A study of pyridinium‐type functional polymers. IV. Behavioral features of the antibacterial activity of insoluble pyridinium‐type polymers

The antibacterial activity of insoluble pyridinium‐type polymers with different structures against Escherichia coli suspended in sterilized and distilled water was investigated by a colony count method. The results show that the antibacterial activity of insoluble pyridinium‐type polymers, except for one containing I⁻, is characterized by an ability to capture bacterial cells in a living state by adsorption or adhesion, with the process of capturing bacterial cells being at least partially irreversible. This feature differs from the antibacterial activity of the corresponding soluble polymers, which is characterized by the ability to kill bacterial cells in water. In addition, insoluble pyridinium‐type polymers can also capture dead bacterial cells. This implies that insoluble pyridinium‐type polymers possess broad prospects for development in new water treatment techniques and whole‐cell immobilization techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 676–684, 2000     

Synthesis and characterization of quaternized poly(4‐vinylpyridine‐co‐styrene) membranes

Copolymers of 4‐vinylpyridine and styrene [P(4VP–St)s] with varied molar ratios were synthesized by means of radical mass polymerization with 2,2′‐azobisisobutyronitrile as an initiator. The insoluble (linear) pyridinium‐type polymers in the octyl‐pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP–St) with 1‐bromooctane. A series of membranes were prepared for use in electrochemistry. These membranes, prepared with quaternized poly(styrene‐co‐4‐vinylpyridine), were characterized by IRspectroscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetory, tensile strength measurements, scanning electron microscopy, and an electrochemistry workstation. Our emphasis was to select a membrane with appropriate properties for use in the electrochemistry field. A promising membrane was selected to use in the field of electrochemistry by these characterizations. This study could be the preparation for a study on the electrochemical properties of pyridinium‐type polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2146–2153, 2005     

A study of pyridinium-type functional polymers. I. Preparation and characterization of soluble pyridinium-type functional polymers

Copolymerization of 4-vinylpyridine (4VP) with styrene (St) was performed in ethanol using 2,2′-azobisisobutyronitrile (AIBN) as an initiator, and then a random copolymer P(4VP–St) was obtained. A soluble pyridinium-type polymer containing N-benzyl-4-vinylpyridinium bromide [Q-P(4VP–St)], was prepared by quaternization of P(4VP–St) with benzyl bromide (BzBr). The structures of P(4VP–St) and its quaternized product Q-P(4VP–St) were identified by FTIR. The 4VP content in P(4VP–St) and the pyridinium group content (C_q) in Q-P(4VP–St) were determined by nonaqueous titration and argentometry, respectively. The molecular weight of p(4VP–St) was characterized by intrinsic viscosity. In addition, the charge density σ of the soluble pyridinium-type polymers was measured by colloid titration, and the mathematical relation between σ and C_q was established as follows: σ = −0.090 + 0.942 C_q. A preliminary investigation was made into the viscosity behavior and electroconductivity of the Q-P(4VP–St)/polar solvent system. © 1996 John Wiley & Sons, Inc.     

Polyimide films with antibacterial surfaces from surface‐initiated atom‐transfer radical polymerization

BACKGROUND: Materials with antibacterial surface properties have attracted extensive scientific interest for research and development in the battle against microbial contamination. The application of antimicrobial polymers minimizes environmental problems and enhances the efficiency, selectivity and lifetime of the antimicrobial agents. In this paper polyimide (PI) films are chosen as the polymeric substrate to be modified due to the good thermal, mechanical and physicochemical properties of PI. The method of preparing PI films with antibacterial surfaces using surface‐initiated atom‐transfer radical polymerization (ATRP) is described. RESULTS: The results from X‐ray photoelectron spectroscopy showed that the surfaces at each stage were modified successfully. The pyridinium groups introduced on the PI surface possessed antibacterial properties and the bactericidal effect of the functionalized PI films on Escherichia coli was evaluated. Quaternization of the pyridine rings of the poly(4‐vinylpyridine) (P4VP) brushes gave rise to a high concentration of quaternary pyridinium groups on the PI film surfaces. The antibacterial efficiency of the modified PI film was dependent on the amount of quaternary pyridinium groups on the surface. CONCLUSION: In this research, functional polymer brushes of P4VP were prepared via surface‐initiated ATRP from PI films, followed by alkylation of the grafted P4VP with hexyl bromide. The surface functionalization method described has the advantage of being effective in conferring antibacterial properties on polymeric materials. Copyright © 2008 Society of Chemical Industry     

Study on synthesis and morphology control of poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres

Monodispersed crosslinked cationic poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] seed latexes were prepared by soapless emulsion polymerization, using 2,2′‐azobismethyl(propionamidine)dihydrochloride (V₅₀) as an initiator and divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The optimum condition to obtain monodispersed stable latex was investigated. It was found that the colloidal stability of the P4VP latex can be improved by adding an adequate amount of BA (BA/4VP = 1/4, w/w), and adopting a semicontinuous monomer feed mode. Subsequently, poly(4‐vinylpyridine‐co‐butyl acrylate)/Poly(styrene‐co‐butyl acrylate) [P(4VP‐BA)/P(ST‐BA)] composite microspheres were synthesized by seeded polymerization, using the above latex as a seed and a mixture of ST and BA as the second‐stage monomers. The effects of the type of crosslinker, the degree of crosslinking, and the initiators (AIBN and V₅₀) on the morphology of final composite particles are discussed in detail. It was found that P(4VP‐BA)/P(ST‐BA) composite microspheres were always surrounded by a PST‐rich shell when V₅₀ was used as initiator, while sandwich‐like or popcorn‐like composite particles were produced when AIBN was employed. This is because the polarity of the polymer chains with AIBN fragments is lower than for the polymer with V₅₀ fragments, hence leading to higher interfacial tension between the second‐stage PST‐rich polymer and the aqueous phase, and between PST‐rich polymer and P4VP‐rich seed polymer. As a result, the seed cannot be engulfed by the PST‐rich polymer. Furthermore, the decrease of T_g of the second‐stage polymer promoted phase separation between the seeds and the PST‐rich polymer: sandwich‐like particles formed more preferably than popcorn‐like particles. It is important knowledge that various morphologies different from PST‐rich core/P4VP‐rich shell morphology, can be obtained only by changing the initiator, considering P4VP is much more hydrophilic than PST. The zeta potential of composite particles initiated by AIBN in seeded polymerization shifted from a positive to a negative charge. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1190–1203, 2002     

Metal‐chloride‐anion‐containing polymers with expanded π‐conjugation systems derived from through‐space interactions in the piperazinium ring

Reactions of N‐(2,4‐dinitrophenyl)pyridinium chloride (salt(Cl)) with H⁺MCl₄^?1 (M ≡ Fe and Bi) resulted in an anion exchange between Cl^? and MCl₄^? to yield Zincke salts with metal chloride anions, namely salt(Fe) and salt(Bi), respectively. Reactions of the Zincke salts with piperazine resulted in ring‐opening of the pyridinium ring, yielding ionic polymers with 5‐piperazinium‐2,4‐dienylideneammonium metal chloride units, namely polymer(Fe) and polymer(Bi). The corresponding model compounds were synthesized via reactions using salt(Bi) or salt(Cl) as starting materials. The UV–visible spectra of the polymers had absorption maxima at longer wavelengths than those of the model compounds. This indicated that the π‐conjugation system is expanded along the polymer main chain. Superconducting quantum interference device measurements indicated that polymer(Fe) was paramagnetic. Cyclic voltammetry analysis suggested that the polymers underwent electrochemical oxidation. © 2019 Society of Chemical Industry     

Characterization of macroporous 1‐vinyl‐2‐pyrrolidone copolymers obtained by suspension polymerization

Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m²/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of heat‐resistant branched poly(styrene‐alt‐NPMI) by ATRP with divinylbenzene as the branching agent

Heat‐resistant branched poly(styrene‐alt‐NPMI) has been prepared via atom transfer radical polymerization (ATRP) of styrene (St) and N‐phenyl maleimide (NPMI) with divinylbenzene (DVB) as the branching agent in anisole at 80°C. Gas chromatography (GC) was used to determine the conversion of the reactants. Triple detection gel permeation chromatography (TD‐GPC) was used to analyze the copolymers. The results show that the polymerization yields primary chains predominately in the early stages and the formation of branched molecules occurs mainly when conversion is higher than 50%. As expected, higher dosage of DVB in our investigation range favors the formation of polymers with higher degree of branching. All the resulting branched poly(styrene‐alt‐NPMI)s have glass transition temperature (T_g) above 175°C, extrapolated initial weight loss temperature (T_i) above 410°C and statistic heat‐resistant index above 200°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polystyrene/poly(4‐vinylpyridine) triblock copolymers by reversible addition–fragmentation chain transfer polymerization and their self‐assembled aggregates in water

Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (M_w/M_n < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003     

Synthesis and biological activity of medium molecular weight polymers containing 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil

A new monomer, 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil (ETBFU), was synthesized by reaction of 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl chloride and 5‐fluorouracil. The homopolymer of ETBFU and its copolymers with acrylic acid (AA) or vinyl acetate (VAc) were prepared by photopolymerization using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETBFU and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The ETBFU content in poly(ETBFU‐co‐AA) and poly(ETBFU‐co‐VAc) was 43 and 14 mol%, respectively. The apparent number‐average molecular weight (M_n) of the polymers determined by GPC ranged from 8400 to 11 300. The in vitro cytotoxicity of the samples against mouse mammary carcinoma (FM3A), mouse leukaemia (P388), and human histiocytic lymphoma (U937) cancer cell lines decreased in the order 5‐FU ≥ ETBFU > poly(ETBFU) > poly(ETBFU‐co‐AA) > poly(ETBFU‐co‐VAc). The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐fluorouracil at all doses tested. © 2000 Society of Chemical Industry     

Water‐soluble copolymers. I. Biodegradability and functionality of poly[(sodium acrylate)‐co‐(4‐vinylpyridine)]

As a biodegradable functional polymer, poly[(sodium acrylate)‐co‐(4‐vinylpyridine)] [P(SA‐co‐4VP)] containing a small amounts of 4‐vinylpyridine groups were prepared and their biodegradability, dispersity, and complex performance were analyzed. The polymers can be useful as detergent builders and dispersants. It was found that the biodegradation of P(SA‐co‐4VP) was more conspicuous when content of the 4‐vinylpyridine in the copolymer was larger. This indicates that the 4‐vinylpyridine, which acts as biodegradable segments, should be incorporated into the polymer main chain in such a manner that they are digested by activated sludge. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1953–1957, 1999     

Synthesis of well‐defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations

This review presents firstly the synthesis of various dendritic hyperbranched polymers with well‐defined structures by generation‐based growth methodologies using living/controlled polymerization. Secondly, the synthesis of dendritic hyperbranched poly(methyl methacrylate)s (PMMAs) and their functionalized block copolymers using a novel iterative methodology is described. The methodology involves a two‐reaction sequence in each iterative process: (a) a linking reaction of α‐functionalized living anionic PMMA with tert‐butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)‐chain‐end‐functionalized polymer and (b) a transformation reaction of the SMP groups into BnBr functions. This reaction sequence is repeated several times to construct high‐generation (maximum seventh generation) dendritic hyperbranched polymers. Similar branched architectural block copolymers have also been synthesized by the same iterative methodology using other α‐functionalized living anionic polymers. Surface structures of the resulting dendritic hyperbranched block copolymers composed of PMMA and poly(2‐(perfluorobutyl)ethyl methacrylate) segments have been characterized using X‐ray photoelectron spectroscopy and contact angle measurements. Solution behaviors of dendritic hyperbranched PMMAs with different generations and branch densities are discussed based on their intrinsic viscosities, g′ values and R_h values. Copyright © 2007 Society of Chemical Industry     

Functionalization of poly(4‐vinyl pyridine) grafted cellulose by quaternization reactions and a study on the properties of postquaternized copolymers

Graft copolymers of 4‐vinyl pyridine (4‐VP) synthesized by using simultaneous gamma irradiation method were further functionalized by post polymer quaternization reactions at N: of the pyridine ring of the graft copolymers. Using the optimum grafting conditions reported earlier for the grafting of 4‐VP onto extracted cellulose, graft copolymer was synthesized in bulk and was further functionalized by quaternization with hexyl bromide (C₆H₁₃Br), benzyl chloride (C₆H₅CH₂Cl), n‐butyl bromide (C₄H₉Br), and maleic anhydride (MAnh). The quaternized polymers were studied for treatment of hardness of water, antibacterial action, emulsification properties, metal ion uptake and stability toward thermal degradation, and enzymatic and alkaline hydrolysis to evaluate the suitability of these polymers in harsh chemical, microbial, and thermal environments. The functionalized polymers were also characterized for surface morphology (SEM), elemental analysis and FTIR for investigations of structural aspects, and to obtain evidence for quaternization. The functionalized copolymers exhibit a range of properties that can be used in many fields of water purification technologies including antibacterial agents and ion exchangers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2454–2464, 2004     

Synthesis and spectral characterization of surface‐enriched polymer‐supported phase transfer catalysts and their effects on alkylation of phenylacetone

Polymer‐supported phase transfer catalysts with active sites mostly on the surface were prepared by suspension copolymerization of styrene (St), divinylbenzene (DVB), and vinylbenzyl chloride (VBC) with AIBN, followed by the quaternization of the resulting copolymer beads with triethylamine. Active sites on the surface were achieved by the delayed addition of functional monomer (VBC) to the partially copolymerized St/DVB. Polymer beads enriched with active sites were characterized by SEM, EDAX, FTIR, and ESCA. The electron micrographs showed that the exterior surface of delayed‐addition functional monomer catalysts (type 1) has a large number of nodules attached to the surface compared to the smooth surface exhibited by the conventional type 2 catalyst upon the simultaneous addition of all three monomers. In the EDAX analysis up to a depth of 100 Å, the surface chloride of type 1 peak intensity is greater (compared with type 2), indicating the  CH₂Cl enrichment on the surface. In FTIR, the peak intensities of the C N stretching (quaternary onium group) in type 1 are greater than those of type 2, confirming the evidence of more quaternization on the surface than in the bulk. From ESCA analysis to a depth of about 30 Å, it was found that type 1 (beads) contains 26% and type 2 contains 14% of covalent chloride on the surface, which strongly supports the grafting of VBC on St/DVB. In the estimation found by the Volhard method, type 1 has 4.73 m eq g⁻¹ and type 2 has 2.29 m eq g⁻¹ of ionic chloride, thus supporting the surface grafting of VBC. The catalytic activity of these two different catalysts was tested by studying the reaction, that is, the C‐alkylation of phenylacetone. The rate constants of this reaction for type 1 are almost twofold greater than those of type 2, a finding that could uphold the preceding experimental observations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 408–418, 2000     

Composite anion exchange membrane for alkaline direct methanol fuel cell: Structural and electrochemical characterization

A copolymer of 4‐vinylpyridine (4‐VP) and styrene was synthesized by radical mass polymerization using 2,2′‐azobisisobutyronitrile as initiator. An insoluble (linear) pyridinium‐type polymer was prepared by the reaction of P (4VP–St) with 1‐bromooctane. An anion exchange membrane was prepared using a composite of pyridinium‐type polymer and a fibrous woven structure for use in electrochemistry. The composite membrane was characterized by X‐ray diffraction, tensile strength, scanning electron microscopy, and electrochemistry measurements. The experimental results showed that the fibrous woven product had improved the tensile strength more than had the membrane made of a pyridinium‐type polymer alone. The composite membrane was used in alkaline fuel cells, and its properties were measured by electrochemical analysis. The ionic conductivity of the membrane was acceptable, but its performance as a direct methanol fuel cell (DMFC) was not. The primary reason for this was analyzed, and research is ongoing, with analysis to be discussed in later reports. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2248–2251, 2006     

Divinyl benzene cross‐linked HTPB‐based polyurethaneurea membranes for separation of p‐/o‐xylene mixtures by pervaporation

Cross‐linked hydroxy terminated polybutadiene (HTPB)‐based polyurethaneurea (PU), HTPB‐divinyl benzene (DVB)‐PU, was synthesized by a three‐step polymerization process. It was first used as membrane material to separate p‐/o‐xylene mixtures by pervaporation (PV). The effects of the content of cross‐linker DVB, feed concentration, and operating temperature on the PV performance of HTPB‐DVB‐PU membranes were investigated. The membranes demonstrated p‐xylene permselectivity as well as high total flux. The introduction of DVB significantly enhanced the temperature resistance ability of the HTPB‐DVB‐PU membranes. With increasing DVB content, the separation factor increased while the total flux decreased a little. The highest separation factor reaches 2.01 and the total flux is 33 g/m²h with feed concentration of 10 wt % p‐xylene at 30°C. These PV performances with increasing DVB content were explained in terms of the view point of chemical compositions and physical structures of the HTPB‐DVB‐PU membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Solid‐state NMR characterization of cyclomaltoheptaose (β‐cyclodextrin) polymers using high‐resolution magic angle spinning with gradients

Solid‐state nuclear magnetic resonance (NMR) techniques were used to characterize cyclomaltoheptaose (β‐cyclodextrin, β‐CD) polymers. These insoluble materials have been investigated by cross‐polarization magic angle spinning with dipolar decoupling (CP/MAS), magic angle spinning without dipolar decoupling (MAS), and high‐resolution magic angle spinning with gradients (HRMAS). These NMR spectra allow the assignment of the principal ¹H and ¹³C signals. The presence of two distinct components (cross‐linked β‐CD and polymerized epichlorohydrin) in the materials was clearly demonstrated. These polymers were used as sorbents and the resulting NMR spectra are presented and discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1288–1295, 2000     

New polymers from epoxidized soybean oil with pyridine derivatives

In this study 4‐methylpyridine (4MP), 4‐vinylpyridine (4VP) and poly(4‐vinylpyridine) (P4VP) were separately reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil based thermoset polymers. The addition reaction of pyridine with epoxide followed by a rearrangement results in formation of pyridone units and these were polymerized via a Diels–Alder reaction. DMA, DSC, TGA and IR spectroscopy were used for the characterization of the products. 4MP‐ESO, P4VP‐ESO and P4VP‐ESO‐in situ polymers were crosslinked yielding rigid infusible polymers. Glass transition temperatures (T_g) of 4MP‐ESO and P4VP‐ESO‐in situ were found as ?10.5 and 70.5 (32.3 as shoulder) °C respectively, by DMA analysis. Storage moduli of 4MP‐ESO and P4VP‐ESO‐in situ at 25°C were 13.7 and 187.2 MPa, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of nano‐sized poly(ethylene oxide) star microgels via reversible addition‐fragmentation transfer polymerization in selective solvents

Poly(ethylene oxide) (PEO) star microgels with a cross‐linked polystyrene core were successfully prepared by reversible addition‐fragmentation transfer polymerization of styrene (St) and divinylbenzene (DVB) with dithiobenzoate‐terminated PEO monomethyl ether (DTB‐MPEO) as macro chain transfer agent in mixtures of ethanol and tetrahydrofuran (THF). The formation of star polymers was affected by polymerization time, solvents and St:DVB:DTB‐MPEO molar ratios. Narrow polydispersed star microgels with high molecular weight were obtained under appropriate polymerization conditions. Transmission electron micrographs suggest that PEO star polymers could form nano‐size spherical micelles in mixtures of water and THF, which further demonstrates the amphiphilic nature of the star polymers. Copyright © 2006 Society of Chemical Industry     

Preparation of poly(divinylbenzene‐co‐N‐isopropylacrylamide) microspheres and their hydrogen‐bonding assembly behavior for raspberry‐like core‐corona polymer composite

Narrowdisperse poly(divinylbenzene‐co‐N‐isopropylacrylamide) (poly(DVB‐co‐NIPAM)) functional microspheres with the diameter in the range of 630 nm and 2.58 μm were prepared by distillation–precipitation polymerization in neat acetonitrile in the absence of any stabilizer. The effect of N‐isopropylacrylamide (NIPAM) ratio in the comonomer feed on the morphology of the resultant polymer particles was investigated in detail with divinylbenzene (DVB) as crosslinker and 2,2′‐azobisisobutyronitrile (AIBN) as initiator. The monodisperse poly(DVB‐co‐NIPAM) microspheres with NIPAM fraction of 20 wt % were selected for the preparation of raspberry‐like core‐corona polymer composite by the hydrogen‐bonding self‐assembly heterocoagulation with poly(ethyleneglycol dimethacrylate‐co‐acrylic acid) [poly(EGDMA‐co‐AA)] nanospheres. Both of the functional poly(DVB‐co‐NIPAM) microspheres and the core‐corona particles were characterized with scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and elemental analysis (EA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1350–1357, 2007