Poly(α-isobutyl-β-D,L-aspartate)s: Polymerization effects on configuration and crystal structure of the stereocopolymers

Different polymerization methods were used for the preparation of poly(α-isobutyl-β-D ,L -aspartate)s containing variable ratios of D - to L -aspartic units and the microstructure of the resulting stereocopolymers was examined by NMR spectroscopy. Anionic ring-opening polymerization in solution of enantiomeric mixtures of α-isobutyl-β-D - and L -aspartalactams was found to proceed stereoselectively rendering block copolymers composed of right- and left-handed helical sequences. Configurationally statistical copolymers were obtained instead when the enantiomeric lactam mixtures were polymerized in the bulk. Random stereocopolymers could be prepared also by polycondensation in solution of mixtures of pentachlorophenyl α-isobutyl-β-D and -L -aspartates. The conformation in solution and the crystal structure of the resulting copolymers were investigated in connection with their stereochemical configuration and these features compared with those displayed by optically pure poly(α-isobutyl-β-L -aspartate). © 1996 John Wiley & Sons, Inc.     

Poly(vinyl alcohol)–Thioxanthone as One‐Component Type II Photoinitiator for Free Radical Polymerization in Organic and Aqueous Media

A novel one‐component type II polymeric photoinitiator, poly(vinyl alcohol)–thioxanthone (PVA–TX), is synthesized by a simple acetalization process and characterized. PVA–TX enables photopolymerization of methyl methacrylate and acrylamide in both organic and aqueous media. Photopolymerization proceeds even in the absence of a co‐initiator since PVA–TX possesses both chromophoric and hydrogen donating sites in the structure.

     

Radical copolymerization of novel trifluorovinyl ethers with ethyl vinyl ether and vinyl acetate: Estimating reactivity ratios and understanding reactivity behavior of the propagating radical

Two novel trifluorovinyl ether (TFVE) monomers were copolymerized with either ethyl vinyl ether (EVE) or vinyl acetate (VAc) in a redox‐initiated aqueous emulsion: 1‐(2‐phenoxyethoxy)‐1,2,2‐trifluoroethene (Ph‐TFVE) and 1‐[2‐(2‐ethoxyethoxy)ethoxy]‐1,2,2‐trifluoroethene (Et‐TFVE). Previous studies demonstrated a propensity for radical hydrogen abstraction from the oligoether pendant group during the homopolymerization of Et‐TFVE with continued propagation of the resulting radical, thereby providing the rationale to investigate the copolymerization of our new TFVEs with EVE or VAc. Reactivity ratios were estimated using the error‐in‐variables model from a series of bulk free radical copolymerizations of Ph‐TFVE with EVE or VAc. The reactivity ratios were r_Ph‐TFVE = 0.25 ± 0.07, r_EVE = 0.016 ± 0.04; r_Ph‐TFVE = 0.034 ± 0.04, r_VAc =0.89 ±0.08. Partial hydrolysis of polymers containing VAc to vinyl alcohol (VA) resulted in two terpolymers: poly(Ph‐TFVE‐co‐VAc‐co‐VA) and poly(Et‐TFVE‐co‐VAc‐co‐VA), respectively. We investigated the possibility of hydrogen abstraction from VAc during polymerization by comparing the molar mass before and after hydrolysis. Abstraction from VAc was not apparent during polymerization; however, abstraction from the oligoether pendant group of Et‐TFVE was again evident and was more significant for those copolymers having a greater fraction of Et‐TFVE in the monomer feed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1344–1354, 2000     

Mechanistic Insight into the Stereochemical Control of Lactide Polymerization by Salan–Aluminum Catalysts

Alkyl aluminum complexes of chiral salan ligands assembled around the 2,2′‐bipyrrolidine core form as single diastereomers that have identical configurations of the N donors. Active catalysts for the polymerization of lactide were formed upon the addition of benzyl alcohol. Polymeryl exchange between enantiomorphous aluminum species had a dramatic effect on the tacticity of the poly(lactic acid) (PLA) in the polymerization of racemic lactide (rac‐LA): The enantiomerically pure catalyst of the nonsubstituted salan ligand led to isotactic PLA, and the racemic catalyst exhibited lower stereocontrol. The enantiomerically pure catalyst of the chloro‐substituted salan ligand led to PLA with a slight tendency toward heterotacticity, whereas the racemic catalyst led to PLA of almost perfect heterotacticity following an insertion/auto‐inhibition/exchange mechanism.     

Macrocycles IV. Macrocyclic polylactones as bifunctional monomers for polycondensations

Tin containing macrocyclic polylactones were prepared by di-n-butyl-2-stanna-1,3-dioxepane-initiated polymerizations of ε-caprolactone in bulk. The average ring size was varied from 10 to 100 monomer units via the monomer/initiator (M/I) ratio. Addition of terephthaloyl or sebacoyl chloride to the in situ prepared macrocycles yielded polycondensates under elimination of di-n-butyl tin dichloride. The molecular weights increased with the reaction temperature (e.g., 80–140°C) and with the size of the macrocycles. Number-average molecular weights (M_ns) up to 90,000 and polydispersities between 1.65 and 2.0 were obtained. Further polycondensations were conducted with isophthaloyl chloride, 4,4′-biphenyldicarbonylchloride and 4,4′-phenylenebisacryloylchloride. Several polycondensations were performed with macrocyclic poly (δ-valerolactone) and poly (β-D ,L -butyrolactone). In those cases the increase of the molecular weight was lower. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1373–1378, 1998     

Synthesis and Ring Opening Polymerization of a New Functional Lactone, α‐Iodo‐ε‐caprolactone: A Novel Route to Functionalized Aliphatic Polyesters

A new functional lactone, α‐iodo‐ε‐caprolactone (αIεCL), was synthesized from ε‐caprolactone by anionic activation using a non‐nucleophilic strong base (lithium diisopropylamide) followed by an electrophilic substitution with iodine chloride. Ring‐opening (co)polymerizations of the resulting monomer with ε‐caprolactone were carried out using tin 2‐ethylhexanoate as a catalyst in toluene at 100 °C. Homopolymerization of αIεCL was achieved, and poly(αIεCL) was fully characterized by SEC, ¹H NMR and elemental analysis. Random copolymerizations of αIεCL with εCL were controlled with experimental molecular weights close to the theoretical values, narrow molecular weight distributions and a good agreement between experimental and theoretical molar compositions of αIεCL.

     

Synthesis and characterization of mid‐ and end‐chain functional telechelics by controlled polymerization methods and coupling processes

Well‐defined polystyrene‐ (PSt) or poly(ε‐caprolactone) (PCL)‐based polymers containing mid‐ or end‐chain 2,5 or 3,5‐ dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). 1,4‐Dibromo‐2‐(bromomethyl)benzene, 1,3‐dibromo‐5‐(bromomethyl)benzene, and 1,4‐dibromo‐2,5‐di(bromomethyl)benzene were used as initiators in ATRP of styrene (St) in conjunction with CuBr/2,2′‐bipyridine as catalyst. 2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene initiated the ROP of ε‐caprolactone (CL) in the presence of stannous octoate (Sn(Oct)₂) catalyst. The reaction of these polymers with amino‐ or aldehyde‐functionalized monoboronic acids, in Suzuki‐type couplings, afforded the corresponding telechelics. Further functionalization with oxidable groups such as 2‐pyrrolyl or 1‐naphthyl was attained by condensation reactions of the amino or aldehyde groups with low molecular weight aldehydes or amines, respectively, with the formation of azomethine linkages. Preliminary attempts for the synthesis of fully conjugated poly(Schiff base) with polymeric segments as substituents, by oxidative polymerization of the macromonomers, are presented. All the starting, intermediate, or final polymers were structurally analyzed by spectral methods (¹H NMR, ¹³C NMR, and IR). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 727–743, 2006     

Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of 2-hydroxyethyl acrylate

The application of atom transfer radical polymerization (ATRP) to the homopolymerization of 2-hydroxyethyl acrylate, a functional monomer, is reported. The polymerizations exhibit first-order kinetics, and molecular weights increase linearly with conversion. Polydispersities remain low throughout the polymerization (M_w/M_n ≈ 1.2). Reactions were conducted in bulk and in 1 : 1 (by volume) aqueous solution; the latter demonstrates the resilience of ATRP to protic media. Analysis of poly(2-hydroxyethyl acrylate) by MALDI-MS and ¹H-NMR shows M_n,exp to be much closer to M_n,th than those observed by SEC using polystyrene standards. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1417–1424, 1998     

Ring‐Opening Polymerization of ε‐Caprolactone by Poly(ethylene glycol) by an Activated Monomer Mechanism

Summary: The polymerization of ε‐caprolactone (CL) in the presence of HCl · Et₂O by an activated monomer mechanism was performed to synthesize diblock or triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(ε‐caprolactone) (PCL). The obtained PCLs had molecular weights close to the theoretical values calculated from the CL to PEG molar ratios and exibited monomodal GPC curves. We successfully prepared PEG and PCL block copolymers by a metal‐free method.

The non‐metal catalyzed living ring‐opening polymerisation of ε‐caprolactone by PEG.     

Molecular characterization of maleic anhydride-functionalized polypropylene

This work deals with the molecular characterization of maleic anhydride melt-functionalized polypropylene (PP-g-MA). The functionalization mechanism, the nature, the concentration, and the location of grafted anhydride species onto the polypropylene chain are discussed. The polypropylene functionalization was performed using a pre-heated Brabender Plastograph (190°C, 4 min of mixing time). Several concentrations of maleic anhydride and organic peroxide were used for this study. In those experimental conditions, the organic peroxide undergoes an homolytic rupture and carries out a polypropylene tertiary hydrogen abstraction. The resulting macroradical undergoes a β-scission leading to a radical chain end which reacts with maleic anhydride. When a termination reaction occurs at this first step a succinic type anhydride chain end is obtained. However, oligomerization of maleic anhydride is found to occur more frequently leading to poly (maleic anhydride) chain end. Concentration of both anhydride types and minimal length of the grafted poly (maleic anhydride) were determined. A fraction of maleic anhydride does not react with polypropylene or homopolymerize leading to nongrafted poly (maleic anhydride). © 1995 John Wiley & Sons, Inc.     

Synthesis and Characterization of β‐CD‐Coated Polystyrene Microspheres by γ‐Ray Radiation Emulsion Polymerization

Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization.     

Simultaneous reversible addition fragmentation chain transfer and ring‐opening polymerization

The simultaneous ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) and 2‐hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ε‐CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) under typical ROP conditions (T > 100 °C) using toluene as the solvent in order to lead to the graft copolymer PHEMA‐g‐PCL. Graft copolymer formation is evidenced by a combination of size‐exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000–10,000 g mol^?1) the copolymer grafting density is higher than 90%. The ratio of free HEMA‐PCL homopolymer produced during the “one‐step” process was found to depend on the HEMA concentration, as well as the half‐life time of the radical initiator used. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058–3067, 2008     

Discrete Metal Catalysts for Stereoselective Ring‐Opening Polymerization of Chiral Racemic β‐Lactones

Poly(β‐hydroxyalkanoate)s (PHAs) are a class of aliphatic polyesters that can be efficiently synthesized by ring‐opening polymerization (ROP) of β‐lactones. The case of chiral racemic β‐substituted β‐lactones is particularly appealing since these monomers open the way to original tacticities and materials different from those biotechnologically produced. In this overview, after briefly surveying general considerations associated to the ROP of β‐lactones and metal‐based catalysts used in stereoselective ROP of racemic β‐butyrolactone, special emphasis is given to discrete rare earth catalysts that have allowed the preparation of highly syndiotactic poly(3‐hydroxybutyrate)s. Recent developments – such as preparation of stereocontrolled PHAs with pendant structural groups via (co)polymerization of functional β‐substituted β‐lactones, and highly alternating copolymers obtained by ROP of mixtures of enantiomerically pure but different monomers – are also discussed.

     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Preparation of novel poly(ethylene oxide‐co‐glycidol)‐graft‐poly(ε‐caprolactone) copolymers and inclusion complexation of the grafted chains with α‐cyclodextrin

A well‐defined comblike copolymer of poly(ethylene oxide‐co‐glycidol) [(poly(EO‐co‐Gly)] as the main chain and poly(ε‐caprolactone) (PCL) as the side chain was successfully prepared by the combination of anionic polymerization and ring‐opening polymerization. The glycidol was protected by ethyl vinyl ether to form 2,3‐epoxypropyl‐1‐ethoxyethyl ether (EPEE) first, and then ethylene oxide was copolymerized with EPEE by an anionic mechanism. The EPEE segments of the copolymer were deprotected by formic acid, and the glycidol segments of the copolymers were recovered after saponification. Poly(EO‐co‐Gly) with multihydroxyls was used further to initiate the ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate. When the grafted copolymer was mixed with α‐cyclodextrin, crystalline inclusion complexes (ICs) were formed, and the intermediate and final products, poly(ethylene oxide‐co‐glycidol)‐graft‐poly(ε‐caprolactone) and ICs, were characterized with gel permeation chromatography, NMR, differential scanning calorimetry, X‐ray diffraction, and thermogravimetric analysis in detail. The obtained ICs had a channel‐type crystalline structure, and the ratio of ε‐caprolactone units to α‐cyclodextrin for the ICs was higher than 1:1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3684–3691, 2006     

氧化偶联聚合的方法合成新型电活性聚醚砜及其结构表征

通过氧化偶联聚合的方法我们制备了一种新型电活性聚芳醚砜,这种聚合物主链上含有苯基封端的苯胺四聚体齐聚物单元。我们通红外、核磁和XRD对其结构进行了表征。在1.0M的硫酸水溶液介质中我们对其电活性进行了研究,聚合物展现出两对氧化还原峰。此外,我们使用TGA测试手段对其热稳定性也做了研究。在室温质子酸掺杂的条件下聚合物的导电率为1.37 × 10-7 S·cm-1。     

Preparation and properties of poly(alkyl vinyl ether-2-ethyl-2-oxazoline) diblock copolymers

A method for the synthesis of well-defined poly(alkyl vinyl ether–2-ethyl-2-oxazoline) diblock copolymers with hydrolytically stable block linkages has been developed. Monofunctional poly(alkyl vinyl ether) oligomers with nearly Poisson molecular weight distributions were prepared via a living cationic polymerization method using chloroethyl vinyl ether together with HI/ZnI₂ as the initiating system and lithium borohydride as the termination reagent. Using the resultant chloroethyl ether functional oligomers in combination with sodium iodide as macroinitiators, 2-ethyl-2-oxazoline was polymerized in chlorobenzene/NMP to afford diblock copolymers. A series of poly(methyl vinyl ether–2-ethyl-2-oxazoline) diblock materials were found to have polydispersities of ≈ 1.3–1.4 and are microphase separated as indicated by two T_g's in their DSC thermograms. These copolymers are presently being used as model materials to study fundamental parameters important for steric stabilization of dispersions in polar media. © 1993 John Wiley & Sons, Inc.     

Poly(N-phenyl-2-hydroxytrimethylene amine): Its blends with poly(ϵ-caprolactone) and water-soluble polyethers

A new polymer with pendant hydroxyl groups, namely, poly(N-phenyl-2-hydroxytrime-thylene amine) (PHA), was synthesized by a direct condensation polymerization of aniline and epichlorohydrin in an alkaline medium. The new polymer is amorphous with a glass transition temperature (T_g) of 70°C. Blends of PHA with poly(ϵ-caprolactone) (PCL), as well as with two water-soluble polyethers, poly(ethylene oxide) (PEO) and poly(vinyl methyl ether) (PVME), were prepared by casting from a common solvent. It was found that all the three blends were miscible and showed a single, composition dependent glass transition temperature (T_g). FTIR studies revealed that PHA can form hydrogen bonds with PCL, PEO, and PVME, which are driving forces for the miscibility of the blends. © 1997 John Wiley & Sons, Inc.     

Control of reaction mechanisms in cationically polymerized epoxy resins facilitates the adjustment of morphology and mechanical properties

Structure–property relations of cationically polymerized epoxy thermosets with different morphologies are examined. The morphology adjustment of amorphous epoxy based copolymers and partially crystalline polymer alloys is carried out with star‐shaped poly(ε‐caprolactone) (SPCL) bearing various numbers of hydroxyl end groups. These hydroxyl groups are known for their reactivity toward epoxides following the activated monomer (AM) mechanism. For this reason, four‐armed SPCL was synthesized with four hydroxyl end groups (SPCL‐tetraol) and, in addition, with successively esterified ones down to a SPCL with four ester end groups (SPCL‐tetraester). SPCL species bearing fewer or no hydroxyl end groups segregate into needle‐like nanodomains within the epoxy networks and, if the concentration is high enough, also into crystalline domains. The stronger phase separation of SPCL‐tetraester within the epoxy network compared with SPCL‐tetraol is due to a reduction of the AM mechanism. The mechanical properties resulting from different morphologies lead to a trade‐off between higher storage moduli and T_g values in the case of the more phase separated (and partially crystalline) polymer alloys and higher strain at break in the case of the amorphous copolymers. Nevertheless, in both cases toughness is improved or at least kept on the same level as for the pure epoxy resin. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2188–2199