Maleimide‐based thiol reactive multiarm star polymers via Diels‐Alder/retro Diels‐Alder strategy

Multiarm star polymers containing thiol‐reactive maleimide groups at their core have been synthesized by utilization of atom transfer radical polymerization (ATRP) of various methacrylates using a masked maleimide containing multiarm initiator. One end of the initiator contains multiple halogen groups that produce the star architecture upon polymerization and the other end contains a masked maleimide functional group. Unmasking of the maleimide group after the polymerization provides the thiol reactive maleimide core that is widely used in bioconjugation. Functionalization of the core maleimide group with a thiol containing tripeptide was used to demonstrate facile reactivity of the core of these multiarm polymers under reagent‐free conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2546–2556, 2010     

Synthesis of complex macromolecules using iterative copper(0)‐mediated radical polymerization

Copper(0) mediated radical polymerization is an efficient and versatile polymerization technique which allows the control of acrylates and methacrylates with an unprecedented maintenance of end group fidelity (～100%) during the polymerization. In this highlight, we summarize recent works using Cu(0)‐mediated radical polymerization for the synthesis of multiblock copolymers via an iterative approach. This approach has been successfully implemented for the synthesis of decablock copolymers, constituted of blocks with a degree of polymerization ranging from 3–4 to 100 units as well as for the preparation of multiblock star polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2083–2098     

Radical polymerization of various alkyl methacrylates in liquid crystalline solvents

The polymerization of methacrylates of methyl, ethyl, butyl, hexyl, octyl, dodecyl, and octadecyl alcohols was studied with 2,2′-azobisisobutyronitrile in the smectic, nematic, cholesteric, and isotropic liquid phases at 50–75°C. N-(4-Methoxyphenylmethylene)phenylamine, N-(4-ethoxyphenyl-methylene)-4-butylphenylamine, cholesteryl octadecanoate, and benzene were used as the solvents. The viscosities of the polymers were enhanced in the mesomorphic solvents. The polymer was converted to the corresponding poly(methyl methacrylate) through hydrolysis and esterification. Tacticities of the resultant poly(methyl methacrylates) were determined by nuclear magnetic resonance spectroscopy. The isotacticities of the polymers obtained in the smectic and the nematic phases were basically the same and appeared to be larger than those of the polymers in the cholesteric and isotropic liquid states. The polymerization of the methacrylates of butyl and longer-chain alcohols deviated from Bernoullian statistics and gave polymers more isotactic than those of methyl and ethyl methacrylates.     

Patterning on nonplanar substrates: flexible honeycomb films from a range of self-assembling star copolymers

The effect of glass transition temperature, Tg, on the self-assembly of "honeycomb" microstructures on nonplanar substrates was probed by the synthesis of a library of core cross-linked star polymers with different arm compositions. Star polymers based on poly(dimethyl siloxane), poly(ethyl acrylate), poly(methyl acrylate), poly(tert-butyl acrylate), and poly(methyl methacrylate) were synthesized by the "arm first" strategy using atom-transfer radical polymerization. Reaction conditions were optimized, and a series of high molecular weight star polymers were prepared in high yield. The glass transition temperature of the star polymers ranged from -123 to 100 degrees C which allowed the suitability for the formation of porous honeycomb-like films via the "breath figure" technique on nonplanar surfaces to be investigated. All star compositions successfully formed ordered films on flat surfaces. However, only star polymer compositions with a Tg below 48 degrees C could form homogeneous honeycomb coatings on the surface of nonplanar substrates.     

Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange

Reversible chain transfer catalyzed polymerization(RTCP) is a practical and efficient process for the precise synthesis of polymers with special architecture by using simple phenols(2,4,6-trimethylphenol, TMP) or hydrocarbons(xanthene, XT) as efficient organocatalysts. Herein,alkyl iodide(R-I), which was generated from in situ bromine-iodine transformation of alkyl bromide(R-Br) with sodium iodide(NaI), was served as initiator to mediate RTCP with TMP or XT. MMA and other functional methacrylates, including GMA, DEAM, DMAEMA and BzMA, were successfully initiated by combining organocatalysts and azo initiators to yield polymers with low-polydispersity(Mw/Mn=1.1-1.5) and ideal monomer conversions(50%-90%) at moderate temperature. Moreover, 3-armstar polymers were also obtained by this method. The high chain-end fidelity of the obtained poly(methyl methacrylate) with iodine as chain-end group(PMMA-I) was confirmed by chain-extension reaction. The environmentally friendly initiators and organocatalysts exhibit powerful polymerization properties toward RTCP, providing a significant method to synthesize functional polymers.     

Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange

Reversible chain transfer catalyzed polymerization(RTCP) is a practical and efficient process for the precise synthesis of polymers with special architecture by using simple phenols(2,4,6-trimethylphenol, TMP) or hydrocarbons(xanthene, XT) as efficient organocatalysts. Herein,alkyl iodide(R-I), which was generated from in situ bromine-iodine transformation of alkyl bromide(R-Br) with sodium iodide(NaI), was served as initiator to mediate RTCP with TMP or XT. MMA and other functional methacrylate...     

Highly efficient disulfide bridging polymers for bioconjugates from radical-compatible dithiophenol maleimides

The direct synthesis of dithiophenol maleimide functional polymers by living radical polymerisation is described without the need for protecting group chemistry. The synthesised polymers have been successfully employed as disulfide bridging agents for salmon calcitonin when used in equimolar quantities, negating the requirement for complex purification strategies, traditionally associated with peptide bioconjugation.     

One-pot RAFT/"click" chemistry via isocyanates: efficient synthesis of α-end-functionalized polymers

A new methodology has been developed for preparing α-functional polymers in a one-pot simultaneous polymerization/isocyanate "click" reaction. Our original synthetic strategy is based on the preparation of a carbonyl-azide chain transfer agent (CTA) precursor that undergoes the Curtius rearrangement in situ during reversible addition-fragmentation chain transfer (RAFT) polymerization yielding well-controlled α-isocyanate modified polymers. This strategy overcomes numerous difficulties associated with the synthesis of a polymerization mediator bearing an isocyanate at the R group and with the handling of such a reactive functionality. This new carbonyl-azide CTA can control the polymerization of a wide range of monomers, including (meth)acrylates, acrylamides, and styrenes (M(n) = 2-30 kDa; ? = 1.16-1.38). We also show that this carbonyl-azide CTA can be used as a universal platform for the synthesis of α-end-functionalized polymers in a one-pot RAFT polymerization/isocyanate "click" procedure.     

Stereocontrol in radical polymerization

The stereospecific radical polymerization of vinyl esters, methacrylates, and alpha-substituted acrylates was studied. Fluoroalcohols, as a solvent, have remarkable effects on the stereoregularity of the radical polymerizations of vinyl acetate, vinyl pivalate, and vinyl benzoate, affording polymers rich in syndiotacticity, heterotacticity, and isotacticity, respectively. This method was successfully applied to the polymerization of methacrylates to give syndiotactic polymers. The steric repulsion between the entering monomer and the chain-end monomeric unit bound by the solvent through hydrogen bonding is important for the stereochemical control in these systems. Lewis acid catalysts, such as lanthanide trifluoromethanesulfonates and zinc salts, were also effective for the stereocontrol during the radical polymerization of methyl methacrylate, to reduce the syndiotacticity and alpha-(alkoxymethyl)acrylates to synthesize isotactic and syndiotactic polymers. Radical polymerization of the methacrylates bearing a bulky ester group, such as the triphenylmethyl methacrylate derivatives, gave highly isotactic polymers, as in the case of anionic polymerization. In addition, the control of one-handed helical conformation was attained in the radical polymerization of 1-phenyldibenzosuberyl methacrylate using chiral neomenthanethiol or cobalt(II) complexes as an additive.     

Fullerene-containing branched polymethacrylates and polymer networks: Synthesis,structure, and properties

Branched poly(methyl methacrylates) containing covalently and noncovalently attached fullerene C₆₀ are synthesized and characterized by IR and UV spectroscopy. The basic physicochemical characteristics of the branched poly(methyl methacrylate) comprising covalently attached fullerene and the non-functionalized branched polymer of the same composition are compared. The effect of fullerene-containing branched poly(methyl methacrylates) on the kinetics of the crosslinking radical polymerization of 1,6-hexanediol dimethacrylate and on the structural-physical (mechanical, thermomechanical, and diffusion-sorption) properties of the resulting polymers is examined. The role of fullerene attached to the branched poly(methyl methacrylate) as an inhibitor of the crosslinking radical polymerization of dimethacrylate and as a modifier of the structure and properties of the polymers is ascertained.     

Polymerization of N-(fluoro phenyl) maleimides

Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. These include N-(2-fluoro phenyl), N-(3-fluoro phenyl), N-(4-fluoro phenyl), N-(2,4-difluoro phenyl), N-(2,5-difluoro phenyl), N-(2,3,5,6-tetrafluoro phenyl), and N-(pentafluoro phenyl). The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by AIBN in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. On the basis of the comparison between the overall activation energy of the thermal degradation of poly[N-(fluoro phenyl) maleimide]s and NMR spectra of their corresponding monomers, it can be concluded that the ¹H shifts due to ethylenic protons are so characteristic in sign and magnitude as to be useful in thermal stability elucidation. Some qualitative explanations were given on the stability of these polymers as affected by the type and size of the substituent. The x-ray diffractograms of all samples show two rather broad peaks indicative of noncrystalline structures. The location of the peaks does not depend upon preparation conditions and temperature. Poly(N-maleimide)s of fluoroanilines have not been hitherto described.     

Preparation of 3‐arm star polymers (A3) via Diels–Alder click reaction

Diels–Alder click reaction was successfully applied for the preparation of 3‐arm star polymers (A₃) using furan protected maleimide end‐functionalized polymers and trianthracene functional linking agent (2) at reflux temperature of toluene for 48 h. Well‐defined furan protected maleimide end‐functionalized polymers, poly (ethylene glycol), poly(methyl methacrylate), and poly(tert‐butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained star polymers were characterized via NMR and GPC (refractive index and triple detector detection). Splitting of GPC traces of the resulting polymer mixture notably displayed that Diels–Alder click reaction was a versatile and a reliable route for the preparation of A₃ star polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 302–313, 2008     

Alpha-aldehyde terminally functional methacrylic polymers from living radical polymerization: application in protein conjugation "pegylation"

Application of proteins and peptides as human therapeutics is expanding rapidly as drug discovery becomes more prevalent. Conjugation of polymers to proteins can circumvent many problems and pegylation of proteins is now emerging as acceptable practice. This paper describes the synthesis of alpha-aldehyde-terminated poly(methoxyPEG)methacrylates from Cu(I) mediated living radical polymerization (Mn = 11 000, 22 000 and 32 000; PDi < 1.15), and their efficient conjugation to lysozyme, as a model protein. This offers an attractive and flexible alternative to linear poly(ethylene glycol) opening up the possibility of using the full power of living radical polymerization.     

Free-radical synthesis of block copolymers on an industrial scale

Controlled free-radical polymerization has been monitored with great interest in recent years since it offers an opportunity to combine the advantages of conventional free-radical polymerization with those of living ionic polymerization. We present the 1,1-diphenylethene (DPE) method which enables us to produce block copolymers on an industrial scale by a free-radical mechanism. This DPE process enables industrially relevant monomers, such as styrene, methacrylates, acrylates, methacrylic acid, acrylic acid and N-vinyl compounds, to be converted into block copolymers. The synthesis can be carried out in organic solvents, without solvents or in water. We have been able to demonstrate, that the addition of 1,1-diphenylethylene to a normal free-radical polymerization results in polymers whose molar mass, after a short uncontrolled phase, increases in a linear manner with conversion. The amount of 1,1-diphenylethylene added also determines the order of magnitude of the final molar mass. It was also possible to employ the polymers isolated during this polymerization as initiators for the polymerization of a further monomer, resulting in the formation of block copolymers. With possibly somewhat reduced claims on the perfection of the structures, a wide variety of possibilities arise with the known advantages of free-radical polymerization. The one-pot synthesis is carried out by simple successive addition of the desired monomers and has already been used successfully on an industrially relevant scale.     

Thermal and radical polymerization of anthracene acrylates and methacrylates

The thermal and radical-induced polymerizations of 9-anthrylmethyl acrylate ( I ), 9-anthrylmethyl methacrylate ( II ), 1′-(9-anthryl)ethyl acrylate ( III ), and 1′-(9-anthryl)ethyl methacrylate ( IV ) have been studied. It was found that the radical-induced polymerization takes place for the methacrylates only, while thermal polymerization leads to polymers for both types of monomers and takes place by Diels–Alder cycloaddition in the case of acrylates, and by both normal enchainment and Diels–Alder cycloaddition in the case of methacrylates.     

Advances in cycloaddition polymerizations

Cycloaddition reactions have been employed in polymer synthesis since the mid-nineteen sixties. This critical review will highlight recent notable advances in this field. For example, [2 + 2] cycloaddition reactions have been utilized in numerous polymerizations to enable the construction of strained polymer systems such as poly(2-azetidinone)s that can, in turn, afford polyfunctional beta-amino acid derived polymers. Polymers have also been synthesized successfully via (3 + 2) cycloaddition methods utilizing both thermal and high-pressure conditions. 'Click chemistry'--a process involving the reaction of azides with olefins, has also been adopted to generate linear and hyperbranched polymer architectures in a very efficient manner. [4 + 2] Cycloadditions have also been utilized under thermal and high-pressure conditions to produce rigid polymers such as polyimides and polyphenylenes. These cycloaddition polymerization methods afford polymers with potential for use in high performance polymers applications such as high temperature resistant coatings and polymeric organic light emitting diodes.     

Positive working resists sensitive to visible light,I: poly(tert-butyl and 2-phenylpropyl-2 methacrylates) sensitized with diphenyliodonium salt — p-aminobenzylidene dye system

Visible-light-sensitive positive type resists have been developed. The chemistry to form images is based on the cleavage of side chain ester bonds of poly(methacrylates) catalyzed by an acid which is generated on sensitized photodecomposition of a diphenyliodonium (DPI) salt. Homopolymers and copolymers of tert-butyl methacrylate (BMA) and 2-phenylpropyl-2 methacrylate (PPMA) were used as acid labile polymers. Exposure of thin films of the poly(methacrylates) containing DPI salt and p-dimethylaminobenzylidene derivatives to an Ar laser beam emitting 488 nm light and subsequent heat treatment resulted in solubility alteration of the polymers, which became soluble in a protic solvent system. Considerable reduction of film thickness was observed after heating an image-wise exposed thin film of PPMA polymers. The minimum exposure energies of 488 nm light for the positive image formation were 60 mJ/cm² and 40 mJ/cm² for BMA and PPMA homopolymers, respectively.     

Branching of anionic poly(methyl methacrylate)

A viscometric determination of the degree of branching γ, of poly(methyl methacrylate) obtained by anionic polymerization proved the reaction of the growing center of poly(methyl methacrylate) with the ester group of another polymer molecule, accompanied by the formation of a trifunctional branch point. This reaction occurs if the solution polymerization of methyl methacrylate is initiated: (1) with butyllithium at ?78°C only on attaining 100% conversion and after a long time or at +20°C immediately after the polymerization has set in; (2) with lithium tert-butoxide at +20°C after a long time. The degree of branching of poly(methyl methacrylates) obtained under similar conditions in the presence of tetrahydrofuran reaches higher values than for polymers prepared in toluene. The tacticity of polymers does not affect the experimentally determined γ values.     

RAFT polymerization of activated 4‐vinylbenzoates

The reversible addition fragmentation chain transfer (RAFT) polymerization of five active ester monomers based on 4‐vinylbenzoic acid had been investigated. Pentafluorophenyl 4‐vinylbenzoate could be polymerized under RAFT conditions yielding polymers with very good control over molecular weight and narrow molecular weight distributions. Following the synthesis of diblock copolymers consisting of polystyrene, polypentafluorostyrene, poly(4‐octylstyrene), or poly(4‐acetoxystyrene) as an inert block and poly(pentafluorophenyl 4‐vinylbenzoate) as a reactive block was successfully performed. The diblock copolymer poly(pentafluoro styrene)‐block‐poly(pentafluorophenyl 4‐vinylbenzoate) had been analyzed by ¹⁹F NMR spectroscopy in solution, demonstrating the synthetic potential of pentafluorophenyl 4‐vinylbenzoate as an extremely valuable monomer for the synthesis of highly functionalized polymeric architectures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1696–1705, 2009     

Thermogravimetric analysis of poly(alkyl methacrylates) and poly(methylmethacrylate-g-dimethyl siloxane) graft copolymers

The thermal stabilities of various poly(alkyl methacrylate) homopolymers and poly(methyl methacrylate-g-dimethyl siloxane) (PMMA-g-PSX) graft copolymers have been determined by thermogravimetric analysis (TGA). As expected, the thermal stabilities of poly(alkyl methacrylates) were a function of the ester alkyl group, and polymerization mechanism. In particular, thermally labile linkages, which result from termination during free radical or nonliving polymerization mechanisms, decrease the ultimate thermal stabilities of the polymers. However, graft copolymers, which were prepared by the macromonomer technique with free radical initiators, exhibited enhanced thermal stability compared to homopolymer controls. A more complex free radical polymerization mechanism for the macromonomer modified polymerization may account for this result. © 1994 John Wiley & Sons, Inc.