An ambient self‐curable latex based on colloidal dispersions in water of two functionalized polymers and the thermally reversible crosslinked films generated

An ambient self‐curable latex (ASCL) was prepared by mixing colloidal dispersions in water of a chloromethylstyrene (CMS)‐functionalized polymer and a tertiary‐amine‐functionalized polymer. The two dispersions were obtained via the conventional emulsion copolymerization of CMS and 2‐(dimethylamino)ethylacrylate (DMAEA), respectively, with styrene (St), butyl acrylate (BA), or both. No visible coagulation was observed either in the blends after 6 months of storage or after the latexes were introduced into aqueous media with pHs in the range of 3–11. Continuous, transparent, crosslinked elastic films with smooth surfaces were obtained via casting and drying the ASCL at room temperature, when one or both of the two functional polymer particles contained BA monomeric units. Thermocompression cycles; swelling experiments; solubility tests; and ¹H NMR, IR, DSC, and transmission electron microscopy tests were carried out to investigate the crosslinking and morphology of the films. The following observations were made: (1) the crosslinks in the films were generated via the Menschutkin reaction (quaternization) between the  CH₂‐Cl groups of the CMS containing particles and the amine groups of the DMAEA containing particles; (2) the crosslinked films were thermally remoldable due to reversible decrosslinking (dequaternization) on heating and recrosslinking (requaternization) on cooling; and (3) phase separation in the films was observed when one of the functional polymers (for instance, the nonpolar CMS‐St copolymer) was incompatible with the other one (for instance, the polar BA‐DMAEA copolymer). The present ASCL might be useful in producing water‐borne coatings and adhesives, elastic films, and functional membranes. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 389–397, 2001     

Toughening of nylon‐6 with epoxy‐functionalized acrylonitrile‐butadiene‐styrene copolymer

Glycidyl methacrylate (GMA) functionalized acrylonitrile‐butadiene‐styrene (ABS) copolymers have been prepared via an emulsion polymerization process. The epoxy‐functionalized ABS (e‐ABS) particles were used to toughen nylon‐6. Molau tests and FTIR results showed the reactions between nylon‐6 and e‐ABS have taken place. Scanning electron microscopy (SEM) displayed the compatibilization reaction between epoxy groups of e‐ABS and nylon‐6 chain ends (amine or carboxyl groups), which improve disperse morphology of e‐ABS in the nylon‐6 matrix. The presence of only a small amount of GMA (1 wt %) within the e‐ABS copolymer was sufficient to induce a pronounced improvement of the impact strength of nylon‐6 blends; whereas further increase of the GMA contents in e‐ABS resulted in lower impact strength because of the crosslinking reaction between nylon‐6 and e‐ABS, resulting in agglomeration of the ABS particles. SEM results showed shear yielding of the nylon‐6 matrix and cavitation of rubber particles were the major toughening mechanisms. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2170–2180, 2005     

Emulsion procedures for thermally reversible covalent crosslinking of polymers

Quaternization and dequaternization of tertiary amine compounds were employed to obtain thermally reversible ionene networks from aqueous colloidal polymer dispersions prepared via emulsion polymerization. Chlorine‐functionalized polymers prepared via the emulsion copolymerization of styrene (St), butylacrylate (BA), or both with chloromethylstyrene, and amino‐functionalized polymers prepared via the emulsion copolymerization of St, BA, or both with 2‐(dimethylamino)ethylacrylate or 4‐vinylpyridine, were reacted without polymer separation, with a ditertiaryamine crosslinker and a dihalide crosslinker, respectively, to obtain crosslinked polymers. Crosslinked polymers were also obtained via the reaction of a chlorine‐functionalized polymer dispersion with an amino‐functionalized polymer dispersion or via the drying of the polymer blend prepared from the two kinds of dispersions. Reactive solubility experiments, flowability investigations (by thermocompression at ca. 215 °C), IR, and ¹H NMR analyses of the obtained crosslinked polymers indicated that the generated ionene bridges dequaternized on heating and requaternized on cooling. In comparison with solution crosslinking, no organic solvent was employed, and simple procedures were required for the preparation of the thermally reversible covalent crosslinked polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4373–4384, 2000     

Functionalized block copolymers for preparation of reactive self‐assembled surface patterns

Two phase separating block copolymers equipped with functional groups (acid and alkyne) were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization. Thin films of these materials were prepared and examined with regard to surface morphology, surface composition, and film stability. Self‐assembled structures with domain sizes of about 40 nm were detected through atomik force microscopy (AFM) analysis while X‐ray photoelectron spectroscopy measurements revealed a balanced surface exposure of the two segregated phases. Thus, reactive groups being present in both phases are specifically provided within nanoscopic surface areas. The films showed good stability on exposure to various solvents but the self‐organized surface patterns were only resistant toward ethanol. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Free radical and thermal curing of terpyridine‐modified terpolymers

Terpolymers bearing terpyridine as well as (meth)acrylates as free radical curable groups (UV‐curing) or hydroxyl groups (thermal curing with bis‐isocyanates) were synthesized and characterized using ¹H NMR, IR and UV‐vis spectroscopy as well as GPC. Subsequently, the ability of covalent crosslinking via the UV‐initiated polymerization of the acrylate groups was investigated. Moreover, the thermal covalent crosslinking via the reaction of hydroxyl functionalized terpolymer and bis‐isocyanate compounds could be successfully achieved. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4028–4035, 2004     

Synthesis of well‐defined polymers end‐functionalized with crosslinkable aziridine groups by living anionic polymerization

Well‐defined end‐functionalized polystyrene, poly(α‐methylstyrene), and polyisoprene with polymerizable aziridine groups were synthesized by the termination reactions of the anionic living polymers of styrene, α‐methylstyrene, and isoprene with 1‐[2‐(4‐chlorobutoxy)ethyl]aziridine in tetrahydrofuran at ?78 °C. The resulting polymers possessed the predicted molecular weights and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.1) as well as aziridine terminal moieties. The cationic ring‐opening polymerization of the ω‐monofunctionalized polystyrene having an aziridinyl group with Et₃OBF₄ gave the polymacromonomer, whereas the α,ω‐difunctional polystyrene underwent crosslinking reactions to afford an insoluble gel. Crosslinking products were similarly obtained by the reaction of the α,ω‐diaziridinyl polystyrene with poly(acrylic acid)‐co‐poly(butyl acrylate). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4126–4135, 2005     

Theoretical perspective on properties of DNA‐functionalized surfaces

The molecular recognition properties of DNA gave rise to many novel materials and applications such as DNA biosensors, DNA‐functionalized colloidal materials, DNA origami and DNA‐based directed surface assembly. The DNA‐functionalized surfaces are used in biosensors and for programmed self‐assembly of biological, organic and inorganic moieties into novel materials. However, surface density, length, and linker design of the surface functionalized DNAs significantly influence the properties of DNA‐driven assemblies and materials. This perspective discusses the understanding of structure and dynamics of DNA immobilized on the surfaces from the theoretical point of view including recent progress in analytical theories, atomistic simulations, and coarse‐grained models. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1563–1568, 2011     

Synthesis,characterization, and applications in photovoltaic cells of oxetane‐functionalized P3HT derivatives

Several crosslinkable oxetane‐functionalized copolymers, containing regio‐regular segments of 3‐hexylthiophene, are synthesized using the Grignard metathesis polymerization. The optical and electrochemical properties of the new polymers, both in the soluble and crosslinked forms, are reported. These polymers are used in the preparation of organic photovoltaics upon blending with PCBM as electron‐acceptor. The effect of the crosslinking of these copolymers, once the blend films are formed, on the devices performance is also studied. In particular, the insertion of the oxetane‐functionalized thiophene comonomers leads to a decrease of the devices performance, which is further decreased upon crosslinking of the copolymer. However, the stability of the devices overall improves upon crosslinking of the copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 652–663     

Characterization of electron beam irradiation blends based on metallocene ethylene‐1‐octene copolymer

Binary blends using metallocene ethylene‐1‐octene copolymer as matrix were prepared and subjected to electron beam (EB) irradiation (50, 100, and 200 kGy). Gel content and melt flow index values indicated that the blends were crosslinking. Fourier transform infrared‐ATR spectroscopy was used to study the crosslinking and oxidative degradation of the blends via tertiary carbon and carboxyl group formation, respectively. Thermal and mechanical properties were studied showing that the crystallinity of both matrix and dispersed phase decreased with irradiation dose, and that the thermoplastic elastomers with good mechanical properties may be obtained by EB irradiation. Chain branching and scission were also detected at all irradiation doses, although at the highest doses (200 kGy) a crosslinking reaction was the most predominantly observed effect. The successive self‐nucleation annealing technique was used to determine the EB irradiation effects on crystallization of some blends in which crosslinking and chain branching take place, modifying the chain's structure and therefore crystalline regions in the matrix and the dispersed phase. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2432–2440, 2007     

Miktoarm star copolymers via combination of RAFT arm‐first technique and aldehyde–aminooxy click reaction

A facile synthetic pathway to miktoarm star copolymers with multiple arms has been developed by combining reversible addition–fragmentation chain transfer (RAFT) arm‐first technique and aldehyde–aminooxy “click” coupling reaction. Star polystyrene (PS) with aldehyde functionalized core was initially prepared by RAFT arm‐first technique via crosslinking of the preformed linear macro‐RAFT agents using a newly designed aldehyde‐containing divinyl compound 6,6′‐(ethane‐1,2‐diylbis(oxy))bis(3‐vinylbenzaldehyde) (EVBA). It was then used as a multifunctional coupling agent for the subsequent formation of the second generation poly(ethylene glycol) (PEG) arms via the click coupling reaction between its aldehyde groups and aminooxy‐terminated PEGs. The possible formation of PS‐PEG miktoarm star copolymer with Janus‐like segregated structure in cyclohexanone was also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3323–3330, 2010     

Synthesis of well‐defined glycidyl methacrylate based block copolymers with self‐activation and self‐initiation behaviors via ambient temperature atom transfer radical polymerization

Well‐defined glycidyl methacrylate (GMA) based di‐ and triblock copolymers, with self‐activation and self‐initiation behaviors by incorporation of 2‐(diethylamino) ethyl methacrylate (DEA) blocks, were synthesized via ambient temperature atom transfer radical polymerization (ATRP). The stability of the GMA pendant oxirane rings in tertiary amine environments at ambient temperature was investigated. More importantly, both self‐activation behavior in oxirane ring opening addition reaction and self‐initiation behavior in post‐cure oxirane ring opening crosslinking of these block copolymers were evidenced by ¹H NMR studies. The results demonstrated that the reactivity of pendent oxirane rings was strongly dependant on the nucleophilicity and steric hindrance of tertiary amine moieties and temperature. This facilitated the synthesis of well‐defined block copolymers of GMA and DEA via sequential monomer addition ATRP, particularly for polymerization of GMA monomer at ambient temperature. Moreover, these one‐component GMA based block polymers have novel self‐activation and self‐initiation properties, rendering some potential applications in both enzyme immobilization and GMA‐based thermosetting materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2947–2958, 2007     

UV‐induced crosslinking of ring opening metathesis block copolymer micelles

Statistical and amphiphilic block copolymers bearing cinnamoyl groups were prepared by ring opening metathesis polymerization (ROMP). The UV‐induced [2 + 2] cycloaddition reaction of polymer bound cinnamic acid groups was studied in polymer thin films as well as in block copolymer micelles. In both cases, exposure to UV‐light for 10 min led to a crosslinking conversion of about 60%, as determined by FT‐IR spectroscopy and UV–vis absorption measurements. Time based IR‐spectroscopy revealed a maximum conversion of 78% reached after an irradiation time of about 16 min. For micelles obtained from polymers bearing 5 mol % or more cinnamoyl groups, the crosslinking reaction proceeded smoothly, yielding in crosslinked particles which were stable in a non‐selective solvent (CHCl₃). Diameters determined by dynamic light scattering in the selective solvent (MeOH) were similar for both, non‐crosslinked and crosslinked micelles, whereas diameters of crosslinked micelles in the non‐selective solvent (CHCl₃) were significantly larger compared to MeOH samples. This strategy of direct self assembly of block‐copolymers in a selective solvent followed by “clean” crosslinking, without the need for additional crosslinking reagents or crosslinking initiators, provides a straight forward approach toward ROMP‐based polymeric nano‐particles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2402–2413, 2008     

Covalent stabilization of nanostructures: Robust block copolymer templates from novel thermoreactive systems

Structurally robust block copolymer templates with feature sizes of approximately 10 nm were prepared from functionalized poly(methyl methacrylate)‐b‐polystyrene block copolymers. By the inclusion of benzocyclobutene crosslinking groups in the polystyrene block, the covalent stabilization of thin films to both thermal treatment and solvent exposure became possible. In addition, the crosslinking of the poly(styrene‐benzocyclobutene) domains at 220 °C, followed by the removal of poly(methyl methacrylate), provided a robust, crosslinked nanostructure with greater processing and fabrication potential. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1028–1037, 2005     

Tuning amphiphilicity/temperature‐induced self‐assembly and in‐situ disulfide crosslinking of reduction‐responsive block copolymers

New poly(ethylene oxide)‐based block copolymers (ssBCs) with a random copolymer block consisting of a reduction‐responsive disulfide‐labeled methacrylate (HMssEt) and a thermoresponsive di(ethylene glycol)‐containing methacrylate (MEO₂MA) units were synthesized. The ratio of HMssEt/MEO₂MA units in the random P(MEO₂MA‐co‐HMssEt) copolymer block enables the characteristics of well‐defined ssBCs to be amphiphilic or thermoresponsive and double hydrophilic. Their amphiphilicity or temperature‐induced self‐assembly results in nanoaggregates with hydrophobic cores having different densities of pendant disulfide linkages. The effect of disulfide crosslinking density on morphological variation of disulfide‐crosslinked nanogels is investigated. In response to reductive reactions, the partial cleavage of pendant disulfide linkages in the hydrophobic cores converts the physically associated aggregates to disulfide‐crosslinked nanogels. The occurrence of in‐situ disulfide crosslinks provides colloidal stability upon dilution. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2057–2067     

Facile preparation of core‐crosslinked micelles from azide‐containing thermoresponsive double hydrophilic diblock copolymer via click chemistry

Double hydrophilic diblock copolymer, poly(N,N‐dimethylacrylamide)‐b‐poly(N‐isopropylacrylamide‐co‐3‐azidopropylacrylamide) (PDMA‐b‐P(NIPAM‐co‐AzPAM), containing azide moieties in one of the blocks was synthesized via consecutive reversible addition‐fragmentation chain transfer polymerization. The obtained diblock copolymer molecularly dissolves in aqueous solution at room temperature, and can further supramolecularly self‐assemble into core‐shell nanoparticles consisting of thermoresponsive P(NIPAM‐co‐AzPAM) cores and water‐soluble PDMA coronas above the lower critical solution temperature of P(NIPAM‐co‐AzPAM) block. As the micelle cores contain reactive azide residues, core crosslinking can be facilely achieved upon addition of difunctional propargyl ether via click chemistry. In an alternate approach in which the PDMA‐b‐P(NIPAM‐co‐AzPAM) diblock copolymer was dissolved in a common organic solvent (DMF), the core‐crosslinked (CCL) micelles can be fabricated via “click” crosslinking upon addition of propargyl ether and subsequent dialysis against water. CCL micelles prepared by the latter approach typically possess larger sizes and broader size distributions, compared with that obtained by the former one. In both cases, the obtained (CCL) micelles possess thermoresponsive cores, and the swelling/shrinking of which can be finely tuned with temperature, rendering them as excellent candidates as intelligent drug nanocarriers. Because of the high efficiency and quite mild conditions of click reactions, we expect that this strategy can be generalized for the structural fixation of other self‐assembled nanostructures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 860–871, 2008     

Synthesis and self‐assembly of thymine‐ and adenine‐containing homopolymers and diblock copolymers

Atom transfer radical polymerizations (ATRPs) of 1‐(4‐methacryloyloxy‐benzyl)thymine (MAT) and 9‐(2‐methacryloyloxyethyl)adenine (MAA) were conducted for the synthesis of DNA‐base functionalized polymers. The association equilibrium constant K_asso between MAT and MAA and the complexation equilibrium constant K_comp between the corresponding polymers PMAT and PMAA were determined. A zipper‐like diblock copolymer, PMAT‐b‐PMAA, was prepared by anchoring the PMAT and PMAA blocks on the ortho‐positions of a pyridine ring via a successive two‐step ATRP. Dynamic light scattering and atom force microscopy confirmed that the block copolymer had a V‐shaped configuration in dimethylsulfoxide/N,N‐dimethylformamide. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5995–6006, 2006     

Synthesis and characterization of highly conjugated side‐group‐substituted benzo[1,2‐b:4,5‐b′]dithiophene‐based copolymer for use in organic solar cells

A new donor–acceptor (D–A) conjugated copolymer based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) was synthesized via a Stille cross‐coupling reaction. A highly conjugated thiophene‐based side group, tris(thienylenevinylene) (TTV), was incorporated into each BDT unit to generate the two‐dimensional D–A copolymer (PBDT‐TTV). An alkoxy‐substituted BDT‐based TPD copolymer (PBDT‐OR) was synthesized using the same polymerization method for comparison. PBDT‐TTV thin films produced two distinct absorption peaks. The shorter wavelength absorption (458 nm) was attributed to the BDT units containing the TTV group, and the longer wavelength band (567–616 nm) was attributed to intramolecular charge transfer between the BDT donor and the TPD acceptor. The highest occupied molecular orbital energy levels of PBDT‐OR and PBDT‐TTV were calculated to be −5.53 and −5.61 eV, respectively. PBDT‐TTV thin films harvested a broad solar spectrum covering the range 300–700 nm. A comparison with the PBDT‐OR films revealed stronger interchain π–π interactions in the PBDT‐TTV films and, thus, a higher hole mobility. A polymer solar cell device prepared using PBDT‐TTV as the active layer was found to exhibit a higher power conversion efficiency than a device prepared using PBDT‐OR under AM 1.5 G (100 mW/cm²) conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 653–660     

Facile one‐pot/one‐step technique for preparation of side‐chain functionalized polymers: Combination of SET‐RAFT polymerization of azide vinyl monomer and click chemistry

An azido‐containing functional monomer, 11‐azido‐undecanoyl methacrylate, was successfully polymerized via ambient temperature single electron transfer initiation and propagation through the reversible addition–fragmentation chain transfer (SET‐RAFT) method. The polymerization behavior possessed the characteristics of “living”/controlled radical polymerization. The kinetic plot was first order, and the molecular weight of the polymer increased linearly with the monomer conversion while keeping the relatively narrow molecular weight distribution (M_w/M_n ≤ 1.22). The complete retention of azido group of the resulting polymer was confirmed by ¹H NMR and FTIR analysis. Retention of chain functionality was confirmed by chain extension with methyl methacrylate to yield a diblock copolymer. Furthermore, the side‐chain functionalized polymer could be prepared by one‐pot/one‐step technique, which is combination of SET‐RAFT and “click chemistry” methods. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Syntheses of polyolefin‐based stereoregular diblock copolymers for self‐assembled nanostructures

The preparation of polyolefin‐based stereoregular diblock copolymers by postpolymerization of ethenyl‐capped syndiotactic polypropylene‐based propylene/norbornene copolymer (sPP‐based P‐N copolymer) led to the successful generation of a structurally uniform stereoregular diblock copolymer for self‐assembly studies. The ethenyl‐capped prepolymer was prepared by conducting propylene/norbornene copolymerization in the presence of Me₂C(Cp)(Flu)ZrCl₂/MAO. Ozonolysis of ethenyl‐capped sPP‐based P‐N copolymer provided the formyl group end‐capped, end‐functionalized prepolymer with a quantitative functional group conversion ratio. Subsequently, connecting the formyl end‐group of the stereoregular prepolymer by coupling with living anionic polystyrene resulted in the high yield production of stereoregular diblock copolymer (sPP‐based P‐N‐block‐polystyrene), which is difficult to prepare by other methods. The resulting stereoregular diblock copolymer possesses precise chemical architecture to self‐organize into consistent nanostructures as evidenced by transmission electron microscopy and small angle X‐ray scattering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4843–4856, 2008     

End‐functionalization of syndiotactic polystyrene by vinylsilane inducing selective chain transfer reactions

Structurally well‐defined end‐functionalized syndiotactic polystyrene (sPS) can be prepared by conducting a simultaneous selective chain transfer reaction during the syndiospecific polymerization of styrene in the presence of vinylsilanes. The production of vinylsilane end‐capped sPS involves a unique selective chain transfer pathway via the incorporation of a terminal vinylsilane unit at the polymer chain end by 2,1‐insertion. This unusual insertion pattern situates the bulky silyl functional group at a closer β‐position from the active catalyst center, thus deactivating the propagating chain by a steric jam between the vinylsilane end group and the active catalyst. Subsequently, chain releasing by hydrogen addition (in the presence of H₂) or by β‐elimination (in the absence of H₂) can take place, which leads to the production of end‐functionalized sPS with precise controls of stereoregularity and of the location of functionality. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1690–1698, 2010