Nitroxide-Mediated Photo-Controlled/Living Radical Polymerization of Methacrylic Acid

The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.

Elucidation of Acceleration Mechanisms by a Photosensitive Onium Salt for Nitroxide-Mediated Photocontrolled/Living Radical Polymerization

The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.

CONTROLLED/"LIVING" RADICAL POLYMERIZATION OF STYRENE IN AN AQUEOUS DISPERSION SYSTEM

Atom transfer radical polymerization (ATRP) of styrene catalyzed by cuprous (CuX)/1,10-phenanthroline (Phen) and CuX/CuX2/Phen was conducted in an aqueous dispersed system. A stable latex was obtained by using ionic surfactant sodium lauryl sulfonate (SLS) or composite surfactants, such as SLS/polyoxyethylene nonyl phenyl ether (OP-10), SLS/hexadecanol and SLS/OP-10/hexadecanol, Among which SLS and SLS/OP-10/hexadecanol systems established better dispersed effect during the polymerization, It was found that Phen was a more suitable ligand than N,N,N',N',N'-pentamethyldiethylenetriamine (PMDETA) to maintain an appropriate equilibrium of the activator Cu(I) and the deactivator Cu(II) between the organic phase and the water phase, The effect of several initiators (such as EBiB, CCl4 and 1-PEBr) and the temperature on such a kind of ATRP system was also observed. The number-average molar mass (M-n) of polystyrene (PS) increased with the conversion and the molar mass distribution (M-w/M-n) remained narrow. These experimental data show that the polymerization could be controlled except for the quick increase of monomer conversion and the number-average molar mass of PS in the initial stage of polymerization. Furthermore, the initiator efficiency was found to be low (similar to57%) in CuX/Phen catalyzed system. To overcome this problem, Cu(II)X-2 (20 mol%-50 mol% based on CuX) was introduced into the polymerization system. In this case, higher initiator efficiency (60%-90%), low M-w/M-n of PS (as low as 1.08) were achieved and the molar masses of the PS fit with the theoretical ones.

“LIVING”/CONTROLLED RADICAL POLYMERIZATION OF ETHYL METHYLACRYLATE WITH 2,2’-AZOBISISOBUTYRONITRILE/FERRIC CHLORIDE/TRIPHENYLPHOSPHINE INITIATION SYSTEM

'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.

Controlled Radical Polymerization of Styrene in the Presence of Different Copper Complexes and Organic Halides

The polymerization behaviors of Styrene (St) in the presence of CuX/L [X=Cl or Br; L= 2,2 bipyridine (bpy), 1,10 phenanthroline (phen) or 4,7 diphenyl 1,10 phenanthroline (DPP) ] and R X (R=trichloromethyl, benzyl or allyl; X=Cl or Br) have been studied and examined. In a CuCl/bpy/RCl/St system, a bimodal GPC peak at the early stage of polymerization was observed, and a concept of multi active species was proposed to explain this phenomenon. In a CuCl/phen (DPP)/RCl/St system, the \%M\%\-n of polystyrene (PS) increased linearly with St conversion and ln[M] o/[M] also increased linearly with time, indicating the living nature of this system. Furthermore, the stability of the propagating active species in a CuBr/phen/RBr/St system is higher than that in the CuBr/phen/RBr/St system.

Controlled Radical Polymerization of Methyl Methacrylate Catalyzed by Hybrid Supported Iron Catalyst

A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/ Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved（Mw/Mn = 1.23-1.73 ）, affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also he recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.

CONTROLLED RADICAL COPOLYMERIZATION OF STYRENE AND MALEIC ANHYDRIDE UNDER GAMMA RADIATION IN THE PRESENCE OF BENZYL DITHIOBENZOATE

The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.

Synthesis of super high molecular weight copolymer of AM/NaA/AMPS by oxidation–reduction and controlled radical polymerization

Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.

THE EFFECTS OF MONOMER STRUCTURE OF CYCLIC KETENE ACETALS ON THE BEHAVIOR OF CONTROLLED RADICAL RING-OPENING POLYMERIZATION

Polymerization of three cyclic ketene acetals: i.e., 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), 2-methylene-4phenyl-1,3-dioxolane (MPDO) and 4,7-dimethyl-2-methylene-1,3-dioxepane (DMMDO) were carried out in the presence of ethyl alpha -bromobutyrate/CuBr/2,2'-bipyridine respectively. The structures of poly(BMDO), poly(MPDO) and poly(DMMDO) were characterized by H-1 and C-13-NMR spectra. The effects of monomer structure on the behavior of atom transfer free radical ring-opening polymerization were investigated and the mechanism of controlled free radical ring-opening polymerization was discussed.

RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials (i.e., molecularly imprinted polymers, MIPs) with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.

SYNTHESIS OF TRIBLOCK COPOLYMERS OF STYRENE AND ISOPRENE BY A NITROXIDE-MEDIATED LIVING FREE RADICAL POLYMERIZATION

The controlled free radical polymerization of styrene and isoprene initiated with benzoyl peroxide (BPO) in the presence of 2,2,6,6-tetramethyl piperidine-N-oxyl (TEMPO) at 125 'C were performed. The obtained polyisoprene and polystyrene homopolymers served as macroinitiators for block copolymerization of isoprene and styrene to synthesize poly- (styrene-b-isoprene) and poly(isoprene-b-styrene) diblock copolymers. Diblock copolymers with well-defined structures as well as controlled and narrow molecular weight distribution were obtained from the lower-mass polystyrene and polyisoprene homopolymers. These copolymers were found to be active as macroinitiators in the synthesis of the poly(styrene-b-isoprene-b-styrene) and poly(isoprene-b-styrene-b-isoprene) triblock copolymers. 1H-NMR spectroscopy and gel permeation chromatography (GPC) were used for the investigation of polymer structure, molecular weight and polydispersity (PD).

Studies on the Self-condensing Vinyl Living Radical Polymerization of a Novel Acrylate Inimer

A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION(ATRP)

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

AMPHIPHILIC STAR-BLOCK COPOLYMERS BY IODIDE-MEDIATED RADICAL POLYMERIZATION

Amphiphilic star-block copolymers composed of polystyrene and poly（acrylic acid） were synthesized by iodide- mediated radical polymerization. Firstly, free radical polymerization of styrene was carried out with AIBN as initiator and 1,1,1-trimethyolpropane tri（2-iodoisobutyrate） as chain transfer agent, giving iodine atom ended star-shaped polystyrene with three arm chains, R（polystyrene）3. Secondly, tert-butyl acrylate was polymerization using polystyrene obtained as macro-chain transfer agent, and star-block copolymer, R（polystyrene-b-poly（tert-butyl acrylate））3 with controlled molecular weight was obtained. Finally, amphiphilic star-block copolymer, R（polystyrene-b-poly（acrylic acid））3 was obtained by hydrolysis of R（polystyrene-b-poly（tert-butyl acrylate））3 under acidic condition.

AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

An overview of aqueous polymerizations, which include emulsion, miniemulsion and suspension polymerizations, under stable free radical polymerization (SFRP) conditions is presented. The success of miniemulsion and suspension SFRP polymerizations is contrasted with the difficulties associated with obtaining a stable emulsion polymerization. A recently developed unique microprecipitation technique is referenced as a means of making submicron sized particles that can be used to achieve a stable emulsion SFRP process.

"LIVING" FREE RADICAL SYNTHESIS OF NOVEL RODCOIL DIBLOCK COPOLYMERS WITH POLYSTYRENE AND MESOGEN-JACKETED LIQUID CRYSTAL POLYMER SEGMENTS

The synthesis of rod-coil diblock copolymers was achieved for the first time by TEMPO-mediated 'living' free radical polymerization of styrene and 2,5-bis [(4-methoxyphenyl)oxycarbonyl] styrene(MPCS). The block architecture of the two diblock copolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was confirmed by GPC, DSC studies and the formation of multimolecular micelles. (Author abstract) 10 Refs.

A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3) as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.

LIVING/CONTROLLED GRAFTING FROM POLYMER MICROSPHERES

A review is given of grafting-from methods using living polymerizations, with emphasis on grafting from polymermicrospheres using ATRP.

REVERSE ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE WITH COPPER-BASED CATALYST

'Living'/controlled radical polymerization of styrene was carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl2/bipyridine (bipy) initiation system at 120 degreesC. The molecular weights of resultant PSt increased with the monomer conversion and the polydispersities were in the range of 1.37 similar to1.52. A linear ln([M](o)/[M]) versus time plot was also obtained indicating the constant concentration of growing radicals during the polymerization with this initiation system. End group analysis by H-1-NMR spectroscopic studies showed that the end groups of the polymer obtained is omega -functionalized by a chlorine group from the catalyst and alpha -functionalized by a (carbethoxy-cyano-phenyl)methyl group from the fragments of the initiator. Having CI atom at the chain end, the PSt obtained can be used as a macroinitiator to promote a chain-extension reaction with fresh St and block copolymerization reaction with a second monomer, such as methyl methacrylate, in the presence of CuCl/bipy catalyst via a conventional ATRP process.

Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

Chemoselective,living/controlled polymerizations of allyl methacrylate(AMA) and vinyl methacrylate(VMA) with/without methyl methacrylate(MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs(LPs) have been realized.The P-ylide-2/AIMe(BHT)_(2)(Pylide-2=Ph_(3)P=CHMe and BHT=2,6-iBu_(2)-4-MeC_(6)H_(2)O) was demonstrated to be superior by which homopolymers PAMAs(M_(n)=27.6-111.5kg/mol and ■=1.14-1.25) and PVMAs(M_(n)=28.4-78.4 kg/mol and ■=1.12-1.18) and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-bPMMA,PMMA-b-PAMA-b-PMMA,PAMA-b-PMMA-b-PAMA,and PAMA-b-PVMA-b-PAMA were synthesized.In the polymerizations,all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups.The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical "thiol-ene" reaction using PhCH_(2)SH.The thiolether side group-containing polymers PAMA-SCH_(2)Ph and PAMA-SCH_(2)Ph-b-PMMA-b-PAMA-SCH_(2)Ph were thus prepared.