Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006     

Cationic ring‐opening copolymerization behavior of trioxane and seven‐membered cyclic carbonate

Cationic ring‐opening copolymerization behavior of trioxane (TOX) and a seven‐membered cyclic carbonate, 1,3‐dioxepan‐2‐one (7CC) is described. When TOX and 7CC were cationically copolymerized under various feed ratios using trifluoromethane sulfonic acid (TfOH) as an initiator in nitrobenzene at 30 °C, 7CC was consumed faster than TOX and the decarboxylation was accompanied to afford the corresponding polyacetal–polycarbonate type copolymers containing poly(oxytetramethylene) units. The copolymer composition could be controlled by the feed ratio of 7CC, whose increase resulted in the high copolymer composition of the 7CC unit. The solubility of the copolymers increased as the increase of the 7CC content. Thermogravimetric, size‐exclusion chromatographic, and X‐ray analyses of the copolymers suggest that the sequences of the copolymer chains consist of the segments containing the units originated from 7CC and those with TOX unit‐rich compositions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 733–739, 2008     

Copolymerization of glycolide and trimethylene carbonate

The bulk ring‐opening copolymerization of glycolide with trimethylene carbonate was performed under different conditions. The influence of the composition, temperature, reaction time, and catalyst on the chain microstructure was studied by means of ¹H and ¹³C NMR spectroscopy. The final microstructure was found to be highly dependent on the transesterification reactions. The thermal behavior was sensitive to the composition and to the length of the glycolyl microblocks. Differential scanning calorimetry and X‐ray diffraction demonstrated that glycolyl‐rich sequences could give rise to a single crystalline phase, whereas trimethylene carbonyl units were incorporated into the amorphous phase. The synthesis of copolymers from the melt‐state transesterification of polyglycolide and poly(trimethylene carbonate) homopolymer mixtures was also studied. The hydrolytic degradation rate of the copolymers was found to depend on the microstructure and in general was enhanced with the degree of randomness. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 993–1013, 2006     

Obtaining aliphatic branched polycarbonates via simple copolymerization of trimethylene carbonate with cyclic carbonate containing pendant ester groups

Different possibilities for obtaining branched, functional carbonate copolymers are presented in this study. Copolymers were synthesized according to the ring‐opening polymerization (ROP) of the cyclic carbonate monomers, containing pendant ester groups. As an example, we chose copolymerization of ethyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate (MTC‐Et) with trimethylene carbonate (TMC), using zinc (II) and lanthanum (III) acetylacetonates as ROP initiators. The transesterification processes of ester groups in pendant, short chains, appearing during conducted copolymerization, led to the establishment of two different fractions: first‐branched and high molecular weight fraction and second‐linear and low molecular weight. The content of this high‐molecular‐weight fraction increased with both: the amount of MTC‐Et in started reaction mixture and the time of conducted copolymerization. Reactivity constants in studied reaction were determined. It was possible to obtain the copolymer fraction (ca. 30%) with molecular weight of up to a million g/mol, with a highly branched chain microstructure using lanthanum (III) acetylacetonate as initiator. Conclusions were based on detailed NMR analysis, determining microstructure of the copolymer chains and additionally on GPC and DSC measurement. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 808–819     

Synthesis and enzymatic degradation of 2‐methylene‐1,3‐dioxepane and methyl acrylate copolymers

Copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and methyl acrylate (MA) containing ester units both in the backbone and as pendant groups were synthesized by free‐radical copolymerization. The influence of reaction conditions such as the polymerization time, temperature, initiator concentration, and comonomer feed ratio on the yield, molecular weight, and copolymer composition was investigated. The structure of the copolymers was confirmed by ¹H NMR, ¹³C NMR, and IR spectroscopy. Differential scanning calorimetry indicated that the copolymers had a random structure. An NMR study showed that hydrogen transfer occurred during the copolymerization. The reactivity ratios of the comonomers were r_MDO = 0.0235 and r_MA = 26.535. The enzymatic degradation of the copolymers obtained was carried out in the presence of proteinase K or a crude enzyme extracted from earthworms. The experimental results showed that the higher ester molar percentage in the backbone caused a faster degradation rate. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2898–2904, 2003     

Isothiourea‐based lewis pairs for homopolymerization and copolymerization of 2,2‐dimethyltrimethylene carbonate with ε‐caprolactone and ω‐pentadecalactone

In this study, the homopolymerization of 2,2‐dimethyltrimethylene carbonate (DTC) and its copolymerizations with ε‐caprolactone (CL) were carried out in detail using the isothiourea‐based Lewis pairs comprised 2,3,6,7‐tetrahydro‐5H‐thiazolo(3,2‐a)pyrimidine and magnesium halides (MgX₂) with benzyl alcohol (BnOH) as the initiator. The copolymerization of DTC and CL via one‐pot addition produced randomly sequenced copolymers. On the other hand, a well‐defined linear poly(ε‐caprolactone)–block–poly(2,2‐dimethyltrimethylene carbonate) (PCL‐b‐PDTC) diblock copolymer was prepared by simple sequential ring‐opening polymerization of CL and DTC. In addition, poly(ω‐pentadecalactone)–block–PDTC diblock copolymer was successfully prepared by the same strategy. Moreover, PDTC–poly(ethylene glycol) (PEG)–PDTC triblock copolymer was synthesized in the presence of PEG 2000. The effects of different polymerization conditions on the polymerization reactions have been systematically discussed. The resulting polymers were characterized by the ¹H and ¹³C NMR spectra, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐ToF MS). The block copolyester structures were confirmed by the ¹³C NMR spectroscopy and DSC characterizations. These results indicated that the supposed mechanism was a dual catalytic mechanism. The proposed mechanism involved activation of the monomer via coordination to the MgX₂, and the initiator alcohol was deprotonated by base. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2349–2355     

Synthesis and properties of polyethylene with side‐chain triphenylamines as hole‐transporting materials

The copolymerization of ethylene with triphenylamine (TPA)‐containing α‐olefin monomer 1 using a rac‐Et(Ind)₂ZrCl₂ ( EBIZr )/MAO catalytic system was investigated to prepare polyethylene with pendent TPA groups. Despite the presence of a large excess of TPA moieties, the polymerization reactions efficiently produce copolymers of high‐molecular‐weight with the comonomer incorporation up to 6.1 mol % upon varying the comonomer concentration in the feed. Inspection of the aliphatic region of the ¹³C‐NMR spectrum and the estimated copolymerization parameters (r ₁ ≈ 0 for 1 and r_E ≈ 43 for ethylene) reveal the presence of isolated comonomer units in the polymer chain. While UV–vis absorption measurements of the copolymers show an invariant absorption feature, PL spectra exhibit a slightly red‐shifted emission with increasing content of 1 in the polymer chain. All the copolymers show high thermal stability (T_d5 > 436 °C), and the electrochemical stability toward oxidation is also observed. Particularly, the copolymer displays hole‐transporting ability for the stable green emission of Alq₃ when incorporated into the hole‐transporting layer of an electroluminescence device. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5816–5825, 2008     

Influence of chain microstructure on the hydrolytic degradation of copolymers from 1,3‐trimethylene carbonate and L‐lactide

Ring‐opening copolymerization of L ‐lactide (LLA) and 1,3‐trimethylene carbonate (TMC) blends with LLA/TMC feed ratios from 90/10 to 50/50 was realized at 110 or at 180 °C for various time periods, using low toxic zirconium (IV) acetylacetonate (Zr(Acac)₄) as initiator. The resulting copolymers exhibit different chain microstructures. Copolymers obtained at 110 °C exhibit a gradient chain structure with the presence of lactidyl sequences next to very short ones, and are semicrystalline. In contrast, copolymers obtained at 180 °C are amorphous because of a more random chain microstructure with the presence of larger amounts of medium sequences. Degradation of the copolymers was carried out in pH 7.4 phosphate buffer at 37 °C. Analytical techniques such as ¹H NMR, DSC, GPC, and XRD were used to monitor the degradation. Initially amorphous copolymers can remain amorphous during degradation because of the highly random unit's distribution, and equivalent LLA and TMC contents. However, initially amorphous copolymers containing larger amounts of lactidyl units are able to crystallize during degradation because of the presence of relatively long LLA blocks. Insofar, as initially semicrystalline copolymers are concerned, degradation occurs preferentially in the amorphous zones. Therefore, various degradation behaviors and degradation rates can be obtained by varying the chemical composition, chain microstructure, and morphology of PLLA‐PTMC copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3869–3879, 2009     

Chain microstructure of homogeneous ethylene‐1‐alkene copolymers and characteristics of single site catalysts using a direct 13C NMR peak method I. Theory and models

To describe the detailed microstructure of homogeneous ethylene‐1‐alkene copolymer chains and to study the characteristics of single site catalysts, Markov statistics are used to fit peak intensities of all relevant ¹³C NMR signals of series of copolymers. In the case of the occurrence of inverted comonomer units, a first‐order Markov terpolymer is applied, otherwise a second‐order Markov copolymer model. Chain propagation probabilities are obtained via modeling of the entire NMR spectrum. This procedure results in an accurate reproduction of the chain microstructure, including ethylene, 1‐alkene, and methylene sequence length distributions. If the experimental (co)monomer feeds are known, the reactivity ratios and the theoretical (co)monomer feeds are also found providing information about the copolymerization kinetics and the characteristics of the catalyst. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 722–737, 2006     

Amphiphilic PEG‐grafted poly(ester‐carbonate)s: Synthesis and diverse nanostructures in water

Novel biodegradable amphiphilic graft copolymers containing hydrophobic poly(ester‐carbonate) backbone and hydrophilic poly(ethylene glycol) (PEG) side chains were synthesized by a combination of ring‐opening polymerization and “click” chemistry. First, the ring‐opening copolymerization of 5,5‐dibromomethyl trimethylene carbonate (DBTC) and ε‐caprolactone (CL) was performed in the presence of stannous octanoate [Sn(Oct)₂] as catalyst, resulting in poly(DBTC‐co‐CL) with pendant bromo groups. Then the pendant bromo groups were completely converted into azide form, which permitted “click” reaction with alkyne‐terminated PEG by Huisgen 1,3‐dipolar cycloadditions to give amphiphilic biodegradable graft copolymers. The graft copolymers were characterized by proton nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectra and gel permeation chromatography measurements, which confirmed the well‐defined graft architecture. These copolymers could self‐assemble into micelles in aqueous solution. The size and morphologies of the copolymer micelles were measured by transmission electron microscopy and dynamic light scattering, which are influenced by the length of PEG and grafting density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Cinnamate‐functionalized poly(ester‐carbonate): Synthesis and its UV irradiation‐induced photo‐crosslinking

A functionalized cyclic carbonate monomer containing a cinnamate moiety, 5‐methyl‐5‐cinnamoyloxymethyl‐1,3‐dioxan‐2‐one (MC), was prepared for the first time with 1,1,1‐tri(hydroxymethyl) ethane as a starting material. Subsequent polymerization of the new cyclic carbonate and its copolymerization with L ‐lactide (LA) were successfully performed with diethyl zinc (ZnEt₂) as initiator/catalyst. NMR was used for microstructure identification of the obtained monomer and copolymers. Differential scanning calorimetry (DSC) was used to characterize the functionalized poly(ester‐carbonate). The results indicated that the copolymers displayed a single glass transition temperature (T_g) and the T_g decreased with increasing carbonate content and followed the Fox equation, indicative of a random microstructure of the copolymer. The photo‐crosslinking of the cinnamate‐carrying copolymer was also demonstrated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 161–169, 2009     

Microstructural characterization of acrylonitrile/pentyl acrylate copolymers by one and 2‐D NMR spectroscopy

Acrylonitrile/pentyl acrylate (A/P) copolymers of different monomer composition were prepared by solution polymerization using benzoyl peroxide as initiator. Copolymer compositions were determined by elemental analysis and quantitative ¹³C¹H‐NMR spectroscopy. The comonomer reactivity ratios, determined by both Kelen Tudos (KT) and nonlinear error in variables (EVM) methods are r_A = 0.75 and r_p = 0.45. 2‐D heteronuclear correlation spectroscopy (HSQC) was used to simplify the complex ¹H spectra of A/P copolymers in terms of configurational and compositional sequences. The microstructure was obtained in terms of the distribution of A‐ and P‐ centered triad sequences from ¹³C¹H‐NMR spectra of the copolymers. The copolymerization mechanism was found to follow a first order Markov Model. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 533–543, 1999     

Copolymerization with the feeding of one of the comonomers: Cationic activated monomer copolymerization of ε‐caprolactone with ethylene oxide

The cationic copolymerization of ε‐caprolactone with ethylene oxide (EO) under the conditions of activated monomer polymerization, that is, with a low‐molecular‐weight diol as an initiator and BF₃ etherate as a catalyst, was studied. To ensure the uniform composition of the resulting copolymers (telechelic oligodiols), the copolymerization was conducted with incremental feeding of the EO comonomer, which was more reactive in the cationic process. ¹H NMR analysis of samples isolated at different stages of the copolymerization indicated that the average composition of the copolymer was indeed nearly constant over the course of the copolymerization. Matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the products revealed, however, that for the same degree of polymerization, macromolecules containing different numbers of EO units were present. The observed distribution was compared with the distribution simulated under the assumption that the probability of incorporating a given unit depended only on the feed composition (nearly constant during the copolymerization). With this assumption, a good agreement between the observed and simulated spectra was obtained. This indicated that, even when the optimum conditions for the formation of a uniform copolymer were created, the individual macromolecules differed in composition because of the statistical character of the copolymerization. The results of differential scanning calorimetry analysis were compatible with such a conclusion; two melting peaks appeared on differential scanning calorimetry curves when a sample was heated immediately after fast cooling, and this may indicate the presence of different types of crystallites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3788–3796, 2005     

Helix‐sense‐selective copolymerization of triphenylmethyl methacrylate with chiral 2‐isopropenyl‐4‐phenyl‐2‐oxazoline

The asymmetric induction leading to a one‐handed helix was investigated in the anionic and radical copolymerization of triphenylmethyl methacrylate (TrMA) and (S)‐2‐isopropenyl‐4‐phenyl‐2‐oxazoline ((S)‐IPO), and highly isotactic copolymers with a reasonable optical activity were obtained. In the anionic copolymerization, the optical activity of the obtained copolymers depended on the polarity of solvents, and a highly optically active copolymer was produced in the copolymerization in toluene. The chiral oxazoline monomer functioned not only as a comonomer but also as a chiral ligand to endow the polymer with large negative optical rotation in the copolymerization with TrMA. The copolymers with small positive optical rotation were obtained in THF, indicating that IPO unit may work only as the chiral monomer that dictates the helical sense via copolymerization with TrMA. The isotacticity of the obtained copolymers depended on the contents of TrMA units in the copolymers, but was almost independent of the solvent for copolymerization. In the radical copolymerization, the obtained copolymers exhibited small optical activities. It seemed that the chiral monomer cannot induce one‐handed helical structure of TrMA sequences even if the sequences probably have a high isotacticity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 441–447     

Synthesis and Characterization of Novel Biodegradable Di‐ and Tri‐Block Copolymers Based on Ethylene Carbonate Polymer as Hydrophobic Segment

Synthesis of novel amphiphilic biodegradable block copolymers based on ethylene carbonate is reported in this study. Polyethylene glycol monomethyl ether (MeO‐PEO) and polyethylene glycol (PEG) of varying molar masses are used as macro‐initiator for ring‐opening polymerization of ethylene carbonate in the presence of sodium stannate trihydrate as a heterogeneous transesterification catalyst. Earlier elution of block copolymer from macro‐initiator in size exclusion chromatography (SEC) indicated the successful synthesis of the block copolymers. Ratios of both types of blocks are varied systematically. Liquid chromatography at critical conditions is used for the analysis of the non‐critical individual blocks, and if there are any critical segments that are not attached to the non‐critical block. To the best of our knowledge, this is the first report on the synthesis of ethylene carbonate‐based amphiphilic block copolymers. Chromatographic critical conditions of the ethylene carbonate polymer are also reported for the first time. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1887–1893     

Butadiene–isoprene copolymerization with V(acac)3‐MAO. Crystalline and amorphous trans‐1,4 copolymers

Butadiene‐isoprene copolymerization with the system V(acac)₃‐MAO was examined. Crystalline or amorphous copolymers were obtained depending on isoprene content. Both butadiene and isoprene units exhibit a trans‐1,4 structure and are statistically distributed along the polymer chain. Polymer microstructure, comonomer composition, and distribution along the polymer chain were determined by ¹³C and ¹H NMR analysis. The thermal and X‐ray behaviors of the copolymers were also investigated and compared with results from solid‐state ¹³C NMR experiments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4635–4646, 2007     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

Chain composition dependence of luminescence properties for copolymers of 2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene and 2,3‐diphenyl‐5‐octyl‐1,4‐phenylenevinylene

The copolymers of 2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene (MEH‐PV) and 2,3‐diphenyl‐5‐octyl‐1,4‐phenylenevinylene were prepared via the Gilch route with their chain compositions and the reactivity ratios of the monomers estimated by ¹H NMR spectroscopy. The results indicated that the copolymers tended to form an alternative copolymer as the feed ratio of the monomers closed to one‐half. When an individual copolymer solution in tetrahydrofuran was spun‐cast to form a film, the MEH‐PV units were able to attract the like units from the adjacent chains. As a result, the ultraviolet–visible absorption spectrum of the alternative copolymer in film form was broader than the spectra of those with different compositions. The photoluminescence spectra of the copolymers in film form exhibited the characteristic shoulder of poly(2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene), even though the content of MEH‐PV units was not great enough for the formation of repeat units in sequence. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2180–2186, 2003     

Novel aliphatic poly(ester‐carbonate) with pendant allyl ester groups and its folic acid functionalization

A series of novel poly(ester‐carbonate)s bearing pendant allyl ester groups P(LA‐co‐MAC)s were prepared by ring‐opening copolymerization of L ‐lactide (LA) and 5‐methyl‐5‐allyloxycarbonyl‐1,3‐dioxan‐2‐one (MAC) with diethyl zinc (ZnEt₂) as initiator. NMR analysis investigated the microstructure of the copolymer. DSC results indicated that the copolymers displayed a single glass‐transition temperature (T_g), which was indicative of a random copolymer, and the T_g decreased with increasing carbonate content in the copolymer. Then NHS‐activated folic acid (FA) first reacted with 2‐aminoethanethiol to yield FA‐SH; grafting FA‐SH to P(LA‐co‐MAC) in the presence of TEA produced P(LA‐co‐MAC)/FA. The structure of P(LA‐co‐MAC)/FA and its precursor were confirmed by ¹H NMR and XPS analysis. Cell experiments showed that FA‐grafted P(LA‐co‐MAC) had improved adhesion and proliferation behavior of vero cells on the polymer films. Therefore, the novel FA‐grafted block copolymer is expected to find application in drug delivery or tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1852–1861, 2008