 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ) as an electron acceptor proved that these monomers would act as electron donors, they were subsequently polymerized into homopolymers via ROMP. The experimental results showed that a methanol:chloroform mixed solvent system enhanced the rate of polymerization over a single solvent (chloroform) system. Studies also showed that the alkylated piperazine‐containing monomer had a faster rate of polymerization than the secondary piperazine monomer. These monomers were used to make piperazine‐containing homopolymers via ROMP and the resulting polymers, like the monomers, also functioned as electron donors. Potential functions of these polymers include electronics, solar cells, optical systems, and biological applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5034–5043, 2009     

RAFT cryopolymerizations of N,N‐dimethylacrylamide and N‐isopropylacrylamide in moderately frozen aqueous solution

Aqueous reversible addition‐fragmentation chain transfer (RAFT) cryopolymerizations of N,N‐dimethylacrylamide (DMA) and N‐isopropylacrylamide (NIPAM) with potassium persulfate/sodium ascorbate as redox initiators were performed at ?15 °C. For the homopolymerizations, water‐soluble chain transfer agents (CTAs) of 2‐(1‐carboxy‐1‐methylethyl‐sulfanylthiocarbonylsulfanyl)‐2‐methylpropionic acid and 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methylpropionyl‐capped methoxy poly(ethylene glycol) were used. For the sequential block copolymerizations, the obtained trithiocarbonate‐functionalized polymers were used as macro‐CTAs. Although well‐defined homo and block polymers of DMA and NIPAM were synthesized and these RAFT cryopolymerizations were well controlled, their behavior depended on the monomers and CTAs. The polymerization kinetic and polymer structure were studied by proton nuclear magnetic resonance analysis and gel permeation chromatography measurement. Poly(N,N‐dimethylacrylamide)‐based cryogels crosslinked with reductively cleavable disulfide‐containing diacrylamide, N,N′‐bisacryloylcystamine, were synthesized via RAFT cryopolymerization. Scanning electron microscopy observation revealed that the porous structure of cryogels depended on the CTA used. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Synthesis of high-molecular-weight polyamine by radical polymerization ofN,N-diallyl-N-methylamine

The first synthesis of high-molecular-weight poly(N,N-diallyl-N-methylamine) by thermal (at 30 and 50°C) and photoinduced (at 21 °C) radical polymerization ofN,N-diallyl-N-methylamine (DAMA) in aqueous solution in the presence of an equimolar amount of trifluoroacetic acid (TFA) and by polymerization of the newly synthesized equimolar DAMA·TFA salt is reported. Data of¹H NMR spectroscopy indicate that the molecules of the monomer under chosen conditions are in the protonated form. This leads to a decrease in the contribution of the reaction of degradative chain transfer to the monomer and its transformation into effective chain transfer to the monomer. A bimolecular chain termination mechanism was estabilished and the possibility of controlling the polymerization rate and the molecular weight of the polymer was demonstrated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 430–436, March. 2000.     

Side‐chain ferrocene‐containing (meth)acrylate polymers: Synthesis and properties

A comprehensive investigation on the synthesis and properties of a series of ferrocene‐containing (meth)acrylate monomers and their polymers that differ in the linkers between the ferrocene unit and the backbone was carried out. The side‐chain ferrocene‐containing polymers were prepared via atom transfer radical polymerization. The kinetic studies indicated that polymerization of most monomers followed a “controlled”/living manner. The polymerization rates were affected by the vinyl monomer structures and decreased with an increase of the linker length. Methacrylate polymerization was much faster than acrylate polymerization. The optical absorption of monomers and polymers was affected by the linkers. Thermal properties of these polymers can be tuned by controlling the length of the linker between the ferrocene unit and the backbone. By increasing the length of the linker, the glass transition temperature ranged from over 100 to ?20 °C. Electrochemical properties of both monomers and polymers were characterized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011