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).

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.

Controlled/"Living"?Radical Polymerization of (-)-Menthyl Methacrylate

The atom transfer radical polymerization(ATRP) of (-)-menthyl methacrylate((-)-MnMA) mediated by CuCl/bipyridine and ethyl 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied. The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obtained was investigated.

Bifurcation control and eigenstructure assignment in continuous solution polymerization of vinyl acetate

The major difficulty in achieving good performance of industrial polymerization reactors lies in the lack of understanding of their nonlinear dynamics and the lack of well-developed techniques for the control of nonlinear processes, which are usually accompanied with bifurcation phenomenon. This work aims at investigating the nonlinear behavior of the parameterized nonlinear system of vinyl acetate polymerization and further modifying the bifurcation characteristics of this process via a washout filter-aid controller, with all the original steady state equilibria preserved. Advantages and possible extensions of the proposed methodology are discussed to provide scientific guide for further controller design and operation improvement.

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.

“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.

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.

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.

THE CONTROL OF POLYMETHACRYLATE MOLECULAR STRUCTURE BY GROUP TRANSFER POLYMERIZATION

INTRODUCTION Group transfer polymerization (GTP) is a method for controlling the structure of acrylic polymers in which reactive chain ends are covalentiy bound to a trimethylsilyl group. In the presence of a catalyst, monomer inserts into these chain ends between the silyl group and the last monomer unit. The process is illustrated by equation (1) for methyl methacrylate. GTP is a living polymerization, i. e., there is little or no chain termination and no chain transfer. A significant advantage of GTP is that it

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.

Accelerated heterogenous ring-opening polymerization towards well-defined helical poly(N-allyl alanine)with clickable side chains

Well-defined poly(N-allyl alanine)has been synthesized by heterogenous ring-opening polymerization(HROP)of less reactive N-allyl-alanine N-carboxyanhydride,using acetic acid as the catalyst and benzylamine as the initiator,in non-polar n-hexane.Interestingly,the polymerization exhibited typical features of living polymerization though both monomer(liquid)and polymer(solid)have minimal solubility in n-hexane.The obtained polymer showed a stable helix structure independent of the temperatures screened,as evidenced by circular dichroism analysis.Also,the preliminary study demonstrated that the side chains can be post-functionalized through thiol-ene click chemistry with quantitative conversion.Together,this work provides guidance for the development of accelerated HROP of other liquid monomers bearing low reactivity.Besides,the helical and functionalizable poly(N-allyl alanine)could be a useful“clickable platform”for the design of variable biomaterials via efficient click chemistry.

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.

Living/controlled polymerization of vinylpyridines into sequence-regulated copolymers by Lewis pair

The poly(vinylpyridine)(PVP) based(co)polymers are of particular interest in materials science, due to their multifunctionality and diverse applications. So far, there is no report on the sequence-regulated copolymerization of vinylpyridines(VPs) and methacrylate monomer in one-step manner yet. Here we designed and synthesized a series of guanidine phosphines as Lewis base(LB), which is combined with bulky organoaluminium to construct Lewis pairs(LPs) for polymerization of VPs. The living/controlled polymerization of 4-vinylpyridine(4-VP) or 2-vinylpyridine(2-VP) can be accomplished with remarkable efficiency by such Lewis pair polymerization(LPP), furnishing polymers with high molecular weight(up to 288 kg/mol) and narrow molecular weight distribution(as low as 1.17). Mechanistic studies reveal the interaction of LPs and formation of zwitterionic intermediates, providing solid evidences to support the proposed polymerization mechanism. More importantly, by simply adjusting the LA dosage, this LPP strategy realizes the unprecedented control over the sequence regulation of 2-VP-based copolymers from gradient to block in one-step manner, regardless of the monomer ratio, which greatly expands the versatility of the LPP.

Progress of polymer reaction engineering:From process engineering to product engineering

Polymer reaction engineering studies the design,operation,and optimization of reactors for industrial scale polymerization,based on the theory of polymerization kinetics and transfer processes(e.g.,flow,heat and mass transfer).Although the foundation and development of this discipline are less than80 years,the global production of polymers has exceeded 400 million tons per annum.It demonstrates that polymer reaction engineering is of vital importance to the polymer industry.Along with the matu rity of production processes and market saturation for bulk polymers,emerging industries such as information technology,modern transportation,biomedicine,and new energy have continued to develop.As a result,the research objective for polymer reaction engineering has gradually shifted from maximizing the efficiency of the polymerization process to the precise regulation of high-end product-oriented macro molecules and their aggregation structures,i.e.,from polymer process engineering to polymer product engineering.In this review,the frontiers of polymer reaction engineering are introduced,including the precise regulation of polymer chain structure,the control of primary aggregation structure,and the rational design of polymer products.We narrow down the topic to the polymerization reaction engineering of vinyl monomers.Moreover,the future prospects are provided for the field of polymer reaction engineering.

SYNTHESIS AND CHARACTERIZATION OF WELL-DEFINED BLOCK COPOLYMERS CONTAINING PENDANT,SELF-COMPLEMENTARY QUADRUPLE HYDROGEN BONDING SITES

The title block copolymer (defined as PSUEA) containing pendant,self-complementary quadruple hydrogen bonding sites has been prepared successfully by three steps.First,poly(styrene-b-2-hydroxyethyl acrylate) (defined as PSHEA) was prepared by living radical polymerizing 2-hydroxyethyl acrylate (HEA) initiated by polystyrene (PSt) macro- initiator,which was prepared via nitroxide-mediated polymerization (NMP) technique.After treated by excessive 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI),...

INVESTIGATION OF THE ATRP OF n-BUTYL METHACRYLATE USING THE Cu(I)/N,N,N',N",N"-PENTAMETHYLDIETHYLENETRIAMINE CATALYST SYSTEM

The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N',N',N'-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a salt in conjunction with the N,N,N',N',N'- pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCl is used as the species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, species and the initiator structure were determined.

Preparation and performance of fluorescent polyacrylamide microspheres as a profile control and tracer agent

Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recovery and is already present in production fluids. In order to detect polyacrylamide microspheres in the reservoir pro- duced fluid, fluorescent polyacrylamide microspheres P（AM-BA-AMCO）, which fluoresce under ultraviolet irradiation, were synthesized via an inverse suspension polymerization. In order to keep the particle size distribu- tion in a narrow range, the synthesis conditions of the polymerization were studied, including the stirring speed and the concentrations of initiator, NaaCO3, and dispersant. The bonding characteristics of microspheres were deter- mined by Fourier transform infrared spectroscopy. The surface morphology of these microspheres was observed under ultraviolet irradiation with an inverse fluorescence microscope. A laboratory evaluation test showed that the fluorescent polymer microspheres had good water swelling capability, thus they had the ability to plug and migrate in a sand pack. The plugging rate was 99.8 % and the residual resistance coefficient was 800 after microsphere treatment in the sand pack. Furthermore, the fluorescent microspheres and their fragments were accurately detected under ultra- violet irradiation in the produced fluid, even though theyhad experienced extrusion and deformation in the sand pack.

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.