Starch‐graft‐copolymer latexes initiated and stabilized by ozonolyzed amylopectin

A method is presented for synthesizing surfactant‐free latexes comprising a starch‐graft‐vinyl polymer, (1) starting with a suspension of the highly branched starch amylopectin, either native or degraded, (2) then using ozonolysis to create free‐radical initiation sites on this amylopectin scaffold, and (3) finally adding the monomer and inducing polymerization. The ozone simultaneously thins the starch and creates initiating/grafting sites on the starch, from which starch‐graft‐copolymer latexes can be grown. The encapsulation of starch inside the hydrophobic polymer particles created by a heterogeneous free‐radical polymerization process is demonstrated with energy‐dispersive spectroscopy; this is the first time that the particle morphology of such a latex has been so characterized. The data unambiguously prove that low‐molar‐mass degraded starch can be encapsulated within a latex particle. The underlying mechanisms have been explored, and data quantifying the rates of production of hydroperoxides by ozone, the thermal decomposition of the starch hydroperoxides so formed, and the degradation of amylopectin by ozone are reported. The activation energy for the thermal decomposition of the starch macroinitiator, determined in this work to be 125 ± 8 kJ mol⁻¹, is consistent with the proposition that the initiating species are mainly hydroperoxides. Colloidally stable poly(styrene‐co‐n‐butyl acrylate) latexes based on high‐molar‐mass amylopectin have been developed. These are stable against electrolytes (several months in 4 mol L⁻¹ NaCl), with 20% of the starch effectively grafted to the particles. Films cast from such latexes are more pliable than starch films and are readily redispersed in water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5832–5845, 2006     

A macromonomer approach to the synthesis of poly(1,1‐bis(ethoxycarbonyl)‐2‐vinyl cyclopropane‐graft‐dimethyl siloxane)

Poly(1,1‐bis(ethoxycarbonyl)‐2‐vinyl cyclopropane (ECVP)‐graft‐dimethyl siloxane) copolymers were prepared using a macromonomer approach. Poly(dimethyl siloxane) (PDMS) macromonomers were prepared by living anionic polymerization of cyclosiloxanes followed by sequential chain‐end capping with allyl chloroformate. These macromonomers were then copolymerized with ECVP. MALDI‐ToF mass spectrometry and ¹H NMR spectroscopy were used to show that the macromonomers had approximately 80% of the end groups functionalized with allyl carbonate groups. Gradient polymer elution chromatography showed that high yields of the graft copolymers were obtained, along with only small fractions of the PECVP and PDMS homopolymers. Differential scanning calorimetry showed that the low glass transition temperature (T_g) of the PDMS component could be maintained in the graft copolymers. However, the T_g was a function of polymer composition and the polymers produced had T_gs that ranged from ?50 to ?120 °C. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts via a combination of ATRP and click chemistry

We report on the synthesis of well‐defined amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts, poly(PMMA‐alt‐PNIPAM), via a combination of atom transfer radical polymerization (ATRP) and click reaction (Scheme 1 ). Firstly, the alternating copolymerization of N‐[2‐(2‐bromoisobutyryloxy)ethyl]maleimide (BIBEMI) with 4‐vinylbenzyl azide (VBA) affords poly(BIBEMI‐alt‐VBA). Bearing bromine and azide moieties arranged in an alternating manner, multifunctional poly(BIBEMI‐alt‐VBA) is capable of initiating ATRP and participating in click reaction. The subsequent ATRP of methyl methacrylate (MMA) using poly(BIBEMI‐alt‐VBA) as the macroinitiator leads to poly(PMMA‐alt‐VBA) copolymer brush. Finally, amphiphilic poly(PMMA‐alt‐PNIPAM) copolymer brush bearing alternating PMMA and PNIPAM grafts is synthesized via the click reaction of poly(PMMA‐alt‐VBA) with an excess of alkynyl‐terminated PNIPAM (alkynyl‐PNIPAM). The click coupling efficiency of PNIPAM grafts is determined to be ～80%. Differential scanning calorimetry (DSC) analysis of poly(PMMA‐alt‐PNIPAM) reveals two glass transition temperatures (T_g). In aqueous solution, poly(PMMA‐alt‐PNIPAM) supramolecularly self‐assembles into spherical micelles consisting of PMMA cores and thermoresponsive PNIPAM coronas, which were characterized via a combination of temperature‐dependent optical transmittance, micro‐differential scanning calorimetry (micro‐DSC), dynamic and static laser light scattering (LLS), and transmission electron microscopy (TEM). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2608–2619, 2009     

RAFT‐mediated emulsion polymerization of styrene using brush copolymer as surfactant macro‐RAFT agent: Effect of the brush copolymer sequence and chemical composition

The nonionic amphiphilic brush polymers such as poly[poly(ethylene oxide) methyl ether vinylphenyl‐co‐styrene] trithiocarbonate [P(mPEGV‐co‐St)‐TTC] and poly[poly(ethylene oxide) methyl ether vinylphenyl‐b‐styrene‐b‐poly(ethylene oxide) methyl ether vinylphenyl] trithiocarbonate [P(mPEGV‐b‐St‐b‐mPEGV)‐TTC] with different monomer sequence and chemical composition are synthesized and their application as macro‐RAFT agent in the emulsion RAFT polymerization of styrene is explored. It is found that the monomer sequence in the brush polymers exerts great influence on the emulsion RAFT polymerization kinetics, and the fast polymerization with short induction period in the presence of P(mPEGV‐co‐St)‐TTC is demonstrated. Besides, the chemical composition in the brush polymer macro‐RAFT agent effect on the emulsion RAFT polymerization is investigated, and the macro‐RAFT agent with high percent of the hydrophobic PS segment leads to fast and well controlled polymerization. The growth of triblock copolymer colloids in the emulsion polymerization is checked, and it reveals that the colloidal morphology is ascribed to the hydrophobic PS block extension, and the P(mPEGV‐co‐St) block almost have no influence just on the size of the colloids. This may be the first example to study the monomer sequence and the chemical composition in the macro‐RAFT agent on emulsion RAFT polymerization, and will be useful to reveal the block copolymer particle growth. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of novel photoactive polymer poly(vinyl alcohol)‐graft‐poly(vinyl naphthalene)

A copolymer of poly(vinyl naphthalene) grafted onto poly(vinyl alcohol) has been synthesized with nitroxide‐mediated controlled radical polymerization. By separating the processes of the generation of grafting sites and polymerization, we can avoid the formation of the homopolymer. Because of its architecture, the polymer is soluble in water, despite the high content of hydrophobic groups. The naphthalene chromophores tend to aggregate, forming hydrophobic microdomains in an aqueous solution. Those aggregates exist in a very constrained environment that leads to extraordinarily large redshifts of both the absorption and emission of the polymer. The polymer acts as an efficient photosensitizer in photoinduced electron transfer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2675–2683, 2006     

Synthesis and gas permeation properties of poly(vinyl chloride)‐graft‐poly(vinyl pyrrolidone) membranes

A series of amphiphilic graft copolymers consisting of poly(vinyl chloride) (PVC) main chains and poly(vinyl pyrrolidone) (PVP) side chains, i.e. PVC‐g‐PVP, was synthesized via atom transfer radical polymerization (ATRP), as confirmed by ¹H NMR, FT‐IR spectroscopy, and gel permeation chromatography (GPC). Transmission electron microscope (TEM) and small angle X‐ray scattering (SAXS) analysis revealed the microphase‐separated structure of PVC‐g‐PVP and the domain spacing increased from 21.4 to 23.9 nm with increasing grafting degree. All the membranes exhibited completely amorphous structure and high Young's modulus and tensile strength, as revealed by wide angle X‐ray scattering (WAXS) and universal testing machine (UTM). Permeation experimental results using a CO₂/N₂ (50/50) mixture indicated that as an amount of PVP in a copolymer increased, CO₂ permeability increased without the sacrifice of selectivity. For example, the CO₂ permeability of PVC‐g‐PVP with 36 wt% of PVP at 35°C was about four times higher than that of the pristine PVC membrane. This improvement resulted from the increase of diffusivity due to the disruption of chain packing in PVC by the grafting of PVP, as confirmed by WAXS analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

Structure–property relationships in modified natural rubber latexes grafted with methyl methacrylate and vinyl neo‐decanoate

A series of modified natural rubber latexes (NRLs) grafted with poly(methyl methacrylate) (PMMA) were prepared by seeded emulsion polymerization with NRL as the seed polymer. Two different redox systems, cumene hydroperoxide (CHP)/tetraethylene pentamine (TEPA) and tert‐butyl hydroperoxide (t‐BHP)/TEPA, were used to initiate polymerization, and phase mixing was promoted by the addition of vinyl neo‐decanoate (VneoD). The CHP/TEPA system was more efficient than t‐BHP/TEPA for the grafting of secondary polymers in modified natural rubber (NR). The enhanced phase mixing in the presence of VneoD was attributed to the solubility parameter of the VneoD‐rich methyl methacrylate–VneoD copolymer formed late in the reaction, lying between that of PMMA and NR, and the extent to which this polymer was grafted to the NR backbone. The viscoelastic properties of the polymers were investigated as a function of composition, temperature, and frequency; changes in viscoelastic behavior consistent with the presence of a high‐T_g PMMA phase (where T_g is the glass‐transition temperature) were observed. This suggested a degree of phase mixing that increased with increasing VneoD content and increasing flux of oxygen‐centered radicals within the NR particles. More phase mixing resulted in poorer film formation, which was consistent with the localization of a high‐T_g secondary polymer phase near the particle surface. The apparent concentration of PMMA near the surface of the particles was also observed with transmission electron microscopy. The localization of PMMA near the particle surfaces was consistent with the presumed locus of radical generation in these systems: the redox couple used to initiate the polymerization consisted of an oil‐soluble hydroperoxide and a water‐soluble amine that reacted predominantly at the water/particle interface. The viscoelastic properties of the modified NRLs that were prepared suggest that these synthetic procedures provide a means of controlling phase mixing and branching, such as for improving the suitability of these modified rubbers in pressure‐sensitive‐adhesive formulations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 809–822, 2002; DOI 10.1002/pola.10165     

Poly(ϵ‐caprolactone‐b‐glycolide) and poly(D,L‐lactide‐b‐glycolide) diblock copolyesters: Controlled synthesis,characterization, and colloidal dispersions

Living ω‐aluminum alkoxide poly‐ϵ‐caprolactone and poly‐D,L ‐lactide chains were synthesized by the ring‐opening polymerization of ϵ‐caprolactone (ϵ‐CL) and D,L ‐lactide (D,L ‐LA), respectively, and were used as macroinitiators for glycolide (GA) polymerization in tetrahydrofuran at 40 °C. The P(CL‐b‐GA) and P(LA‐b‐GA) diblock copolymers that formed were fractionated by the use of a selective solvent for each block and were characterized by ¹H NMR spectroscopy and differential scanning calorimetry analysis. The livingness of the operative coordination–insertion mechanism is responsible for the control of the copolyester composition, the length of the blocks, and, ultimately, the thermal behavior. Because of the inherent insolubility of the polyglycolide blocks, microphase separation occurs during the course of the sequential polymerization, resulting in a stable, colloidal, nonaqueous copolymer dispersion, as confirmed by photon correlation spectroscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 294–306, 2001     

Preparation of a copolymer of methyl methacrylate with a new monomer, 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate,and its initiation of the graft copolymerization of styrene with a controlled radical mechanism

A copolymer [P(MMA‐co‐TBPM)] was prepared by the radical polymerization of methyl methacrylate (MMA) and 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate (TBPM) with azobisisobutyronitrile as an initiator. TBPM was a new monomer containing an activated ester. Both the copolymer and TBPM were characterized with NMR, IR, and gel permeation chromatography in detail. It was confirmed that P(MMA‐co‐TBPM) could initiate the graft polymerization of styrene by the cleavage of the activated ester of the TBPM segment. This process was controllable, and the molecular weight of the graft chain of polystyrene increased with the increment of conversion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4398–4403, 2002     

Synthesis and characterization of synthetic polymer colloids colloidally stabilized by cationized starch oligomers

A method is developed for anchoring enzymatically degraded cationized starch as electrosteric stabilizers onto synthetic latices, using cerium(IV) to create free‐radical grafting sites on the starch. Direct anchoring of debranched starch onto a poly(methyl methacrylate) seed latex yields a latex stabilized by well‐defined oligosaccharides. Using α‐amylase to randomly cleave starch to form (1→4)‐α‐glucans, and a comonomer, N‐isopropyl acrylamide (NIPAM), whose corresponding polymer exhibits a lower critical solution temperature (LCST), creates a means to synthesize block (or graft) oligomers of oligosaccharide and synthetic polymer, which are water soluble at room temperature. Above 30 °C, they become amphiphilic and form self‐emulsifying nanoparticles (sometimes termed “frozen micelles”) from which a synthetic latex is grown after addition of methyl methacrylate, the collapsed NIPAM‐containing entities functioning as a type of in situ seed. This synthesis of stable synthetic latex particles is shown to have a high grafting efficiency. The starch fragments were characterized by ¹H solution‐state NMR before grafting, and ¹³C solid‐state cross‐polarization magic‐angle spinning (CP‐MAS) NMR was used to characterize the starch oligomers actually grafted on the final latex. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1836–1852, 2009     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene by a combination of cobalt‐mediated radical polymerization and atom transfer radical polymerization

Vinyl acetate and vinyl chloroacetate were copolymerized in the presence of a bis(trifluoro‐2,4‐pentanedionato)cobalt(II) complex and 2,2′‐azobis(4‐methoxy‐2,4‐dimethylvaleronitrile) at 30 °C, forming a cobalt‐capped poly(vinyl acetate‐co‐vinyl chloroacetate). The addition of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy after a certain degree of copolymerization was reached afforded 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐terminated poly(vinyl acetate‐co‐vinyl chloroacetate) (PVOAc–MI; number‐average molecular weight = 31,000, weight‐average molecular weight/number‐average molecular weight = 1.24). A ¹H NMR study of the resulting PVOAc–MI revealed quantitative terminal 2,2,6,6‐tetramethyl‐1‐piperidinyloxy functionality and the presence of 5.5 mol % vinyl chloroacetate in the copolymer. The atom transfer radical polymerization (ATRP) of styrene (St) was studied with ethyl chloroacetate as a model initiator and five different Cu‐based catalysts. Catalysts with bis(2‐pyridylmethyl)octadecylamine (BPMODA) or tris(2‐pyridylmethyl)amine (TPMA) ligands provided the highest initiation efficiency and best control over the polymerization of St. The grafting‐from ATRP of St from PVOAc–MI catalyzed by copper complexes with BPMODA or TPMA ligands provided poly(vinyl acetate)‐graft‐polystyrene copolymers with relatively high polydispersity (>1.5) because of intermolecular coupling between growing polystyrene (PSt) grafts. After the hydrolysis of the graft copolymers, the cleaved PSt side chains had a monomodal molecular weight distribution with some tailing toward the lower number‐average molecular weight region because of termination. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 447–459, 2007     

Synthesis and characterization of well‐defined poly(2‐hydroxyethyl methacrylate‐co‐styrene)‐graft‐poly(ε‐caprolactone) by sequential controlled polymerization

A new graft copolymer, poly(2‐hydroxyethyl methacrylate‐co‐styrene) ‐graft‐poly(?‐caprolactone), was prepared by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with coordination‐insertion ring‐opening polymerization (ROP). The copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) was carried out at 60 °C in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDTB) using AIBN as initiator. The molecular weight of poly (2‐hydroxyethyl methacrylate‐co‐styrene) [poly(HEMA‐co‐St)] increased with the monomer conversion, and the molecular weight distribution was in the range of 1.09 ～ 1.39. The ring‐opening polymerization (ROP) of ?‐caprolactone was then initiated by the hydroxyl groups of the poly(HEMA‐co‐St) precursors in the presence of stannous octoate (Sn(Oct)₂). GPC and ¹H‐NMR data demonstrated the polymerization courses are under control, and nearly all hydroxyl groups took part in the initiation. The efficiency of grafting was very high. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5523–5529, 2004     

Synthesis of graft copolymer by ATRP of MMA from poly(phenylacetylene)

The present report describes the synthesis of a densely grafted copolymer consisting of a rigid main chain and flexible side chains by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from an ATRP initiator‐bearing poly(phenylacetylene) [poly(BrPA)]. Poly(BrPA) was obtained by the polymerization of 4‐ethynylbenzyl‐2‐bromoisobutyrate using [Rh(NBD)Cl]₂ in the presence of Et₃N. The ¹H NMR spectrum showed that poly(BrPA) was in the cis‐transoid form. Upon heating at 30 °C for 24 h the cis‐transoid form was maintained. ATRP of MMA from the poly(BrPA) was carried out at 30 °C using CuX (X = Br, Cl) as the catalyst and N,N,N′,N′,N′‐pentamethyldiethylenetriamine as the ligand, and the resulting graft copolymers were investigated with ¹H NMR and SEC. To analyze the graft structure in more detail, the graft copolymers were hydrolyzed with KOH and the resultant poly(MMA) part was investigated with ¹H NMR and SEC. The polydispersity indexes of 1.25–1.45 indicated that the graft copolymers have well‐controlled side chains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6697–6707, 2006     

Polyolefin graft copolymers via living polymerization techniques: Preparation of poly(n‐butyl acrylate)‐graft‐polyethylene through the combination of Pd‐mediated living olefin polymerization and atom transfer radical polymerization

Poly(n‐butyl acrylate)‐graft‐branched polyethylene was successfully prepared by the combination of two living polymerization techniques. First, a branched polyethylene macromonomer with a methacrylate‐functionalized end group was prepared by Pd‐mediated living olefin polymerization. The macromonomer was then copolymerized with n‐butyl acrylate by atom transfer radical polymerization. Gel permeation chromatography traces of the graft copolymers showed narrow molecular weight distributions indicative of a controlled reaction. At low macromonomer concentrations corresponding to low viscosities, the reactivity ratios of the macromonomer to n‐butyl acrylate were similar to those for methyl methacrylate to n‐butyl acrylate. However, the increased viscosity of the reaction solution resulting from increased macromonomer concentrations caused a lowering of the apparent reactivity ratio of the macromonomer to n‐butyl acrylate, indicating an incompatibility between nonpolar polyethylene segments and a polar poly(n‐butyl acrylate) backbone. The incompatibility was more pronounced in the solid state, exhibiting cylindrical nanoscale morphology as a result of microphase separation, as observed by atomic force microscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2736–2749, 2002     

Synthesis of a novel block copolymer poly(ethylene oxide)‐block‐poly(4‐vinylpyridine) by combination of anionic ring‐opening and controllable free‐radical polymerization

The block copolymer poly(ethylene oxide)‐b‐poly(4‐vinylpyridine) was synthesized by a combination of living anionic ring‐opening polymerization and a controllable radical mechanism. The poly(ethylene oxide) prepolymer with the 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy end group (PEO_T) was first obtained by anionic ring‐opening polymerization of ethylene oxide with sodium 4‐oxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy as the initiator in a homogeneous process. In the polymerization UV and electron spin resonance spectroscopy determined the 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy moiety was left intact. The copolymers were then obtained by radical polymerization of 4‐vinylpyridine in the presence of PEO_T. The polymerization showed a controllable radical mechanism. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared, and NMR spectroscopy in detail. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4404–4409, 2002     

Proton conducting grafted/crosslinked membranes prepared from poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) copolymer

Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) (P(VDF‐co‐CTFE)) backbone was grafted with crosslinkable chains of poly(hydroxyl ethyl acrylate) (PHEA) and proton conducting chains of poly(styrene sulfonic acid) (PSSA) to produce amphiphilic P(VDF‐co‐CTFE)‐g‐P(HEA‐co‐SSA) graft copolymer via atom transfer radical polymerization (ATRP). Successful synthesis and microphase‐separated structure of the copolymer were confirmed by ¹H NMR, FT‐IR spectroscopy, and TEM analysis. Furthermore, this graft copolymer was thermally crosslinked with sulfosuccinic acid (SA) to produce grafted/crosslinked membranes. Ion exchange capacity (IEC) increased continuously with increasing SA contents but the water uptake increased up to 6 wt% of SA concentration, above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.062 S/cm at 6 wt% of SA concentration, resulting from competitive effect between the increase of ionic groups and the degree of crosslinking. XRD patterns also revealed that the crystalline structures of P(VDF‐co‐CTFE) disrupted upon graft polymerization and crosslinking. These membranes exhibited good thermal stability at least up to 250°C, as revealed by TGA. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of well‐defined amphiphilic graft copolymer bearing poly(2‐acryloyloxyethyl ferrocenecarboxylate) side chains via successive SET‐LRP and ATRP

A series of well‐defined ferrocene‐based amphiphilic graft copolymers, consisting of poly(N‐isopropylacrylamide)‐b‐poly(ethyl acrylate) (PNIPAM‐b‐PEA) backbone and poly(2‐acryloyloxyethyl ferrocenecarboxylate) (PAEFC) side chains, were synthesized by the combination of single‐electron‐transfer living radical polymerization (SET‐LRP) and atom transfer radical polymerization (ATRP). A new ferrocene‐based monomer, 2‐(acryloyloxy)ethyl ferrocenecarboxylate (AEFC), was prepared first and it can be polymerized via ATRP in a controlled way using methyl 2‐bromopropionate as initiator and CuBr/PMDETA as catalytic system in DMF at 40 °C. PNIPAM‐b‐PEA backbone was synthesized by sequential SET‐LRP of NIPAM and HEA at 25 °C using CuCl/Me₆TREN as catalytic system followed by the transformation into the macroinitiator by treating the pendant hydroxyls with α‐bromoisobutyryl bromide. The targeted well‐defined graft copolymers with narrow molecular weight distributions (M_w/M_n < 1.20) were synthesized via ATRP of AEFC initiated by the macroinitiator. The electro‐chemical behaviors of PAEFC homopolymer and PNIPAM‐b‐(PEA‐g‐PAEFC) graft copolymer were studied by cyclic voltammetry. Micellar properties of PNIPAM‐b‐(PEA‐g‐PAEFC) were investigated by transmission electron microscopy and dynamic light scattering. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4346–4357, 2009     

Tailored surface properties of monodispersed polymer particles with PCL hairy chains synthesized by hydroxyl‐initiated ring‐opening polymerization

Polymeric particles with hydrophobic PCL hairy chains were prepared by ring‐opening polymerization (ROP) from hydrophilic core particles, which were prepared by soap‐free emulsion polymerization of styrene, 2‐hydroxyethyl methacrylate, and divinylbenzene. Due to the incorporation of 2‐hydroxyethyl methacrylate in the core particles, hydroxyl groups on the surface of core particles could be obtained, and in the following ROP of ε‐caprolactone, the hydroxyl groups on the surface of the particles could effectively initiate the polymerization. Various reaction conditions were evaluated to produce hairy particles with optimal grafting efficiency. The presence of hydrophobic polymeric hairs on the surface of particles led to a dramatic improvement in their dispersibility in oil phase. By controlling the grafting amount of PCL on the surface of hydrophilic core particles, the surface properties of the hairy particles could be well tailored, represented the change of water contact angles from 75.0° to 114.6°. The prepared hairy particles were characterized by thermogravimetric analysis, scanning electron microscopy, differential scanning calorimetry, and Fourier transform infrared analysis. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4552–4563, 2007