Synthesis of new siloxane urethane block copolymers and their properties

Siloxane urethane block copolymers were prepared with siloxanes as the soft segment. Films were cast from a variety of solvents. Solvent has an effect on the segregation of soft and hard segments. Surface studies, including ESCA, EDS, and FT-IR, show well segregated block copolymers with enhanced siloxane on the surface. DSC studies show a low mp (-44°C) for the soft segment and a T_g for the hard segment above room temperature. These materials show higher thermal stability compared to polyether urethane block copolymers. These copolymers also show relatively good resistance to exposure to oxygen plasma and show improved flame retardancy compared to nonsiliconated, polyether polyurethane block copolymers. © 1994 John Wiley & Sons, Inc.     

Perfluorocyclobutyl-containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization

Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl‐based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization. The PFCB‐containing acrylate monomer, p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)‐phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2′‐azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number‐average molecular weights (M_n) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (M_w/M_n≦1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4‐cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG‐CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB‐based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.     

Multiblock Copolymers Based on Highly Crystalline Polyethylene and Soft Poly(ethylene-co-butadiene) Segments: Towards Polyolefin Thermoplastic Elastomers

Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were obtained by successive controlled coordinative chain transfer polymerization (CCTP) of a mixture of ethylene and butadiene (80/20) and pure ethylene. EBR-b-PE diblock copolymers were synthesized using the {Me₂Si(C₁₃H₈)₂Nd(BH₄)₂Li(THF)}₂ complex in combination with n-butyl,n-octyl magnesium (BOMAG) used as both the alkylating and chain transfer agent (CTA). Triblock and multiblock copolymers featuring highly semi-crystalline PE hard segments and soft EBR segments were further obtained by the development of a bimetallic CTA, the pentanediyl-1,5-di(magnesium bromide) (PDMB). These new block copolymers undergo crystallization-driven organization into lamellar structures and exhibit a variety of mechanical properties, including excellent extensibility and elastic recovery in the case of triblock and multiblock copolymers.     

Synthese, 13C-NMR-Spektren und räumliche Struktur von ‘Push-Pull’-Diacetylenen

Synthesis, ¹³C-NMR Spectra, and X-Ray Investigation of ‘Push-Pull’ Diacetylenes Phenyl-substituted ‘push-pull’ diacetylenes 1f and 1g have been prepared by acetylation and benzoylation of the appropriate lithiodiynylamines 4 (Scheme 2). ¹³C-NMR spectra of diacetylenes 1a–g (Table 1) are discussed with respect to the expected polarisation of the diacetylene unit by ‘push’ and ‘pull’ substituents. X-Ray investigations of 1c , 1e , and 1f have been performed in view of the planned solid-state polymerisation of ‘push-pull’ diacetylenes. In the crystalline state, diacetylenes 1c and 1f are stacked, however, the stacking parameters do not allow a solid-state polymerisation.     

Parameters affecting transition temperatures of poly(lactic acid‐co‐polydiols) copolymer‐based polyester urethanes and their shape memory behavior

A series of polyester urethanes (PEUs) comprising poly(lactic acid‐co‐polydiol) copolymers as a soft segment, 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (BDO) as a hard segment were systematically synthesized. Soft segments, which were block copolymers of L ‐lactide (LA) and polydiols such as poly(ethylene glycol) and poly(trimethylene ether glycol), were prepared via ring opening polymerization. Glass transition temperatures (T_g) of the obtained PEUs were found strongly dependent on properties of copolymer soft segments. By simply changing composition ratio, type and molecular weight of polydiols in the soft segment preparation step, T_g of PEU can be varied in the broad range of 0–57°C. The synthesized PEUs exhibited shape memory behavior at their transition temperatures. PEUs with hard segment ratio higher than 65 mole percent showed good shape recovery. These findings suggested that it is important to manipulate molecular structure of the copolymer soft segment for a desirable transition temperature and design optimal soft to hard segment ratio in PEU for good shape recovery. Copyright © 2011 John Wiley & Sons, Ltd.     

Methionine sulfoxide and phosphonate containing double hydrophilic block copolypeptides and their mineralization of calcium carbonate

In effort to address challenges in the efficient synthesis of highly functional block copolypeptides, we report use of a combination of functional monomer polymerization and postpolymerization modification to obtain new double hydrophilic block copolypeptides with desirable properties. We prepared copolymers that contain discrete hydrophilic, nonionic poly(l‐ methionine sulfoxide) and Ca²⁺ ion binding poly(l ‐phosphonohomoalanine) segments. The facile and selective postpolymerization conversion of inexpensive, readily prepared poly(l ‐methionine) segments into nonionic, hydrophilic poly(l ‐methionine sulfoxide) segments reduces the need for use of combinations of protecting groups. The complex copolypeptides prepared using this strategy were able to promote formation of CaCO₃ microspheres with tunable polymorphism. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3707–3712     

Synthesis and Thermoreversible Gelation Properties of Main‐Chain Poly(pyridine‐2,6‐dicarboxamide‐triazole)s

A series of main‐chain poly(amide‐triazole)s were prepared by copper(I)‐catalyzed alkyne–azide AABB‐type copolymerizatons between five structurally similar diacetylenes 1 – 5 with the same diazide 6 . The acetylene units in monomers 1 – 5 possessed different degrees of conformational flexibility due to the different number of intramolecular hydrogen bonds built inside the monomer architecture. Our study showed that the conformational freedom of the monomer had a profound effect on the polymerization efficiency and the thermoreversible gelation properties of the resulting copolymers. Among all five diacetylene monomers, only the one, that is, 1 ‐Py(NH)₂ which possesses the pyridine‐2,6‐dicarboxamide unit with two built‐in intramolecular H bonds could produce the corresponding poly(amide‐triazole) Poly‐(PyNH)₂ with a significantly higher degree of polymerization (DP) than other monomers with a lesser number of intramolecular H bonds. In addition, it was found that only this polymer exhibited excellent thermoreversible gelation ability in aromatic solvents. A self‐assembling model of the organogelating polymer Poly‐(PyNH)₂ was proposed based on FTIR spectroscopy, XRD, and SEM analyses, in which H bonding, π–π aromatic stacking, hydrophobic interactions, and the structural rigidity of the polymer backbone were identified as the main driving forces for the polymer self‐assembly process.     

Comparison of micelles formed by amphiphilic star block copolymers prepared in the presence of a nonmetallic monomer activator

In this article, we describe the synthesis of PEG‐b‐polyester star block copolymers via ring‐opening polymerization (ROP) of ester monomers initiated at the hydroxyl end group of the core poly(ethylene glycol) (PEG) using HCl Et₂O as a monomer activator. The ROP of ε‐caprolactone (CL), trimethylene carbonate (TMC), or 1,4‐dioxan‐2‐one (DO) was performed to synthesize PEG‐b‐polyester star block copolymers with one, two, four, and eight arms. The PEG‐b‐polyester star block copolymers were obtained in quantitative yield, had molecular weights close to the theoretical values calculated from the molar ratio of ester monomers to PEG, and exhibited monomodal GPC curves. The crystallinity of the PEG‐b‐polyester star block copolymers was determined by differential scanning calorimetry and X‐ray diffraction. Copolymers with a higher arm number had a higher tendency toward crystallization. The crystallinity of the PEG‐b‐polyester star block copolymers also depended on the nature of the polyester block. The CMCs of the PEG‐b‐PCL star block copolymers, determined from fluorescence measurements, increased with increasing arm number. The CMCs of the four‐arm star block copolymers with different polyester segments increased in the order 4a‐PEG‐b‐PCL < 4a‐PEG‐b‐PDO < 4a‐PEG‐b‐PLGA < 4a‐PEG‐b‐PTMC, suggesting a relationship between CMC and star block copolymer crystallinity. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the PEG‐polyester star block copolymers in aqueous media, increased with decreasing arm number and increasing crystallinity. A key aspect of the present work is that we successfully prepared PEG‐b‐polyester star block copolymers by a metal‐free method. Thus, unlike copolymers synthesized by ROP using a metal as the monomer activator, our copolymers do not contain traces of metals and hence are more suitable for biomedical applications. Moreover, we confirmed that the PEG‐b‐polyester star block copolymers form micelles and hence may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2084–2096, 2008     

Ethylene-Coordinative Chain-Transfer Polymerization-Induced Self-Assembly (CCTPISA)

Block copolymers based on ethylene (E) and butadiene (B) were prepared using the ansa-bis(fluorenyl) complex {Me₂Si(C₁₃H₈)₂Nd(BH₄)₂Li(THF)}₂ in combination with (n-Bu)(n-Oct)Mg (BOMAG) as a chain-transfer agent. The diblock copolymers incorporating a soft poly(ethylene-co-butadiene) segment, called ethylene butadiene rubber (EBR), and a hard polyethylene (PE) one were obtained by simply adjusting the different feeds of monomers during the polymerization. The soluble EBR block was formed first by feeding the catalytic system dissolved in toluene at 70 °C with a mixture of ethylene and butadiene (E/B molar ratio 80 : 20). Then the feeding was stopped leading to the consumption of a large part of the residual monomers. The reactor was finally fed with ethylene to form the PE block. By varying the molar mass of the latter, it is shown that the resulting soft-b-hard block copolymers can self-assemble simultaneously to the growth of the PE block in agreement with a polymerization-induced self-assembly (PISA) mechanism. The self-assembly is discussed considering the reaction conditions, the crystallization of the PE block, and the polymerization mechanism involved.     

Organized multilayers of polydiacetylenes prepared by electrostatic self-assembly

New types of polydiacetylene multilayer are presented. The first type is based on electrostatic self-organization of diacetylene bolaamphiphiles and polyelectrolytes on a charged substrate followed by subsequent ultraviolet (UV) polymerization. The second type is prepared by direct adsorption of a water soluble polydiacetylene and a polyelectrolyte in alternating sequence. The monomeric diacetylenes are of general formula X(CH₂)₉CCC C(CH₂)₉X, with X being a sulfate (1a), phosphate (2) or pyridinium (3) head group. The polydiacetylene (1b) chosen for the multilayer is obtained by γ irradiation of the corresponding diacetylene monomer 1a. It is found that all diacetylene derivatives are well suited for building up self-assembled multilayers and that two of the monomers (1a, 2) can be polymerized on the substrate, while 3 is photo-inactive. The morphology of the multilayers is studied by scanning force microscopy and discussed. The smoothest surface topology is found for multilayers built up from the polydiacetylene 1b and a cationic polyelectrolyte in alternating sequence, while the largest unevenness is found when the anionic diacetylene 1a is alternatingly adsorbed with the cationic bolaamphiphile 3 followed by subsequent UV polymerization on the substrate.     

A novel block copolymer with excellent amphiphobicity synthesized via ARGET ATRP

The poly(methyl methacrylate)‐b‐poly(2‐[[[[2‐(perfluorohexyl)]‐sulfonyl]‐amino]ehthyl] methacrylate) (PMMA‐b‐PC₆SMA) copolymers were successfully synthesized for the first time using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) method. Under optimized reaction conditions, the degree of polymerization (DP) of resulting copolymers increased approximately linearly with monomer conversion. Structures of a well‐defined block copolymer were determined by GPC, FT–IR, and ¹H‐NMR spectra. Results from AFM and contact angle measurements of polymer films revealed the presence of block segments derived from PC₆SMA, as indicated by the obvious increase in hydrophobicity and oleophobicity. The relationship between surface composition and surface wetting ability was confirmed by XPS and AFM spectra. Compared with the random copolymer PMMA‐co‐PC₆SMA, C₆SMA dosages in the PMMA‐b‐PC₆SMA copolymers were greatly decreased, which retained its hydrophobic and oleophobic properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2040–2049     

Structure of Styrene and Acrylate Block Copolymers

Abstract

Using UV light as the energy source and polystyrene- (PS-) or polymethyl methacrylate- (PMMA-) macroinitiators with active aromatic or aliphatic thiyl end groups, PS-PMMA and PMMA-PEA (poly-ethyl acrylate) block copolymers were synthesized. The molecular weights of both block copolymers increased with increasing reaction time. The reactivity of macroinitiators depended on the type of thiyl groups and monomer and not on the length of the polymer chain. The most reactive were macroinitiators containing resonance stabilized non-substituted or substituted aromatic end groups. The decomposition of the macroinitiators took place over the formation of the thiyl radical and macroradical. The bond length, the bond dissociation energy, and the bond order of macroradical end groups were calculated. The most reactive monomer was ethyl acrylate; the less reactive was styrene. The structure, the molecular weight, and the T _g of the styrene-acrylate block copolymers were determined. The PMMA/PEA block copolymer had two of block's T _g s, the first at 105°C, the second at ?24°C, and a third at 16°C which probably represents contacting segments.     

Material Design in Poly(Lactic Acid) Systems: Block Copolymers,Star Homo- and Copolymers,and Stereocomplexes

Abstract

This paper gives a general overview of several approaches we have investigated for designing new PLA-based polymers with a broad range of properties and improved processability. These approaches include: copolymerization (block and stereoblock copolymers), microstructure and architecture control, and stereocomplexation. Multiblock copolymers with alternating “soft” and “hard” segments, synthesized over a broad range of chemical compositions, show properties ranging from hard plastics to elastomers. Stereoblock copolymers with alternating amorphous and semicrystalline PLA blocks combine the advantages of PLA homopolymers (crystallinity) and random copolymers (processability). Independent control of polymer architecture and microstructure allows for the synthesis of star polymers with various arm morphologies. A new method for stereocomplex formation between L-PLA and D-PLA, which combines in-situ polymerization with stereocomplexation, is also described. For the synthesis of these new materials we took advantage of: 1) chirality of lactide monomer, 2) retention of configuration during polymerization, 3) living nature of the ring-opening polymerization (ROP) of lactide in the presence of active hydrogen groups such as OH and NH₂, and 4) control of the level of transesterification reactions.     

Synthesis and properties of block poly(styrene amides) and poly(styrene esters)

Three series of block copolymers, namely, polystyrenecaproamide (I), polystyrenehexamethyleneadipamide (II), and poly(styreneethylene terephthalate) (III), were prepared, and the properties of the copolymers in relation to the block sequence lengths and the compositions were studied. Styrene was polymerized in the presence of aluminum chloride and thionyl chloride to give ω,ω′-dichloropolystyrenes of various degrees of polymerization from 12.0 to 51.0, which were either ammonolyzed to ω,ω′-diaminopolystyrene or hydrolyzed to ω,ω′-dihydroxypolystyrene. ω,ω′-Diaminopolystyre was treated with adipic acid to give the corresponding salts, namely, ω,ω′-diammoniumpolystyrene adipate, which was melt-polymerized either with ε-amino-n-caproic acid to give polystyrenecaproamide (I) or with hexamethylenediammonium adipate to give polystyrenehexamethyleneadipamide (II). ω,ω′-Dihydroxypolystyrene was melt-polymerized with dimethyl terephthalate and ethylene glycol to give poly(styreneethylene terephthalate) (III). All the block copolymers were of high enough molecular weight to be cast or spun into films or filaments. Upon polymerization, the increase of the block sequence of PSt units increased the amide content but decreased the ester content of the resulting copolymers. Also, an increase in n decreased the inherent viscosities of the copolymers at a constant monomer feed f_c counted by the polymer equivalent of PSt but increased the inherent viscosities at a constant monomer feed r_c counted by the monomer equivalent of PSt. The melting points of the copolymers decreased with increasing n values. Also, an increase in n decreased the densities of I and III but increased the density of II at a constant amide or ester composition F_c counted by polymer units but increased the densities of I, II, and III at a constant amide or ester composition R_c counted by the monomer unit.     

Star and Hyperbranched Polyisobutylenes via Terminally Reactive Polyisobutylene-Polystyrene Block Copolymers

Unique, highly branched polyisobutylenes (PIB) were prepared via quasiliving carbocationic copolymerization of isobutylene and styrene (St) monomers. The junction points were formed by Friedel-Crafts self alkylation of PSt segments by the carbocationic chain ends. First, linear PIB was prepared with reactive chain ends. This was reacted with St monomer to form PIB-b-PSt AB, and PSt-b-PIB-b-PSt ABA type triblock copolymers with reactive carbocationic chain ends. The terminal carbonations react with the phenyl group of the polystyrene end-segments of the block copolymers leading to chain coupling, and thus PIB star polymers in the case of AB and hyperbranched PIB from ABA block copolymers. The resulting branched polymers were characterized and the branch formation was confirmed by gel permeation chromatography (GPC) and proton nuclear magnetic resonance spectroscopy (¹H NMR).     

Block copolymerization of tert‐butyl methacrylate with α,ω‐difunctionalized polystyrene macroiniferter and hydrolysis to amphiphilic block copolymer

The block copolymerization of tert‐butyl methacrylate (tBMA) with a difunctionalized polystyrene (PS) macroinitiator was investigated. The polymerizations were performed under UV light irradiation using PS bearing α‐ and ω‐functionalized end groups containing diethyldithiocarbamyl groups as a macroiniferter. Kinetic studies indicate the molecular weights of triblock copolymers increased linearly with the conversion. Block copolymers with different lengths of PtBMA segments were easily prepared by varying the ratio of tBMA and PS macroiniferter or by controlling the monomer conversion. The formations of block copolymers were characterized by gel permeation chromatographic, ¹H NMR, and DSC analyses. PtBMA segments of the triblock copolymer were subsequently hydrolyzed quantitatively to poly(methacrylic acid) segments using concentrated HCl as a catalyst in a refluxing solution of dioxane, and then an amphiphilic ABA triblock copolymer was produced. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1450–1455, 2001     

New processes and designed polymers by cationic techniques

The most important recent development in cationic polymerizations is the emergence of living polymerizations leading to a variety of new potentially useful well-defined macromolecules under conventional laboratory conditions. Three requirements have to coexist for living carbocationic polymerization to occur: Controlled initiation controlled chain-transferless propagation and controlled (quasiliving) termination. The first part of this presentation will briefly discuss the road to these three key requirements. The second part will concern practical consequences and select systems. The synthesis of narrow-molecular-weight-distribution (M̄_w/M̄_n = 1.1 - 1.3) tert-chlorine telechelic polyisobutylenes over a wide molecular weight range (M̄_n from ∼1000 to ∼125, 000 g/mole) will be outlined together with recent work on aromatic olefins, e.g., styrene, tert-butylstyrene and p-chlorostyrene. These developments led to the combination of these living systems for the synthesis of block copolymers by sequential monomer addition. Tri- or higher block copolymers comprising glassy outer segments and rubbery inner segments, for example, poly(styrene-b-isobutylene-b-styrene, poly(p-chlorostyrene-b-isobutylene-b-p-chlorostyrene), have been prepared. These new thermoplastic elastomers exhibit phase-separated microstructures and an interesting combination of physical-mechanical properties.     

Control through monomer placement of surface properties and morphology of fluoromethacrylate copolymers

The arrangement of monomers and morphology of fluorinated copolymers of methyl methacrylate (MMA) were found to be important for controlling the surface energy of the materials when formed into thin films. Novel copolymers of MMA and 2,2,3,3,4,4,4‐heptafluorobutyl methacrylate (F3MA) were prepared with different monomer placement, namely statistical and block arrangements of the monomer units. The surface energies decreased with increasing incorporation of F3MA, in a manner consistent with previous reports for similar copolymers; however, the surface energies of the block copolymers were consistently lower than the statistical copolymers. This was interpreted as arising from conformational restriction of presentation of the fluoromonomers to the surface in the statistical copolymers, and formation of phase‐separated domains at the surface of the block copolymers. The morphology of the block copolymers was confirmed by small angle X‐ray scattering measurements, which allowed calculation of a solubility parameter for the fluorinated segments. The results have implications for the design of more environmentally acceptable materials with ultra‐low surface energies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2633–2641     

Stereospecific sequential block copolymerizations of styrene and 1,3‐butadiene with a C5Me5TiMe3/B(C6F5)3/Al(oct)3 catalyst

This article reports a new methodology for preparing highly stereoregular styrene (ST)/1,3‐butadiene (BD) block copolymers, composed of syndiotactic polystyrene (syn‐PS) segments chemically bonded with cis‐polybutadiene (cis‐PB) segments, through a stereospecific sequential block copolymerization of ST with BD in the presence of a C₅Me₅TiMe₃/B(C₆F₅)₃/Al(oct)₃ catalyst. The first polymerization step, conducted in toluene at ?25 °C, was attributed to the syndiospecific living polymerization of ST. The second step, conducted at ?40 °C, was attributed to the cis‐specific living polymerization of BD. The livingness of the whole polymerization system was confirmed through a linear increase in the weight‐average molecular weights of the copolymers versus the polymer yields in both steps, whereas the molar mass distributions remained constant. The profound cross reactivity of the styrenic‐end‐group active species with BD toward ST led to the production of syn‐PS‐b‐cis‐PB copolymers with extremely high block efficiencies. Because of the presence of crystallizable syn‐PS segments, this copolymer exhibited high melting temperatures (up to 270 °C), which were remarkably different from those of the corresponding anionic ST–BD copolymers, for which no melting temperatures were observed. Scanning electron microscopy pictures of a binary syn‐PS/cis‐PB blend with or without the addition of the syn‐PS‐b‐cis‐PB copolymers proved that it could be used as an effective compatibilizer for noncompatibilized syn‐PS/cis‐PB binary blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1188–1195, 2005     

Synthesis and evaluation of photolytically and thermally crosslinkable polyimide copolymers with diacetylene functionality

The polyimide block copolymers with diacetylene functionality were prepared in a two-step process: (1) oligomeric imide formation terminated with 1-amino-3-ethynylbenzene, and (2) oxidative coupling of the acetylene-terminated polyimides with p- and/or m-diethynylbenzene or bispropargyl ether of Bisphenol A to form block copolymers, or oxidative coupling within themselves in the presence of a copper (I) catalyst. The resulting copolymers were crosslinked with UV irradiation or thermal treatment. The thermal crosslinking process and the thermal stability of the crosslinked materials were studied by differential scanning calorimetry (DSC) and isothermal gravimetric analysis (IGA), respectively.