Synthesis of heteroarm star polymers comprising poly(4-methylphenyl vinyl sulfoxide) segment by living anionic polymerization

<正>A series of 3-arm ABC and AA'B and 4-arm ABCD,AA'BC and AA′A″B heteroarm star polymers comprising one poly(4-methylphenyl vinyl sulfoxide) segment and other segments such as polystyrene,poly(α-methylstyrene), poly(4-methoxystyrene) and poly(4-trimethylsilylstyrene) were synthesized by living anionic polymerization based on diphenylethylene(DPE) chemistry.The DPE-functionalized polymers were synthesized by iterative methodology,and the objective star polymers were prepared by two distinct methodologies based on anionic polymerization using DPE-functionalized polymers.The first methodology involves an addition reaction of living anionic polymer with excess DPE-functionalized polymer and a subsequent living anionic polymerization of 4-methylphenyl vinyl sulfoxide(MePVSO) initiated from the in situ formed polymer anion with two or three polymer segments.The second methodology comprises an addition reaction of DPE-functionalized polymer with excess sec-BuLi and a following anionic polymerization of MePVSO initiated from the in situ formed polymer anion and 3-methyl-1,1-diphenylpentyl anion as well.Both approaches could afford the target heteroarm star polymers with predetermined molecular weight,narrow molecular weight distribution (M_w/M_n1.03) and desired composition,evidenced by SEC,~1H-NMR and SLS analyses.These polymers can be used as model polymers to investigate structure-property relationships in heteroarm star polymers.     

Successive Synthesis of Regular and Asymmetric Star-Branched Polymers by Iterative Methodology Based on Living Anionic Polymerization Using Functionalized 1,1-Diphenylethylene Derivatives

In order to achieve the successive synthesis of star-branched polymers, we have developed a new iterative methodology which involves only three sets of the reactions in each iterative process: (a) a coupling reaction of a living anionic polymer with 1,1-bis(3-chloromethylphenyl)ethylene to prepare a DPE-chain-functionalized polymer, (b) an addition reaction of sec-BuLi to the DPE-chain-functionalized polymer, followed by treatment with 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene to prepare a new DPE-chain-functionalized polymer whose DPE is separated by four methylene units from the main chain, and (c) a coupling reaction of 1,1-bis(3-chloromethylphenyl)ethylene with the polymer anion derived from the newly prepared DPE-chain-functionalized polymer and sec-BuLi. With this methodology, a series of well-defined 4-arm, 8-arm, and 16-arm regular star-branched polystyrenes as well as 4-arm A₂B₂, 8-arm A₄B₄, and 16-arm A₈B₈ asymmetric star-branched polymers comprising polystyrene and poly(α-methylstyrene) segments have been successively synthesized.     

Synthesis of asymmetric star-branched polymers consisting of three or four different segments in composition by means of living anionic polymerization with a new dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene

A series of four-armed A₂BC, AB₂C, and ABC₂ asymmetric star-branched polymers with a three-component system, the A, B, and C segments of which are polystyrene, polyisoprene, and poly(4-trimethylsilylstyrene), respectively, have been successfully synthesized with a methodology based on living anionic polymerization with dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene ( 1 ). These star-branched polymers have well-defined architectures and precisely controlled chain lengths, as confirmed by size exclusion chromatography, ¹H and ¹³C NMR, vapor pressure osmometry, and static light scattering analyses. A simple and convenient one-pot process for star-branched polymer synthesis is an additional advantage of this methodology. One problem to be solved is that the synthetic route is limited in some cases by the inherently low reactivity of polyisoprenyllithium toward the 1,1-diphenylethylene functionality of in-chain-functionalized polymers. A new four-armed ABCD star-branched polymer, the A, B, C, and D segments of which are polyisoprene, poly(4-methoxystyrene), polystyrene, and poly(4-trimethylsilylstyrene), could also be synthesized through the extension of the methodology using 1 to a four-component system. The successful results strongly demonstrate the synthetic versatility and potential of this methodology for a wide variety of well-defined asymmetric star-branched polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4535–4547, 2004     

Synthesis and characterization of “umbrella” shaped polymers

A new strategy has been developed to prepare umbrella polymer, i.e. star polymers with one heteroarm. The synthesis uses living anionic polymerization to prepare a short segment of 1,2-polybutadiene at the end of a linear polystyrene. The vinyl groups of 1,2-polybutadiene are hydrosilylated with dichloro(methyl)silane. The umbrella polymer is then formed by nucleophilic displacement of the silicon-chlorine with 1,4-polybutadienyllithium. An umbrella polymer with poly(2-vinylpyridine) arms is prepared in the same way after hydrosilylation with chlorodimethylsilane. The umbrella polymers are characterized by light scattering, size-exclusion chromatography (SEC), ultraviolet/visible spectroscopy (UV/vis), nuclear magnetic resonance (NMR) and intrinsic viscosity.     

Precise synthesis of thermo-responsive and water-soluble star-branched polymers and star block copolymers by living anionic polymerization

A series of thermo-responsive and water-soluble 4- and 8-arm star-branched poly(2-(2′-methoxyethoxy)ethyl methacrylate) (poly(1)) with well-defined structures were synthesized by living anionic polymerization of 1, followed by a linking reaction with a core compound substituted with either four or eight benzyl bromide moieties. Furthermore, two kinds of sequentially different 4-arm star block copolymers composed of poly(1)-block-poly ((2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate) (poly(4)) were also synthesized by the same linking reaction of the corresponding AB or BA diblock copolymer anion with a core compound substituted with four benzyl bromide moieties. Thus, both well-defined 4-arm (AB)₄ and (BA)₄ star-block copolymers, whose A and B are poly(1) and poly(4) segments, were successfully synthesized. These star-block copolymers were quantitatively converted to the corresponding 4-arm (AC)₄ and (CA)₄ star-block copolymers with the same compositions by hydrolytic acetal cleavage of the poly(4) segment to poly(2,3-dihydroxypropyl methacrylate) (C segment). Poly(1) segments have LCST values and, on the other hand, both water-insoluble poly(4)s and water-soluble poly(2,3-dihydroxypropyl methacrylate)s are non-thermo-responsive segments. The thermo-responsive behavior of the resulting 4- and 8-arm star-branched poly(1) as well as the 4-arm (AB)₄, (BA)₄, (AC)₄, and (CA)₄ star-branched block copolymers has been extensively studied in terms of molecular weight, arm number, composition, and block sequence. As expected, such variables were observed to affect their LCST values. Interestingly, the thermo-responsive behavior of the 4-arm (AC)₄ and (CA)₄ stars was different from that of the block copolymers used as arm segments.     

Synthesis of fluorine‐containing star‐shaped poly(vinyl ether)s via arm‐linking reactions in living cationic polymerization

Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C₄F₉, C₆F₁₃, and C₈F₁₇) at the side chain using cationogen/Et_1.5AlCl_1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of Block Copolymers and Asymmetric Star-Branched Polymers Comprised of Polyacetylene and Polystyrene Segments via Ionic Bond Formation

Novel ion-bonded AB diblock copolymers and three-arm AB₂ asymmetric star-branched polymers comprised of polyacetylene (A) and polystyrene (B) segments have been synthesized by the stoichiometric reaction of tert-amine-chain-end-functionalized poly(phenyl vinyl sulfoxide)s with either chain-end- or in-chain-carboxylated polystyrenes to link the two polymer segments via ionic bond, followed by thermal treatment to convert their poly(phenyl vinyl sulfoxide)s to polyacetylene segments. Periodic lamellar morphologies were observed in the cast films of such polymers by TEM measurement. The isolation of the nano-size sheet consisting of polyacetylene lamellar layers was attempted.     

Synthesis of exact comb polybutadienes with two and three branches

Two methodologies, based on living star polymers and anionic polymerization high vacuum techniques, were used for the synthesis of exact comb polybutadienes (PBds) with two (C‐2 or H‐type) and three identical branches (symmetric, sC‐3, H‐type with an extra identical branch at the middle of the connector and asymmetric, aC‐3, H‐type with the extra identical branch at any other position along the connector). The first methodology involves (a) the selective replacement of the two chlorines of 4‐(dichloromethylsilyl)diphenylethylene (DCMSDPE, key molecule) with 3‐arm star PBds, by titration with identical (C‐2, sC‐3) or different (aC‐3) living 3‐arm star PBds, (b) the addition of s‐BuLi to the double bond of DPE, and (c) the polymerization of butadiene from the newly created anionic site (sC‐3, aC‐3).The second methodology involves the reaction of living stars with dichlorodimethylsilane (C‐2) or the selective replacement of the three chlorines of trichloromethylsilane with star and linear chains (sC‐3, aC‐3). Intermediate and final products were characterized via size exclusion chromatography, low angle laser light scattering and ¹H‐NMR. The first methodology does not require fractionation, but in contrast to the second methodology, cannot afford polymers with branches of identical molecular weight. Both methods are general and can be extended to combs with two or three different branches at controllable positions along the backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2597–2607, 2009     

Synthesis of Block Copolymers and Asymmetric Star-Branched Polymers Comprised of Polyacetylene and Polystyrene Segments via Ionic Bond Formation

Summary. Novel ion-bonded AB diblock copolymers and three-arm AB₂ asymmetric star-branched polymers comprised of polyacetylene (A) and polystyrene (B) segments have been synthesized by the stoichiometric reaction of tert-amine-chain-end-functionalized poly(phenyl vinyl sulfoxide)s with either chain-end- or in-chain-carboxylated polystyrenes to link the two polymer segments via ionic bond, followed by thermal treatment to convert their poly(phenyl vinyl sulfoxide)s to polyacetylene segments. Periodic lamellar morphologies were observed in the cast films of such polymers by TEM measurement. The isolation of the nano-size sheet consisting of polyacetylene lamellar layers was attempted.     

Synthesis of miktoarm star (μ-star) polymers

The synthetic strategies available for the synthesis of miktoarm star (μ-star) polymers with molecular weight, chemical, or topological asymmetry are reviewed. All strategies are based on functional living polymer chains and linking agents. Although each strategy has its weak and strong points, it seems that anionic polymerization combined with chlorosilane methodology yields the widest variety of model single and double μ-stars. These novel architectures open new horizons in polymer science and technology. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 857–871, 1999     

Synthesis and cleavage of core‐labile poly(alkyl methacrylate) star polymers

Core‐cleavable star polymers were synthesized by the coupling of living anionic poly(alkyl methacrylate) arms with either dicumyl alcohol dimethacrylate (DCDMA) or 2,5‐dimethyl‐2,5‐hexanediol dimethacrylate (DHDMA). This synthetic methodology led to the formation of star polymers that exhibited high molecular weights and relatively narrow molecular weight distributions. The labile tertiary alkyl esters in the DCDMA and DHDMA star polymer cores were readily hydrolyzed under acidic conditions. High‐molecular‐weight star polymer cleavage led to well‐defined arm polymers with lower molecular weights. Hydrolysis was confirmed via ¹H NMR spectroscopy and gel permeation chromatography. Thermogravimetric analysis (TGA) of the star polymers demonstrated that the DCDMA and DHDMA star polymer cores also thermally degraded in the absence of acid catalysts at 185 and 220 °C, respectively, and the core‐cleavage temperatures were independent of the arm polymer composition. The difference in the core‐degradation temperatures was attributed to the increased reactivity of the DCDMA‐derived cores. TGA/mass spectrometry detected the evolution of the diene byproduct of the core degradation and confirmed the proposed degradation mechanism. The DCDMA monomer exhibited a higher degradation rate than DHDMA under identical reaction conditions because of the additional resonance stabilization of the liberated byproduct, which made it a more responsive cleavable coupling monomer than DHDMA. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3083–3093, 2003     

Polyhomologation: the living polymerization of ylides

The polymerization of dimethylsufoxonium methylide to produce linear polymethylene polymers is described. The reaction is catalyzed/initiated by trialkylboranes and gives organoboron star polymers as the primary product. The reaction is a living polymerization, providing control over molecular weight and functionality at the polymer chain ends. A variety of novel polymethylene architectures are available by this methodology.     

Synthesis and Rheological Investigation ofModel Symmetric 3-Arm Star Polyethylene简

A variety of linear and 3-arm star polyethylene （PE） model polymers covering a wide range of molecular weight are synthesized by the living polymerization of butadiene and the subsequent hydrogenation. Several rheological parameters of these model linear and 3-arm star PE samples are analyzed for detecting the long chain branching （LCB） structure. It is found that the analyses based on zero shear viscosity, vGP plot and flow activation energy are very sensitive to the 3-arm star PEs. The information on the presence of LCB can be obtained with these methods even for low molecular weight samples, which can not be determined by GPC-MALLS. However the information about the LCB structure can not be obtained by the rheological methods alone.     

活性聚合在星形聚合物合成中的应用

星形聚合物在近年来发展迅速,其结构、形态、合成方法与功能性是高分子科学的研究热点。本文主要从活性离子聚合手段与活性自由基聚合手段两方面对星形聚合物的合成方法进行分类,依托星形聚合物的单体选择、星形臂的特性以及整体功能性进行系统阐述,介绍近年来星形聚合物合成方法、形貌控制以及功能性质的最新研究进展。本文结合现阶段最新的研究成果,对星形聚合物在功能与应用之间的广泛前景与联系进行了展望与预测。     

R‐RAFT approach for the polymerization of N‐isopropylacrylamide with a star poly(ε‐caprolactone) core

Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a more robust and versatile approach than other living free radical polymerization methods, providing a reactive thiocarbonylthio end group. A series of well‐defined star diblock [poly(ε‐caprolactone)‐b‐poly(N‐isopropylacrylamide)]₄ (SPCLNIP) copolymers were synthesized by R‐RAFT polymerization of N‐isopropylacrylamide (NIPAAm) using [PCL‐DDAT]₄ (SPCL‐DDAT) as a star macro‐RAFT agent (DDAT: S‐1‐dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate). The R‐RAFT polymerization showed a controlled/“living” character, proceeding with pseudo‐first‐order kinetics. All these star polymers with different molecular weights exhibited narrow molecular weight distributions of less than 1.2. The effect of polymerization temperature and molecular weight of the star macro‐RAFT agent on the polymerization kinetics of NIPAAm monomers was also addressed. Hardly any radical–radical coupling by‐products were detected, while linear side products were kept to a minimum by careful control over polymerization conditions. The trithiocarbonate groups were transferred to polymer chain ends by R‐RAFT polymerization, providing potential possibility of further modification by thiocarbonylthio chemistry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Functionalization of polymers prepared by ATRP using radical addition reactions

Low molecular weight linear poly(methyl acrylate), star and hyperbranched polymers were synthesized using atom transfer radical polymerization (ATRP) and end‐functionalized using radical addition reactions. By adding allyltri‐n‐butylstannane at the end of the polymerization of poly(methyl acrylate), the polymer was terminated by allyl groups. When at high conversions of the acrylate monomer, allyl alcohol or 1,2‐epoxy‐5‐hexene, monomers which are not polymerizable by ATRP, were added, alcohol and epoxy functionalities respectively were incorporated at the polymer chain end. Functionalization by radical addition reactions was demonstrated to be applicable to multi‐functional polymers such as hyperbranched and star polymers.     

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.     

Preparation of platinum nanoparticles using star-block copolymer with a carboxylic core

Well-defined star polymers containing a functionalized core supply a molecular nanocavity and may be used to control formation of inorganic nanoparticles. Herein, platinum (Pt) nanoparticles of 2-4 nm were prepared by using (poly(acrylic acid)-b-polystyrene)6 (PAA-b-PS)6 amphiphilic star block copolymer as a novel single molecular stabilizer. This PAA core functionalized star polymer was obtained by hydrolysis of (poly(tert-butyl acrylate)-b-polystyrene)6 (PtBA-b-PS)6, which was synthesized by sequential atom transfer radical polymerization (ATRP) of tert-butyl acrylate and styrene with an initiator bearing six 2-bromoisobutyloxyl groups. Pt(IV) ions were loaded by ion exchange to the core of the star polymer and Pt nanoparticle stabilized by single star polymer was produced by a reduction with NaBH4.     

Organosoluble star polymers from a cyclodextrin core

Well‐defined star polymers were synthesized with a combination of the core‐first method and atom transfer radical polymerization. The control of the architecture of the macroinitiator based on β‐cyclodextrin bearing functional bromide groups was determined by ¹³C NMR, fast atom bombardment mass spectrometry, and elemental analysis. In a second step, the polymerization of the tert‐butyl acrylate monomer was optimized to avoid a star–star coupling reaction and allowed the synthesis of a well‐defined organosoluble polymer star. The determination of the macromolecular dimensions of these new star polymers by size exclusion chromatography/light scattering was in agreement with the structure of armed star polymers in a large range of predicted molecular weights. This article describes a new approach to polyelectrolyte star polymers by postmodification of poly(tert‐butyl acrylate) by acrylic arm hydrolysis in a water‐soluble system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5186–5194, 2005     

Quantitative synthesis of star-shaped poly(vinyl ether)s with a narrow molecular weight distribution by living cationic polymerization

Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl compound based on living cationic polymerization. For example, living polymers (DP(n) = 50-300) of isobutyl vinyl ether (IBVE), prepared with a cationogen/EtAlCl(2) at 0 degrees C in hexane in the presence of ethyl acetate, were allowed to react with a small amount of 1,4-cyclohexanedimethanol divinyl ether (DVE-1) to give a star-shaped poly(IBVE) in quantitative yield (100%). In addition, a notable feature of this star-shaped polymer was extremely narrow molecular weight distribution (M(w)/M(n) = 1.1-1.2). The structure of divinyl compounds and reaction conditions for the linking reaction are key factors for achieving quantitative yield of star-shaped polymers. To our best knowledge, this is the first example of selective preparation of star-shaped polymers with narrow molecular weight distribution via one-pot polymer-linking reactions, which has never been achieved in any other mechanisms. The M(w) and the number of arms per molecule ranged from 6 x 10(4) to 30 x 10(4) and 9 to 44, respectively. Thermosensitive star polymers were also synthesized in quantitative yield, and the products were found to undergo sensitive phase separation and physical gelation.