Doris Pospiech

Leibniz Institute of Polymer Research | ipfdd · Department Polymer Structures

Understanding the interplay between the molecular structure of the ionic liquid (IL) subunit, the resulting nanostructure and ion transport in polymerized ionic liquids (PILs) is necessary for the realization of high-performance solid-state electrolytes required in various advanced applications. Herein, we present a detailed structural characteriza...

The solution behavior of poly(butylene terephthalate) (PBT) copolyesters with dilinoleic monomer units (dilinoleic diol (LD) / dilinoleic diacid (LA)) is studied to understand the processing behavior from melt. NMR investigations show that the short‐chain branches are characterized by a distribution of different alkyl chain lengths, where n‐butyl (...

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/Li...

Polymeric single chloride-ion conductor networks based on acrylic imidazolium chloride ionic liquid monomers AACXImCYCl as reported previously are prepared. The chemical structure of the polymers is varied with respect to the acrylic substituents (alkyl spacer and alkyl substituent in the imidazolium ring). The networks are examined in detail with...

The interest in bio‐based alternatives to classical polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) is steadily growing to achieve a more sustainable approach to polymer materials. In this study, PBT/poly(butylene furanoate) (PBF) blends are prepared, characterized and extrusion foamed. PBF as a bio‐base...

Multifunctional metallic nanostructures are essential in the architecture of modern technology. However, their characterization remains challenging due to their hybrid nature. In this study, we present a novel photoreduction-based protocol for augmenting the inherent properties of imidazolium-containing ionic polymers (IIP)s through orthogonal func...

A series of flexible polyurethane foams (FPUFs) were prepared with single and different combinations of flame retardants and additives. Expandable graphite (EG), phosphorous polyol (OP), copper (II) oxide (CuO), and/or castor oil (CAS) were added to FPUF during the foam preparation in a one-step process. The purpose of the study is to evaluate the...

Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fire-retardant moieties through co- or ter-polymerization reactions of styrene with diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl-p-vinylbenzyl phosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methylamino]ethyl ester (ADEPMAE) and maleimide (MI). In...

The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing compounds, am...

Organic, solid‐state batteries require efficient solid electrolytes able to provide stable ion conduction. Here, we present solid electrolytes based on ionic liquid (IL) polymers with chloride counterions as electrolyte materials for batteries. Acrylic monomers with imidazolium substituents with alkyl side groups that are linked by alkyl spacers to...

The effects of covalently bound phosphorus (P-) and nitrogen (N-) bearing groups on the thermal and combustion attributes of polystyrene have been investigated. The necessary chemical modifications were achieved through co - and ter- polymerisation reactions, in a suitable solvent, under radical initiation conditions. The influence of P–N cooperati...

Poly(butylene terephthalate) (PBT) is difficult to foam due to its unfavorable rheological behavior (low melt strength, no strain hardening). In particular, a high expansion as well as a homogeneous cell morphology are difficult to achieve. This can be altered successfully by addition of multifunctional chain extenders. Chain extenders cause non‐de...

In this study, solvogels containing (2-((2-(ethoxycarbonyl)prop-2-en-1-yl)oxy)-ethyl) phosphonic acid (ECPA) and N,N′-diethyl-1,3-bis-(acrylamido)propane (BNEAA) as the crosslinker are synthesized by UV induced crosslinking photopolymerization in various solvents. The polymerization of the ECPA monomer is monitored by the conversion of double bonds...

The aspects of fire retardation in some phosphorus-modified polymethyl methacrylate (PMMA) and polystyrene (PSt) polymers are reported in the present paper. Both additive and reactive strategies were employed to obtain the desired level of loading of the phosphorus-bearing compound/moiety (2 wt.% of P in each case). Test samples were obtained using...

Organic/inorganic hybrid composite materials with the dispersed phases in sizes down to a few tens of nanometers raised very great interest. In this paper, it is shown that silica/epoxy nanocomposites with a silica content of 6 wt % may be obtained with an “in situ” sol–gel procedure starting from two precursors: tetraethyl orthosilicate (TEOS) and...

Advanced oxidation processes are the main way to remove persistent organic trace compounds from water. For these processes, heterogeneous Fenton catalysts with low iron leaching and high catalytic activity are required. Here, the preparation of such catalysts consisting of silica-supported iron oxide (Fe2O3/SiOx) embedded in thermoplastic polymers...

Hydrogels with immobilized enzymes are increasingly applied in biocatalytic industrial processes. Here, polymer hydrogels containing 2-hydroxyethyl methacrylate (HEMA), itaconic acid (ITA), (2-((2-(ethoxycarbonyl)prop-2-en-1-yl)oxy)-ethyl) phosphonic acid (ECPPA), and N,N′-diethyl-1,3-bis (acrylamido)propane (BAAP) as the cross-linker are synthesiz...

Application of lipases (preferentially Candida antarctica Lipase B, CALB) for melt polycondensation of aliphatic polyesters by transesterification of activated dicarboxylic acids with diols allows to displace toxic metal and metal oxide catalysts. Immobilization of the enzyme enhances the activity and the temperature range of use. The possibility t...

Aromatic-aliphatic polyesters can be prepared as bio-based materials by incorporating monomers from biogenic sources. Here, 2-methyl (E)-3-(4-(2-hydroxyethoxy)-3-methoxyphenyl)acrylate, a derivative of ferulic acid, was synthesised and inserted into the structure of...

Novel phosphine containing poly(arylene ether)s with trivalent phosphorus are prepared by reaction of bis(4-fluorophenyl) phenylphosphine with 2,2-bis(4-hydroxyphenyl)propane. The reaction conditions are adjusted to avoid partial oxidation of the phosphine derivative during polycondensation. Solution polycondensation results in copolymers with phos...

Solid polymer electrolytes for bipolar lithium ion batteries requiring electrochemical stability of 4.5 V vs. Li/Li+ are presented. Thus, imidazolium-containing poly(ionic liquid) (PIL) networks were prepared by crosslinking UV-photopolymerization in an in situ approach (i.e., to allow preparation directly on the electrodes used). The crosslinks in...

In this chapter, the development of semifluorinated polymers for potential application in organic electronics is outlined. Organic field effect transistors (OFETs) are employed as example for basic electronic devices which require both semiconducting polymers as well as dielectric polymers. The interface between the materials used has to be optimiz...

Filling of cells with liquid electrolytes is the time-determining step in the production of lithium-ion batteries (LIBs). The influencing factors are not completely understood and need further research. The adhesion of the solid components, i.e. anode, cathode and separators, to the electrolyte and the respective interfaces play an important role....

Poly(methyl methacrylate) (PMMA) is one of the most important polymers for application as a dielectric layer in organic electronics, e.g. in organic field-effect transistors. The key to improve the transistor performance is the optimization of the interface between the semiconductor and the dielectric layer. Here, the surface order in thin films of...

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H‐NMR spectroscopic data (more than 100 data points) are used to construct...

Thermotropic liquid crystalline polyesters with varied chemical structure are synthesized by melt transesterification polycondensation. They are employed as matrix for blends with lignin materials to obtain melt‐spinnable precursors for carbon fibers. The lignin samples are carefully purified by fractionation, enzymatic removal of reducing sugars,...

Bisdithiooxalate has recently been introduced as a new thermo-reversible hetero Diels-Alder dilinker. Here, we demonstrate that the same compound has proved to be a very effective coupling agent for amino-terminated polyamides. Model reactions with aliphatic amines in solution show that bisdithiooxalate possesses four reactive centers which already...

A series of phosphonate-containing compounds based on dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) is presented. BPPO is synthesized by a three–component condensation and is added to activated alkenes with systematically varied structure via phospha-Michael addition. Acrylates, α,β-unsaturated carboxylic acid diesters and benzoquinone are use...

The synthesis of a new side‐chain semifluorinated thiophene monomer obtained by the reaction of 3‐thiophene ethanol with 4,4,5,5,6,6,7,7,8,8,9,9,9‐tridecafluorononan‐1‐ol is reported. The side‐chain semifluorinated monomer is polymerized using Kumada catalyst‐transfer polycondensation to obtain the regioregular side‐chain semifluorinated thiophene...

The phase separation and surface characteristics of poly(propyl methacrylate-b-methyl methacrylate) (PPrMA-b-PMMA) diblock copolymers were studied and compared to strongly phase-separated poly(pentyl methacrylate-b-methyl methacrylate) (PPMA-b-PMMA) block copolymers (BCPs). PPrMA-b-PMMA with varied compositions and molar masses was synthesized by l...

The synthesis of novel phosphonate-containing copolymers with methyl methacrylate (MMA) is reported. As phosphonate comonomers ethyl-2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EDHPOBA), with free phosphonic acid group, and the respective methyl ester ethyl-2-[4-(dimethoxyphosphoryl)-2-oxabutyl]acrylate (EDMPOBA) are employed. The impact of the...

UV-Crosslinkable itaconic copolymers are developed to provide new multifunctional materials for coatings which combine crosslinkable functionalities and the possibility to immobilize enzymes. The polymer-immobilized enzymes were used for water treatment to decompose persistent organic molecules. Introduction of suitable comonomers allows tailoring...

Frontispiece: DOPO-containing polyesters as new flame retardants for biobased polyesters are reported. Their fire behavior is evaluated by cone calorimetry. The cover image shows the residues of five different polyesters with varied phosphorus content after forced-flaming combustion (left) and the chemical structure of selected species found in the...

Polyesters with 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide-containing comonomers are synthesized aiming to improve the flame retardancy of aliphatic polyesters such as poly(butylene succinate) and poly(butylene sebacate). The influence of the chemical structure on the thermal decomposition and pyrolysis is examined using a combination of th...

Printed electronics have been introduced into the commercial markets in recent years. Various printing technologies have emerged aiming to process printed electronic devices with low cost, environmental friendliness, and compatibility with large areas and flexible substrates. The aim of this study is to propose a continuous solution dispensing tech...

Diblock copolymers (BCP) with poly(methyl methacrylate) and poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PsfMA) blocks prepared by anionic polymerization in tetrahydrofuran at −78 °C and atom transfer radical polymerization (ATRP) at 60 °C, respectively, with stepwise varied composition over a wide range in the phase diagram are compared with res...

This study investigates the morphology changes in thin diblock copolymer (DiBCP) films occurring in the interaction with modified nanoparticles (NPs). Magnetite (Fe 3 O 4 ) and silica (SiO x ) were prepared and used. Poly(pentyl methacrylate-b-methyl methacrylate) (PPMA-b-PMMA) (70/30 mol mol ⁻¹ , hcp cylinders of the PMMA phase) DiBCP were employe...

Poly(methacrylate)s with semifluorinated side-chains of the general structure -(CH2)n-(CF2)m-F were studied to elucidate the influence of the side-chain structure on the ordering behavior in the solid state and in thin films. The aim was to find correlations between the chemical structure of the polymer, chemical composition near the surface, order...

In order to prevent freshwater biofouling glass and metal surfaces were coated with novel transparent methacrylate-based copolymers. The multifunctionality of the copolymers, such as adhesion to the substrate, surface polarity, mechanical long-term stability in water, and ability to form metal complexes was inserted by the choice of suitable comono...

Nondestructive flaw detection in polymeric materials is important but difficult to achieve. In this research, the application of magnetite nanoparticles (MNPs) in nondestructive flaw detection is studied and realized, to the best of our knowledge, for the first time. Superparamagnetic and highly magnetic (up to 63 emu/g) magnetite core-shell nanopa...

We present a detailed structural characterization of 6-[4-(4´-cyanophenyl)phenoxy]hexyl methacrylate (CPPHMA) side chain liquid crystal homopolymer and its copolymers with either 4-benzoylphenyl methacrylate (BPMA) or methyl methacylate (MMA) and BPMA. The thermotropic properties of copolymers with stepwise varied chemical composition are investiga...

We present a “one-pot” supercritical approach for creating organized metal nanoparticle arrays. For this an improved method of deposition of micelles formed by semifluorinated poly(methyl methacrylate)-block-poly(perfluoroalkyl methacrylate) diblock copolymers in supercritical CO2 solution is applied. The presented approach provides metal clusters...

Reactive and non-reactive diblock copolymers based on polyethylene oxide (PEO) and a poly(glycidyl methacrylate) (PGMA, reactive) or polystyrene (non-reactive) block, respectively, are prepared via ATRP and those are incorporated into a cycloaliphatic epoxy matrix. Crosslinking of the matrix is then performed by cationic UV curing, producing modifi...

Diblock copolymers (BCPs) show phase separation on mesoscopic length scales and form ordered morphologies in both bulk and thin films, the latter resulting in nanostructured surfaces. Morphologies in thin films are strongly influenced by film parameters, the ratio of film thickness and bulk domain spacing. Laterally structured polymer surfaces may...

Linear aliphatic copolyesters consisting of the biobased diols ethylene glycol, 1,3-propane diol, and 1,4-butane diol, the biobased dicarboxylic acids succinic acid, adipic acid, and sebacic acid, and a 9,10-dihydro-9-oxa-10-phospha-phenanthren-10-oxide (DOPO)-containing diol or dicarboxylic acid are presented. Structural characteristics of the new...

Random copolymers of methyl methacrylate (MMA) and sermifluorinated methacrylate (sfMA), with constant side chain length (H10F10), as comonomers and various sfMA molar contents were studied by Dielectric Relaxation Spectroscopy (DRS) technique with respect to their phase transitions and molecular dynamics. DRS technique was proven a suitable techni...

Diblock copolymers (BCPs) show phase separation on mesoscopic length scales and form ordered morphologies in both bulk and thin films, the latter resulting in nanostructured surfaces. Morphologies in thin films are strongly influenced by film parameters, the ratio of film thickness and bulk domain spacing. Laterally structured polymer surfaces may serve...

The crystallization behavior of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) filled with different amount of multi-walled carbon nanotubes (MWCNT) has been experimentally determined in the entire temperature range between glass transition and melting temperature. Differential fast scanning chip calorimetry, realizing coolin...

Organo-modified aluminophosphate with kanemite-like structure was used for the in situ synthesis of polypropylene (PP) nanocomposites performed by metallocene-catalyzed polymerization. The filler exhibits a layered structure with different organic pending groups arranged in the interlayer space. Melt-compounded composites with the same filler were...

Unlabelled: Polymers for all-organic field-effect transistors are under development to cope with the increasing demand for novel materials for organic electronics. Besides the semiconductor, the dielectric layer determines the efficiency of the final device. Poly(methyl methacrylate) (PMMA) is a frequently used dielectric. In this work, the chemic...

A novel way for destruction-free, volume-oriented component diagnostics is reported. Surface-modified magnetic nanoparticles are applied for impregnation of plasma-activated UHMW PE textiles, which are embedded into an epoxy matrix. Supported by simulations, this comprehensive study from single molecules to composites extends the knowledge of molec...

A comparative study of the decomposition and combustion behavior of systematically varied linear polyether analogs is reported. Properties of aromatic polyethers of bisphenol A/or 4,4'-dihydroxy biphenyl with bis(4-fluorophenyl) derivatives with phosphorus, -CF3 and methoxy -OCH3 constituents were systematically evaluated. All polyethers were synth...

We investigated the thin film morphology of two different asymmetric block copolymers (BCP), polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(n-pentyl methacrylate)-block-poly(methyl methacrylate) (PPMA-b-PMMA), loaded with pre-synthesized iron oxide nanoparticles (NP). The chemical composition of the BCP constituents determines the str...

In the present study, different aromatic moieties, naphthalene and benzene, were introduced into alkynes to constitute 1,3,5-tris(naphthylethynyl)benzene as B-3 monomer. This monomer could be reacted with different ratios of hexane-1,6-dithiol (A(2) monomer) via mono-selective Thiol-Yne reaction (TYR) to form hyperbranched polymers PI. TYR yielded...

This chapter summarizes the synthesis methods for semifluorinated (sf) polymers, and discusses their phase separation behavior in bulk and thin films, derive the consequences of phase separation on the macroscopic wetting behavior, and propose applications for the interesting polymer class. It provides materials for low surface free energy coatings...

Comb-like copolymers based on a polyolefin backbone of poly(10-undecene-1-ol) (PUol) with poly(epsilon-caprolactone) (PCL) side chains are synthesized in two steps. After synthesis of PUol by metallocene-catalyzed polymerization, the side-chain hydroxyl functionalities of this polar polyolefin are used as an initiator for the ring-opening polymeriz...

Polymeric flame retardants offer the possibility to match effective flame retardancy with the requirements of new regulations. Synthesis, properties and efficiency in polymer matrices are discussed for two systems, epoxy resins as well as poly(butylene terephthalate).

Semifluorinated (SF) side chain polymers show phase separation between polymer backbone and SF side chains. Due to strong interaction between SF segments the side chains determine the structure behaviour strongly, often resulting in layered structures in which backbones and layers of SF side chains alternate. The interest in this work was directed...

Abstract Poly(methyl methacrylate)/silica (PMMA/SiO x) nanocomposites were synthesized via sol–gel method and studied by various techniques. The dispersion of the silica particles (10–100 nm) in the matrix was probed by transmission electron microscopy (TEM), while solid‐state NMR and Raman spectroscopy detected the formation of an inorganic networ...

Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus-containing polyesters are suggested as halogen-free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the pea...

Pyrolysis, fire behaviour and mechanical properties of a blend of poly(butylene terephthalate) (PBT) with a phosphorus polyester (PET-P-DOPO) are investigated and compared with PBT/aluminium diethylphosphinate (AlPi-Et) composites. The PBT/PET-P-DOPO is immiscible and exhibits gas-phase and condensed-phase activity, whereas AlPi-Et in PBT results m...

The reactive extrusion of lauryl lactam to polyamide 12 (PA12) of controlled molar mass was successfully performed in a microcompounder. The maximum residual monomer content was less than 1%. The in-situ polymerization in the presence of 1–5 wt.% multiwalled carbon nanotubes (MWCNTs) was studied and the processing conditions were optimized with res...

The surface of single-walled carbon nanotubes (SWCNTs) was functionalized with azide-terminated poly(vinylidene fluoride) (PVDF). Functionalization was confirmed by dispersibility, Raman spectroscopy, and thermogravimetric analyses. Raman spectra show disordering of the SWCNTs, thus, strongly suggesting that PVDF was covalently attached to SWCNTs....

The paper compares building and decomposition pathways of two phosphonic acids, amino trimethylene phosphonic acid (ATMP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).The theoretical formation reactions were composed using elementary reactions and compared to reaction routes published in literature. As result, summary reaction pathways for...

The crystallization and nucleation kinetics of poly(ε-caprolactones) (PCL) with molar masses between 1.4 and 6.1 kDa and negligible number of heterogeneous nuclei has been investigated by differential fast scanning calorimetry (DFSC) applying scanning rates up to 100?000 K/s. The samples were synthesized by ring-opening polymerization and chemicall...

Phosphorus polyesters provide sustainable flame retardancy to conventional polyesters like PET (poly(ethylene terephthalate)) and PBT (poly(butylene terephthalate)). Their use as a flame retardant additive results in the formation of a classical polymer blend. The morphology of such blends should determine the resulting fire behavior and has theref...

Different approaches were applied to obtain new diol compounds based on dibenzo[c.e][1,2]oxaphosphorine 2-oxide (DOPO, 1) and diethanolamine (DEolA). Of four processes investigated, a four-step synthesis of 1 containing propionic acid amide of DEolA proved to be the most efficient one. In addition, the intramolecular amine salt of the DOPO derivati...

The introduction of functionalities into block copolymers opens a wide field of possibilities for subsequent reactions, for instance to stabilize the morphology or to create stable hybrids. Methacrylate-based di- and triblock copolymers were synthesized by sequential anionic polymerization. Allyl methacrylate was used to form the third block and as...

Monomers with phosphorus-containing substituents were incorporated into aromatic–aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic–aliphatic diols. St...

Pyrolysis and fire behaviour of a phosphorus polyester (PET-P-DOPO) have been investigated. The glycol ether of the hydroquinone derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used as a reactive halogen-free flame retardant in PET-P-DOPO. PET-P-DOPO is proposed as an alternative to poly(butylene terephthalate) (PBT) with estab...

The phosphorus-containing aliphatic-aromatic diol 2-[4-(2-hydroxy-ethoxy)-3-(10-oxo-10-H9-oxa-10-λ5-phospha-phenanthrene-10-yl)-phenoxy]-ethanol, a potential flame retardant, was incorporated into poly(butylene terephthalate) (PBT) by solid state polycondensation. Thus, polymers with various ratios of PBT/DOPO-diol and number-average molar masses u...

A series of diblock copolymers of n-pentyl methacrylate and methyl methacrylate (PPMA/PMMA BCP) with one or two terminal functional groups was prepared by sequential anionic polymerization of PMA and MMA using an allyl-functionalized initiator and/or and end-capping with allyl bromide. Allyl functional groups were successfully converted into OH gro...

PET-P-DOPO is a phosphorus-containing polyester prepared from the glycol ether of the hydroquinone derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and dimethyl terephthalate. PET-P-DOPO and a blend of PBT with PET-PDOPO were investigated with respect to pyrolysis and fire behavior. PET-P-DOPO achieves a V-0 rating in the UL...

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