Mn2(CO)10‐induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments

The controlled/living radical polymerization of vinyl acetate (VAc) and its copolymerization with methyl acrylate (MA) were investigated in bulk or fluoroalcohols using manganese complex [Mn₂(CO)₁₀] in conjunction with an alkyl iodide (R? I) as an initiator under weak visible light. The manganese complex induced the controlled/living radical polymerization of VAc even in the fluoroalcohols without any loss of activity. The R? I/Mn₂(CO)₁₀ system was also effective for the copolymerization of MA and VAc, in which MA was consumed faster than VAc, and then the remaining VAc was continuously and quantitatively consumed after the complete consumption of MA. The ¹H and ¹³C NMR analyses revealed that the obtained products are block copolymers consisting of gradient MA/VAc segments, in which the VAc content gradually increases, and homopoly(VAc). The use of fluoroalcohols as solvents increased the copolymerization rate, controllability of the molecular weights, and copolymerizability of VAc. The saponification of the VAc units in poly(MA‐grad‐VAc)‐block‐poly(VAc) resulted in the corresponding poly(MA‐co‐γ‐lactone)‐block‐poly(vinyl alcohol) due to the intramolecular cyclization between the hydroxyl and neighboring carboxyl groups in the gradient segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1343–1353, 2009     

Copper(0)‐mediated living radical polymerization of acrylonitrile: SET‐LRP or AGET‐ATRP

Cu(0)‐mediated living radical polymerization was first extended to acrylonitrile (AN) to synthesize polyacrylonitrile with a high molecular weight and a low polydispersity index. This was achieved by using Cu(0)/hexamethylated tris(2‐aminoethyl)amine (Me₆‐TREN) as the catalyst, 2‐bromopropionitrile as the initiator, and dimethyl sulfoxide (DMSO) as the solvent. The reaction was performed under mild reaction conditions at ambient temperature and thus biradical termination reaction was low. The rapid and extensive disproportionation of Cu(I)Br/Me₆‐TREN in DMSO/AN supports a mechanism consistent with a single electron transfer‐living radical polymerization (SET‐LRP) rather than activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). ¹H NMR analysis and chain extension experiment confirm the high chain‐end functionality of the resultant polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Copper(0)‐mediated living radical polymerization of acrylonitrile at room temperature

The copper(0)‐catalyzed living radical polymerization of acrylonitrile (AN) was investigated using ethyl 2‐bromoisobutyrate as an initiator and 2,2′‐bipyridine as a ligand. The polymerization proceeded smoothly in dimethyl sulphoxide with higher than 90% conversion in 13 h at 25 °C. The polymerization kept the features of controlled radical polymerization. ¹H NMR spectra proved that the resultant polymer was end‐capped by ethyl 2‐bromoisobutyrate species. Such polymerization technique was also successfully introduced to conduct the copolymerization of styrene (St) and AN to obtain well‐controlled copolymers of St and AN at 25 °C, in which the monomer conversion of St could reach to higher than 90%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Controlled/living copolymerization of styrene and acrylamide in DMF with Fe/TMEDA complex as catalyst

In this work, Fe(0)‐mediated single electron‐living radical copolymerization of styrene (St) and acrylamide (AM) was investigated at ambient temperature in N,N‐dimethylformamide using carbon tetrachloride as initiator and tetramethylethylenediamine as ligand. Kinetic studies showed that the copolymerization followed the first‐order kinetics model. The resulting copolymers of St and AM possessed predetermined molecular weights and narrow molecular weight distribution, which agreed with the character of controlled/living polymerization. On the basis of Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (NMR), the monomer reactivity ratios were calculated. The amount of ligand played an important role in copolymerization. The obtained polymer was characterized by FTIR, ¹H NMR, ¹³C NMR, and gel permeation chromatography. The living characteristics were demonstrated by chain extension experiment. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2919–2924     

Synthesis of double hydrophilic poly(ethylene oxide)‐b‐poly(2‐hydroxyethyl acrylate) by single‐electron transfer–living radical polymerization

In this study, the polymerization of (2‐hydroxyethyl) acrylate (HEA), in polar media, using Cu(0)‐mediated radical polymerization also called single‐electron transfer–living radical polymerization (SET‐LRP) is reported. The kinetics aspects of both the homopolymerization and the copolymerization from a poly(ethylene oxide) (PEO) macroinitiator were analyzed by ¹H NMR. The effects of both the ligand and the solvent were studied. The polymerization was shown to reach very high monomer conversions and to proceed in a well‐controlled fashion in the presence of tris[2‐(dimethylamino)ethyl]amine Me6‐TREN and N, N,N′, N″, N″‐pentamethyldiethylenetriamine (PMDETA) in dimethylsulfoxide (DMSO). SET‐LRP of HEA was also led in water, and it was shown to be faster than in DMSO. In pure water, Me₆‐TREN allowed a better control over the molar masses and polydispersity indices than PMDETA and TREN. Double hydrophilic PEO‐b‐PHEA block copolymers, exhibiting various PHEA block lengths up to 100 HEA units, were synthesized, in the same manner, from a bromide‐terminated PEO macroinitiator. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Zero‐valent bimetallic iron/copper catalyzed SET‐LRP: A dual activation by zero‐valent iron

In this work, bimetallic zero‐valent metal (Fe(0) powder and Cu(0) powder) was used to mediate the single electron transfer‐living radical polymerization (SET‐LRP) of methyl methacrylate at 25 °C in dimethyl sulfoxide. Different feed ratios of [Fe(0)]₀/[Cu(0)]₀ (0/1.5, 0.5/1, 0.75/0.75, 1/0.5, and 1.3/0.2) were explored. With the increase of Fe(0) feed, the polymerization rate was mildly depressed with a prolonged induction period. While, the control over the molecular weights was improved upon the increase of Fe(0). A best control (initiation efficiency = 91%) was achieved at [Fe(0)]₀/[Cu(0)]₀ = 1/0.5. A further increase of Fe(0) to the feed ratio of [Fe(0)]₀:[Cu(0)]₀ = 1.3: 0.2 led to a uncontrolled polymerization. Explorations of available solvents and ligands for this polymerization confirmed the SET‐LRP mechanism. It was suggested that Fe(0) might act as a dual role in this process: one was the activation agent for Cu(0), which favored a better control over the molecular weights; The other was an alternative catalyst for the activation of R‐X or P_n‐X to generate radicals, which assured a comparable polymerization rate as that of Cu(0). This work provided an alternative and economical catalyst for SET‐LRP, and would eventually reinforce the SET‐LRP technique. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ligand‐free Cu(0)‐mediated controlled radical polymerization of methyl methacrylate at ambient temperature

For the first time, ligand‐free Cu(0)‐mediated polymerization of methyl methacrylate (MMA) was realized by the selection of ethyl‐2‐bromo‐2‐phenylacetate as initiator at ambient temperature. The polymerization can reach up to 90% conversion within 5 h with dimethyl sulfoxide (DMSO) as solvent, while keeping manners of the controlled radical polymerization. Extensive investigation of this system revealed that for a well‐controlled Cu(0)‐mediated polymerization of MMA, the initiator should be selected with the structure as alkyl 2‐bromo‐2‐phenylacetate, and the solvent should be DMSO or N,N‐dimethylformamide. The selectivity for solvents indicated a typical single‐electron transfer‐living radical polymerization process. Scanning for other monomers indicated that under equal conditions, the polymerizations of other alkyl (meth)acrylates were uncontrollable. Based on these results, plausible reasons were discussed. The ligand‐free Cu(0)‐mediated polymerization showed its superiority with economical components and needless removal of Cu species from the resultant products. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Porphyrin derivatives act as vinylene monomers in TEMPO‐mediated radical copolymerization with styrene

In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)‐mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin (H₂TFPP) was conducted using 1‐phenyl‐1‐(2,2,6,6‐tetramethyl‐1‐piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size‐exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number‐average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO‐mediated mechanism. The traces recorded by the ultraviolet‐visible (UV‐vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H₂TFPP. This also indicated that H₂TFPP acted as a monomer and not as a terminator or a chain‐transfer agent under the conditions used. A benzyl radical addition to H₂TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain‐transfer agent, affording a reduced porphyrin, 2‐benzyl‐5,10,15,20‐tetrakis(pentafluorophenyl)chlorin 1 , via radical addition to the β‐pyrrole position. The UV‐vis spectrum of 1 was fairly similar to that of poly(styrene‐co‐H₂TFPP), indicating that H₂TFPP polymerized at its β‐pyrrole position in the TEMPO‐mediated radical polymerization. TEMPO‐mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)2

The radical polymerization of vinyl acetate (VAc) is moderated by iron(II) acetylacetonate (Fe(acac)₂) by the organometallic route (OMRP), as well as by degenerative transfer polymerization (DTP) when in the presence of excess radicals, through the formation of thermally labile organometallic Fe^III dormant species. The poly(vinyl acetate) (PVAc)‐Fe^III(acac)₂ dormant species has been isolated in the form of an oligomer and characterized by ¹H NMR, EPR, and IR methods, and then used as a single‐component initiator for the OMRP of VAc. The degree of polymerization of this isolated oligomeric species demonstrates the limited ability of Fe(acac)₂, relative to the Co(acac)₂ congener, to rapidly trap the growing PVAc radical chain. Control under OMRP conditions is improved by the presence of Lewis bases, especially PMe₂Ph. On the other hand, iron(II) phthalocyanine inhibits the radical polymerization of VAc completely. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3494–3504     

2‐Cyanoprop‐2‐yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. ¹H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007     

SET‐LRP of acrylates in the presence of radical inhibitors

The Cu(0)/Me₆‐TREN‐catalyzed single‐electron transfer mediated living radical polymerization (SET‐LRP) of methyl acrylate in the presence of the classic 4‐methoxyphenol free radical inhibitor was investigated. Kinetic experiments, combined with ¹H NMR, and MALDI‐TOF MS analysis of the resulting polyacrylates demonstrated that SET‐LRP is a robust synthetic method that does not require the purification of the monomers to remove the radical inhibitor. It is anticipated that these results will contribute to the expansion of technological and fundamental applications of SET‐LRP since it allows the synthesis of polymers with a structural perfection that previously was not accessible by any other method, starting from unpurified monomers, solvents, initiators, and ligands. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3174–3181, 2008     

SET‐LRP of acrylonitrile catalyzed by tin powder

Sn(0)‐mediated single electron transfer‐living radical polymerization (SET‐LRP) of acrylonitrile (AN) with carbon tetrachloride (CCl₄) as initiator and hexamethylenetetramine (HMTA) as ligand in N, N‐dimethylformamide (DMF) was studied. The polymerization obeyed first order kinetic. The molecular weight of polyacrylonitrile (PAN) increased linearly with monomer conversion and PAN exhibited narrow molecular weight distributions. Increasing the content of Sn(0) resulted in an increase in the molecular weight and the molecular weight distribution. Effects of ligand and initiator were also investigated. The block copolymer PAN‐b‐polymethyl methacrylate with molecular weight at 126,130 and polydispersity at 1.36 was successfully obtained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Nitroxide‐mediated radical copolymerization of methyl methacrylate controlled with a minimal amount of 9‐(4‐vinylbenzyl)‐9H‐carbazole

The controlled nitroxide‐mediated homopolymerization of 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) and the copolymerization of methyl methacrylate (MMA) with varying amounts of VBK were accomplished by using 10 mol % {tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino} nitroxide relative to 2‐({tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino}oxy)‐2‐methylpropionic acid (BlocBuilder?) in dimethylformamide at temperatures from 80 to 125 °C. As little as 1 mol % of VBK in the feed was required to obtain a controlled copolymerization of an MMA/VBK mixture, resulting in a linear increase in molecular weight versus conversion with a narrow molecular weight distribution (M_w /M_n ≈ 1.3). Preferential incorporation of VBK into the copolymer was indicated by the MMA/VBK reactivity ratios determined: r_VBK = 2.7 ± 1.5 and r_MMA = 0.24 ± 0.14. The copolymers were found significantly “living” by performing subsequent chain extensions with a fresh batch of VBK and by ³¹P NMR spectroscopy analysis. VBK was found to be an effective controlling comonomer for NMP of MMA, and such low levels of VBK comonomer ensured transparency in the final copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A minimal amount of acrylonitrile turns the nitroxide‐mediated polymerization of methyl methacrylate into an almost ideal controlled/living system

Nitroxide‐mediated controlled/living free‐radical polymerization of methyl methacrylate initiated by the SG1‐based alkoxyamine BlocBuilder was successfully performed in bulk at 80–99 °C with the help of a very small amount of acrylonitrile (AN, 2.2–8.8 mol %) as a comonomer. Well‐defined PMMA‐rich P(MMA‐co‐AN) copolymers were prepared with the number‐average molar mass, M_n, in the 6.1–32 kg mol^?1 range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by ¹H and ¹³C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain‐end functionalization by an alkoxyamine group was performed by means of ³¹P NMR spectroscopy and chain extensions from a P(MMA‐co‐AN)‐SG1 macroinitiator. It demonstrated the very high proportion of SG1‐terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 34–47, 2010     

Effect of catalyst systems and reaction conditions on the synthesis of cellulose‐g‐PDMAam copolymers by controlled radical polymerization

Various copper‐based catalyst systems and reaction conditions were studied in the graft copolymerization of N,N‐dimethylacrylamide (DMAam) with a cellulose‐based macroinitiator by controlled radical polymerization. The cellulose macroinitiator with degree of substitution DS = 0.44 was synthesized from dissolving softwood pulp in a LiCl/DMAc solution. The graft copolymerizations of DMAam, using the cellulose macroinitiator and various copper‐based catalyst systems, were then carried out in DMSO solutions. The copolymerization kinetics was followed by ¹H NMR. Water‐soluble cellulose‐g‐PDMAam copolymers were comprehensively characterized by ATR‐FTIR and ¹H NMR spectroscopies and SEC analyses. DLS and steady‐shear viscosity measurements revealed that when the DP_graft of the cellulose‐g‐PDMAam copolymer is high enough, the copolymer forms a more compact structure in water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Precisely controlled copper(0)‐catalyzed one‐pot reaction: Concurrent living radical polymerization and click chemistry

Copper(0)‐catalyzed one‐pot reaction combining living radical polymerization and “click chemistry” was investigated. By precisely tuning reaction time, three novel well‐defined polymers with different degree of carboxyl substitution, poly(propargyl methacrylate) (PPgMA), poly(1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate) (PCTMMA), and poly(1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate‐co‐propargyl methacrylate) (PCTMMA‐co‐PPgMA) were selectively obtained via Cu(0) powder/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) cocatalyzed LRP and click chemistry. In addition, gel permeation chromatography and ¹H NMR analysis in conjunction with FTIR spectroscopy elucidate that one‐pot process undergoes three steps due to a pronounced rate enhancement of click reaction: (1) generating new monomer, 1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate (CTMMA); (2) copolymerization of two monomers (CTMMA and PgMA); (3) building homopolymer PCTMMA. Surprisingly, in contrast to typical Cu(I)‐catalyzed atom transfer radical polymerization (ATRP), copper(0)‐catalyzed one‐pot reaction showed high carboxylic acid group tolerance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ultrafast SET‐LRP of methyl acrylate at 25 °C in alcohols

Alcohols are known to promote the disproportionation of Cu(I)X species into nascent Cu(0) and Cu(II)X. Therefore, alcohols are expected to be excellent solvents that facilitate the single‐electron transfer mediated living radical polymerization (SET‐LRP) mediated by nascent Cu(0) species. This publication demonstrates the ultrafast SET‐LRP of methyl acrylate initiated with bis(2‐bromopropionyloxy)ethane and catalyzed by Cu(0)/Me₆‐TREN in methanol, ethanol, 1‐propanol, and tert‐butanol and in their mixture with water at 25 °C. The structural analysis of the resulting polymers by a combination of ¹H NMR and MALDI‐TOF MS demonstrates the synthesis of perfectly bifunctional α,ω‐dibromo poly(methyl acrylate)s by SET‐LRP in alcohols. Moreover, this work provides an expansion of the list of solvents available for SET‐LRP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2745–2754, 2008     

Fast and effective copper(0)‐mediated simultaneous chain‐ and step‐growth radical polymerization at ambient temperature

Vinyl‐conjugated monomer (methyl acrylate, MA) and allyl 2‐bromopropanoate (ABP)‐possessing unconjugated C?C and active C? Br bonds were polymerized via the Cu(0)‐mediated simultaneous chain‐ and step‐growth radical polymerization at ambient temperature using Cu(0) as catalyst, N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand and dimethyl sulfoxide as solvent. The conversion was reached higher than 98% within 20 h. The obtained polymers showed block structure consisting of polyester and vinyl polymer moieties. The Cu(0)‐catalyzed simultaneous chain‐ and step‐growth radical polymerization mechanism was demonstrated by NMR, matrix‐assisted laser desorption ionization time‐of‐flight, and GPC analyses. Furthermore, the obtained copolymers of MA and ABP were further modified with poly(N‐isopropylamide) through radical thiol‐ene “click” chemistry from the terminal double bond. The thermoresponsive behavior of this block copolymer was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3907–3916     

Cobalt(II) phenoxy-imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

A series of cobalt(II) phenoxy-imine complexes (Co^II(FI)₂) have been synthesized to mediate the radical polymerization of vinyl acetate (VAc) and methyl acrylate (MA) to evaluate the influence of chelating atoms and configuration to the control of polymerization. The VAc polymerizations showed the properties of controlled/living radical polymerization (C/LRP) with complexes 1a and 3a , but the catalytic chain transfer (CCT) behaviors with complexes 2a , 1b , 2b , and 3b . The control of VAc polymerization mediated by complex 1a could be improved by decreasing the reaction temperature to approach the molecular weights that not only linearly increased with conversions but also matched the theoretical values and relatively narrow molecular weight distributions. The catalytic chain transfer polymerizations (CCTP) mediated by complexes 2a , 1b , 2b , and 3b were characterized by Mayo plots and the polymer chain end double bonds were observed by ¹H NMR spectra. The tendency toward C/LRP or CCTP in VAc polymerization mediated by Co^II(FI)₂ could be determined by the ligand structure. Cobalt complex coordinated by the ligand with more steric hindered and less electron-donating substituents favored the controlled/living radical polymerization. In contrast, the efficiency of CCT process could be enhanced by less steric hindered, more electron-donating ligands. The controlled/living radical polymerization of MA, however, could not be achieved by the mediation of these cobalt(II) phenoxy-imine complexes. Associated with the results of polymerization mediated by other cobalt complexes, this study implied that the configuration and spin state of cobalt complexes were more critical than the chelating atoms to the control behavior of radical polymerization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 101–113     

Synthesis and properties of comb polymers with semirigid mesogen‐jacketed polymers as side chains

A series of novel comb polymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐g‐polystyrene (PMPCS‐g‐PS), with mesogen‐jacketed rigid side chains were synthesized by the “grafting onto” method from α‐yne‐terminated PMPCS (side chain) and poly(vinylbenzyl azide) (backbone) by Cu(I)‐catalyzed 1,3‐dipolar cycloaddition click reaction. The α‐yne‐terminated PMPCS was synthesized by Cu(I)‐catalyzed atom transfer radical polymerization initiated by a yne‐functional initiator. Poly(vinylbenzyl azide) was prepared by polymerizing vinylbenzyl chloride using nitroxide mediated radical polymerization to obtain poly(vinylbenzyl chloride) as the precursor which was then converted to the azide derivative. The chemical structure and architectures of PMPCS comb polymers were confirmed by ¹H NMR, gel permeation chromatography, and multiangle laser light scattering. Both surface morphologies and solution behaviors were investigated. Surface morphologies of PMPCS combs on different surfaces were investigated by scanning probe microscopy. PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. The PMPCS comb polymers transferred to polymer‐modified silicon wafers using the Langmuir‐Blodgett technique showed a worm‐like chain conformation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012