4-(4-Carboxyphenyl)-3,5-dioxo-1,2,4-triazolidin-1-yl moieties resulting from 4-(3,5-dioxo-1,2,4-triazolin-4-yl)benzoic acid (U4A) randomly attached to 1,4-polybutadiene form supramolecular aggregates which act as effective junction zones in new thermoplastic elastomers. Deuteron nuclear magnetic resonance (2H NMR) spectroscopy was used to investigate the molecular dynamics of the polymer backbone and the junction zones in selectively labelled samples. The spectra show motional heterogeneity along the polymer chain as well as in the supramolecular domains. Polybutadiene segments which are adjacent to these polar clusters are restricted in their mobility, even at temperatures 100 K above the …

Infrared spectroscopy on new multiphase thermoplastic elastomers based on hydrogen bond complexes - temperature dependence and orientation behaviour

The structure and deformation behaviour of a new class of thermoplastic elastomers is studied by temperature dependent infrared (IR) spectroscopy and by IR - dichroism spectroscopy. The thermoplastic elastomer is based on polybutadiene with statistically distributed side groups which form an anisotropic supramolecular structure via hydrogen bonds. Changes in the IR spectra at elevated temperatures are related to the melting of the ordered structure. The uniaxial deformation behaviour is studied by linear dichroism Fourier-transform (FT)-IR spectroscopy. A deformation model is developed which accounts for the major experimental results: while the polybutadiene segments behave as flexible cha…

New amphiphilic poly(butadiene)-graft-poly(ethylene oxide)s

Amphiphilic graft copolymers with a poly(butadiene) backbone and poly(ethylene oxide) side chains were synthesized by grafting isocyanateterminated poly(ethylene oxide) on to partially hydroxylated poly(butadiene). The graft copolymers are water soluble if the fraction of hydrophilic poly(ethylene oxide) exceeds 50 wt%. Solutions of graft copolymers in water and tetrahydrofuran were studied by static light scattering and viscosity measurements. By dynamic light scattering in solution it was shown that the graft copolymers form clusters.

Synthesis of aldonamide siloxanes by hydrosilylation

Abstract The synthesis of hydrophobic/hydrophilic hybrid polymers based on polydimethylsiloxanes (PDMS) and carbohydrate derivatives involving a hydrosilylation step is reported. Starting with poly(dimethyl- co -hydromethyl)siloxanes (PDMS- co -HMS), O -acetylated N -allylaldonamides of various sugars can be attached to the siloxane backbone using platinum catalysts. The characteristics of different transition metal complexes in the polymer-analogous formation of SiC bonds are investigated. A generalized reaction pathway applicable to several reducing carbohydrates is established to synthesize aldonamide siloxanes in a broad variety of molecular weight and composition. The products obtaine…

Dilute solution properties of polybutadiene modified by 4-phenyl-1,2,4-triazoline-3,5-dione

The dilute solution properties of 4-phenyl-1,2,4-triazoline-3,5-dione-modified polybutadienes were studied in tetrahydrofuran by static and dynamic light scattering and compared with those from unmodified polybutadiene chains. For the unmodified polymer, the scaling laws were established and the coil interpenetration parameter k f0 was determined in the thermodynamically good solvent tetrahydrofuran ; the chains exhibited common flexible chain behavior. For the modified polybutadiene, the results indicate at infinite dilution a weak extent of intermolecular crosslinking via the urazole groups, coupled with a very high extent of intramolecular ring formation. In order to evaluate the fractio…

“Ball at the wall” — A new lamellar multiphase morphology in a polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock copolymer

Synthesis of a polystyrene-arm-polybutadiene-arm-poly(methyl methacrylate) triarm star copolymer

The straightforward synthesis of a polystyrene-arm-polybutadiene-arm-poly(methyl methacrylate) triarm star copolymer has been successfully realized by a sequence of reactions which involves the sequential addition of a living polybutadienyllithium to a polystyrene macromonomer with a terminal 1,1-diphenylethylene unit and subsequent polymerization of methyl methacrylate. The high-molecular-weight polystyrene-arm-polybutadiene-arm-poly(methyl methacrylate) star copolymer shows microphase separation into three phases.

Poly(styrene-b-methyl methacrylate) block copolymers as compatibilizing agents in blends of poly(styrene-co-acrylonitrile) and poly(2,6-dimethyl-1,4-phenylene ether): 1. Location of block copolymers in ternary blends — compatibilization versus micelle formation

Abstract The compatibilizing effect of the symmetric narrowly distributed block copolymer poly(styrene- b -methyl methacrylate) (P(S- b -MMA)) in blends of high-molecular-weight poly(styrene- co -acrylonitrile) containing 20 wt% (PSAN20) or 43 wt% acrylonitrile (PSAN43) with poly(2,6-dimethyl-1,4-phenylene ether) (PPE) was investigated by dynamic mechanical spectroscopy and transmission electron microscopy. In blends with the PSAN43, P(S- b -MMA) forms spherical micelles in the PPE phase with no dispersing efficiency. In contrast to this, for blends with PSAN20, the block copolymer is located at the phase boundary, causing an extremely fine dispersion of the components. Depending on the loc…

Poly(styrene-b-methyl methacrylate) block copolymers as compatibilizing agents in blends of poly(styrene-co-acrylonitrile) and poly(2,6-dimethyl-1,4-phenylene ether): 2. Influence of concentration and molecular weight of symmetric block copolymers

Abstract The influence of the molecular weight of the symmetric block copolymer poly(styrene-b-methyl methacrylate) (P(S-b-MMA)) in blends with high-molecular-weight poly(styrene-co-acrylonitrile) (PSAN) and poly(2,6-dimethyl-1,4-phenylene ether) (PPE) is investigated by dynamic mechanical analysis and transmission electron microscopy. Total molecular weights of the block copolymers vary from 16 up to 275 kg mol−1. Independent of molecular weight, all block copolymers locate to the interface with strong dispersing efficiency. The different block copolymers also showed approximately the same emulsifying efficiency. The degree of segmental mixing of the blocks with the respective phases is ev…

The glass transition of mixtures of polystyrene with alkyl-terminated oligostyrene — experimental evidence for microphase separation in a polymer blend

Mixtures of high molecular weight polystyrene (P n = 961.5 ; T g = 373 K) and sec-butyl-terminated oligostyrene (P n = 10.6 ; T g = 302 K) show a dependence of the glass transition on the composition (i.e., number-average molecular weight) which cannot be described by the classic equations of Fox & Flory or Kanig & Ueberreiter. Addition of small amounts of the oligostyrene strongly decreases the glass transition, and above an oligomer content of 40 wt.-% the glass transition remains constant within experimental error. This behavior can be attributed to the unfavorable interactions between the alkyl-terminated oligomer and the high molecular weight PS. As a result the oligomer is a bad solve…

Supramolecular structures based on 4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzoic acid (U4A) units act as effective junction zones in functionalized polybutadienes, resulting in the formation of thermoplastic elastomers. The dynamics on a molecular scale of the phenyl rings have been probed by 2H-NMR. In the polymeric system, there are three spatially separated environments, which are reflected in the mobility of the polar units. Phenyl rings which are incorporated in the structures are either rigid or undergo 180° phenyl flips. The small fraction of free functional groups move isotropically and their mobility is coupled to the dynamics of the polybutadiene matrix. In two model compounds, whe…

Synthesis and characterization of amphiphilic comb-polymers via ring-opening metathesis polymerization of exo,exo-5,6-bis(alkoxymethyl)-7-oxabicyclo[2.2.1]hept-2-enes

A number of exo,exo-5,6-bis(alkoxymethyl)-7-oxabicyclo[2.2.1]hept-2-enes (exo,exo-5,6-bis(alkoxymethyl)-7-oxanorbornenes) with long alkyl chains were prepared by reduction of the Diels-Alder adduct of furan and maleic anhydride, followed by alkylation with a series of different n-alkylbromides. These monomers were polymerized via ring-opening metathesis polymerization (ROMP) catalyzed by ruthenium trichloride in ethanolic solution. Contrary to a helical conformation as it was predicted by a previous molecular model study the poly(7-oxanorbornenes) adopt a coil conformation in solution. In bulk the materials show side chain crystallization.

Structural Characterization of the “Knitting Pattern” in Polystyrene-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) Triblock Copolymers

In a polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock copolymer (SBM) a morphological transition from a lamellar (ll) morphology (with sequence ABCB) to the knitting pattern (kp) morphology occurs upon hydrogenation of the center PB block. Structural information of the nonhydrogenated and the hydrogenated material is provided from small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). For the nonhydrogenated SBM sample the SAXS profile correlates well with a simple periodic lamellar structure. The hydrogenated sample forming the kp morphology displays a more complex SAXS pattern. From the TEM images of the knitting pattern the two-dimensional…

Step growth polymerization via tandem ene and diels-alder reactions

In contrast to other electron deficient enophiles or dienophiles which react with 1,4-cyclohexadiene (1,4-CHD) under aromatization, 1,2,4-triazoline-3,5-diones react in a defined reaction sequence. In a first step the 1,4-cyclohexadiene reacts via an ene-reaction. The intermediately formed substituted 1,3-cyclohexadiene immediately reacts in a Diels-Alder reaction. The regiochemistry of the Diels-Alder reaction is controlled by the solvent polarity. This reaction sequence can be used to synthesize polymers. Low-molar-mass model compounds were synthesized to elucidate the stereochemistry of the polymers. By varying the bistriazolinedione, polymers with backbones of different rigidity are ava…

Blends of poly(2,6-dimethyl-1,4-phenylene oxide) with styrene copolymers

Binary blends of poly(2,6–dimethyl–1,4–phenylene oxide) (PPE) with various styrene copolymers were investigated. Poly(styrene–co–acrylonitrile) (SAN), poly[styrene–co–(methyl methacrylate)] (SMMA), poly[styrene–co–(acrylic acid)] (SAA) and poly[styrene–co–(maleic anhydride)] (SMA) are only miscible with PPE when the amount of comonomer is rather small. From calculated binary interaction densities it can be concluded that the strong repulsion between PPE and comonomer limits miscibility. In blends of PPE with SAN, as well as with ABS, the inter-facial tension between the blend components is significantly reduced upon addition of polystyrene–block–poly–(methyl methacrylate) diblock copolymers…

Infrared linear dichroism spectroscopy by a double modulation technique

A linear IR dichroism experiment has been devised using a FTIR instrument in combination with a photoelastic modulator. Based on the Mueller-Stokes calculus, a method to directly obtain the absorbance spectra Av parallel and Av perpendicular from the modulated interferogram is developped, which allows the sensitive evaluation of the dichroic ratio. The photoelastic modulator, in combination with a FTIR instrument, offers high sensitivity, high speed, excellent signal to noise ratio and a broad spectral range from 3300 to 850 cm-1. First experimental results obstained from SBS block copolymer are reported.

Indication of an order-order-transition by a partial disordering in ABC-triblock copolymers

Poly(ethylene-alt-propylene)-block-polyethylethylene-block-polystyrene (PEP-b-PEE-b-PS) triblock copolymers were synthesized by anionic polymerization and subsequent hydrogenation of poly-1,4-isoprene-block-poly-1,2-butadiene-block-polystyrene triblock copolymers (1,4PI-b-1,2PB-b-PS). Differential scanning calorimetry and dynamic mechanical spectroscopy reveal an order-order transition which is induced by the mixing of PEP and PEE above their respective order-disorder transition (ODT).

Ellipsoidal core-shell cylindrical microphases in PS-b -PB-b -PCL triblock copolymers with a crystallizable matrix

Polystyrene-block-polybutadiene-block-poly(e-caprolactone) SBC triblock copolymers with a PCL matrix exhibit microphase separation into three different phases within the spherulitic superstructures. Mixing of the PS-block can occur upon melting of the PCL-block if the molecular weight is low enough. Even though the crystallization takes place well below the PS-glass transition, a deformation of the amorphous microphases into ellipsoidal core-shell cylindrical microdomains is observed by TEM. These copolymers have mechanical properties which are dominated by the PCL (Poly(e-caprolactone)) matrix with an influence of the amorphous blocks.

Cooperative structure formation by combination of covalent and association chain polymers: 4. Designing functional groups for supramolecular structure formation

Abstract A small number of polar functional groups are attached to polybutadiene by a polymer analogous reaction. Depending on their molecular structure, different degrees of supramolecular ordering result from the aggregation of these polar groups. In the case of phenylurazole units, which carry a single site for hydrogen-bond complexation, binary contacts are formed; whereas linear association chain structures are formed in the case of polybutadiene carrying phenylurazole units additionally substituted with a carboxy group in meta or para positions of the phenyl ring. In the latter case, association chains aggregate cooperatively to an ordered supramolecular structure. The different struc…

ABC and BAC triblock copolymers - morphological engineering by variation of the block sequence

Different morphologies and phase transitions of ternary triblock copolymers with different block sequences (ABC and BAC) are discussed qualitatively. The interplay between interfacial energies and elastic energies of the different blocks leads to various morphologies and enhances or prevents mixing of different blocks, depending on composition and topology.

Hydrophilic membranes based on poly(vinyl methyl ether-crosslinked-polystyrene) semi-interpenetrating networks

Microporous membranes were prepared from poly(vinyl methyl ether - crosslinked-polystyrene) (PVME-cross-PS) semi-IPN's by extraction of poly(vinyl methyl ether) (PVME) with water. Membrane morphology and properties are fixed during the process of swelling, phase separation, PVME extraction and vitrification which occurs upon immersing the samples in water. The membranes are characterized by swelling (water uptake), the relative amounts of free and bound water, and their permselectivity towards KCI solution.

Polydimethylsiloxanes with amylose side chains by enzymatic polymerization

Maltoheptaonamide modified polydimethylsiloxane was prepared applying a simplified synthetic pathway in the derivatization sequence of the carbohydrate. The products were characterized by 13C NMR and FT-IR spectroscopy. The glucan side chains of these “sweet siloxanes” were elongated by enzymatic catalysis with potato phosphorylase.

ABC triblock polyampholytes containing a neutral hydrophobic block, a polyacid and a polybase

Well defined ABC triblock copolymers of polystyrene-block-poly(2-vinylpyridine)-block-poly(tert-butyl methacrylate) and polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) were synthesized by sequential living anionic polymerization in tetrahydrofuran. Triblock copolymers with narrow molecular weight distribution were obtained. Hydrolysis of the poly(tert-butyl methacrylate) block yields polystyrene-block-polyvinylpyridine-block-poly(methacrylic acid) which demonstrates pH-dependent solution properties. Interpolymer complexation of the polyvinylpyridine and poly(methacrylic acid) blocks in the micellar solution is studied in dependence of the pH in solution by potent…

Adsorption of di-and triblock copolymers with functionalized butadiene-styrene blocks from dilute solution

Abstract The adsorption behaviour of functionalized polystyrene-block-polybutadiene diblock copolymers, P(S-b-B), and polybutadiene-block-polystyrene-block-polybutadiene triblock copolymers, P(B-b-S-b-B), from dilute solutions in toluene onto silicon wafers was investigated by means of null-ellipsometry. Polar 4-(3,5-dioxo- 1,2,4-triazolidin-4-yl) benzoic acid groups (urazole groups) were attached randomly to the butadiene blocks. The PS blocks and the PB blocks adsorb not on the substrate surface, but only on the polar functional groups. It was verified that the adsorbed amount does not depend on the number of functional groups nor on the degree of polymerization of the polybutadiene block…

Orientation of polybutadiene chains in a thermoplastic elastomer

The orientation of polybutadiene chains in thermoplastic elastomers based on hydrogen bonding complexes is investigated under uniaxial deformation by two-dimensional small-angle neutron scattering (SANS), deuteron magnetic resonance spectroscopy (2H-NMR), optical birefringence and infrared dichroism spectroscopy (FTIR-D). While SANS probes orientation on the length scale of the radius of gyration,2H-NMR, birefringence and FTIR-D monitor orientation on a segmental scale. The deformation of the elastomer chains appears to be affine on the different length scales.

Dynamic mechanical properties of semi-interpenetrating networks based on poly(styrene-co-maleic anhydride): 3. Poly(2,6-dimethyl-1,4-phenylene ether)-cross-poly(styrene-co-maleic anhydride)

Semi-IPN's based on linear poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and diamine crosslinked poly(styrene-co-maleic anhydride) (PScoMA) copolymers containing small amounts of maleic anhydride (PSA=4.7wt.-% MA, PSB=5.8 wt-% MA) are studied with respect to the influence of cross-linking on the phase behavior. Temperature-dependent dynamic mechanical analysis (DMA) and DSC show that the semi-IPN's prepared from concentrated solution show weak crystallinity of the PPE phase. After heating above the PPE melting transition the semi-IPN's remain amorphous and the relaxation in the glass transition region as well as the terminal relaxation of the free PPE chains in the network is studied as a fu…

Einfluss des polymerrückgrats auf eigenschaften von thermoplastischen elastomeren

4-Urazoyl benzoic acid groups were statistically attached to various hydrocarbon elastomers, polar elastomers and partially crystalline polymers via a polymer-analogous reaction. DSC, FTIR, stress-strain experiments and dynamic-mechanical analysis were used to analyse whether these systems, analogous to functionalized polybutadienes, would form ordered supra-molecular structures of the polar side-groups that would lead to a thermoreversible crosslinking. While the structure formation is suppressed for elastomers with a large cross-sectional area of the chain (e.g. butyl rubber) or polar side-groups, (e.g. polychloroprene), the mechanical propertie can be controlled by balancing supermolecul…

Thermodynamically Controlled Morphological Disorder in a Microphase-Separated Cylindrical Block Copolymer

Organometallic ABC-triblock copolymers

The interaction of Fe and Pd complexes with double bonds of the polybutadiene (PB) block in polystyrene-polybutadiene-poly(methyl methacrylate) block copolymers has been studied. The incorporation of Fe(CO)3 fragments into the PB bloc was found to result in an increase in its rigidity. The presence of iron or palladium complexes in the PB block affects strongly the morphology of the triblock copolymers.

Influence of hydrogen bonding on the viscoelastic properties of thermoreversible networks: analysis of the local complex dynamics

Abstract The viscoelastic properties of thermoreversible polybutadiene networks in which junctions are formed by binary contacts between polar stickers (phenylurazole) are investigated by a dynamic mechanical spectroscopy within the frequency range 0.0079–79.5 Hz (0.05–500 rads−1). Time-temperature superposition is applicable in the terminal flow region and the glass transition regime, whereas thermorheologically complex behaviour is observed within the rubbery plateau region. For the terminal relaxation zone the polar stickers enhance the relaxation time and broaden the relaxation time spectrum. The thermorheologically complex behaviour within the rubbery plateau region results from the oc…

Order-disorder-and order-order-transitions in AB and ABC block copolymers: description by a simple model

Based on the description of AB-block copolymers as micellar structures given by Semenov, the phase diagram of AB-diblock copolymers is calculated taking the homogeneously mixed system as a reference state. The predicted value (χN)c = 10.385 for a symmetric AB-diblock copolymer compares very well to the result of the original Random Phase Approximation theory (10.495). The simplicity of the model allows its extension to predict order-order transitions in ABC-triblock copolymers.

Thermal behavior and spherulitic superstructures of SBC triblock copolymers based on polystyrene (S), polybutadiene (B) and a crystallizable poly(ɛ-caprolactone) (C) block

The dynamic crystallization and the melting behavior of polystyrene-block-poly(e-caprolactone) (PS-b-PCL, short notation SC), polybutadiene-block-poly(e-caprolactone) (PB-b-PCL, BC) and polystyrene-block-polybutadiene-block-poly(e-caprolactone) (PS-b-PB-b-PCL, SBC) have been studied using differential scanning calorimetry. The copolymers with high molecular weight exhibit microphase separation into microphases consisting of polystyrene, polybutadiene and poly(e-caprolactone) and partial crystallization of the corresponding PCL block. The crystallization occurs at temperatures below the PS glass transition. Depending on the block copolymer composition, crystallization takes place through a c…

4-Vinylphthalic anhydride

4-Vinylphthalic anhydride can be prepared from phthalic acid via bromination and subsequent olefination (Heck-reaction). Homo- and copolymerization with styrene was accomplished using AIBN as initiator. The copolymer compositions were determined by infrared-spectroscopy. The copolymerization parameters are rs=0,15 and rVPA=3,09, the corresponding Q, e values of 4-vinylphthalic anhydride are estimated as Q=3,34 and e=0.09.

Semi-IPN's of different composition, based on linear poly(methyl vinyl ether) (PVME) and crosslinked polystyrene are studied using stress and birefringence measurements in simple elongation. From quasistatic stress-strain experiments at constant T(experiment)-Tg, it can be deduced that the stress results only from the deformation of the polystyrene network, while the PVME chains do not contribute to the macroscopic stress. The concentration dependence of the network modulus is adequately described by the rubber elastic theories

Polybutadiene model networks —synthesis, mechanical characterization and comparison with rubber elasticity models

Model networks of defined crosslink density are prepared via nonradical statistical crosslinking of polybutadiene in bulk and concentrated solution using a masked bistriazolinedione as crosslinker. The kinetics of crosslinking is monitored by FT-IR-spectroscopy. The reaction follows pseudo-1st-order reaction kinetics. The activation parameter of the crosslinking reaction is estimated from crosslinking at various temperatures. Networks of deuterated polybutadiene are prepared by this reaction in a wide range of crosslink densities. The stress strain behavior is analyzed according to the Junction Constraint-Theory of rubber elasticity (JCT) and to the approach introduced by Graessley accounti…

Evolution of the “knitting pattern” morphology in ABC triblock copolymers

A new morphology of ternary ABC triblock copolymers is presented which results from the asymmetric interaction between a centre block (poly(ethylene-co-butene)) to different end blocks (polystyrene and poly(methyl methacrylate)). This morphology with the appearance of a “knitting pattern” can be described as an intermediate of a morphology of A, B and C lamellae and a morphology of A and C lamellae with B cylinders at the A/C interface.

Phase behaviour of poly(vinyl methyl ether)-cross-polystyrene semi-interpenetrating networks

Semi-interpenetrating polymer networks of varying composition are prepared by crosslinking polystyrene containing a small number of maleic anhydride groups (4.8 mol% of MA units) with hexamethylene-diamine (HMDA) in the presence of linear poly(vinyl methyl ether) (PVME). Lightly crosslinked samples are homogeneous at room temperature and show a phase behaviour similar to uncrosslinked blends, i.e. lower critical solution temperature (LCST) behaviour. The influence of crosslinking on the phase behaviour has been studied by small angle light scattering (SALS) and turbidity measurements. The cloud point strongly depends on the heating rate. The presence of the network reduces the stable single…

Thermoanalytical studies on an order-disorder transition resulting from supramolecular organization of hydrogen bond motifs in an unpolar (polymer-) matrix are reported. Functional groups having two potential sites for hydrogen bonding (4-carboxyphenylarazole) are located statistically along the polybutadiene backbone. Multistep hydrogen bond formation leads to the formation of association chains whose lengths can be controlled by addition of monofunctional groups (phenylurazole) like in conventional stepgrowth polymers. The association chain length is estimated from the variation of transition enthalpy and «melting» temperature

Dynamic mechanical properties of semi-interpenetrating networks based on poly(styrene-co-maleic anhydride)

Semi-interpenetrating networks based on linear anionic polystyrene (PS) and poly(styrene-co-maleic anhydride) P(ScoMA) of low MA content are prepared by crosslinking the P(ScoMA) with 4,4′-diphenylmethanediamine (DPMDA). It is demonstrated by dynamic mechanical analysis and by DSC that immiscible semi-IPN's are obtained for MA contents greater 5 wt.-%. In miscible semi-IPN's the relaxation of free PS chains is observed as a second maximum in the loss tangent at higher temperatures. The position of this maximum is shifted to higher temperatures for a polystyrene of molecular weight 500000 compared to a polystyrene of molecular weight 150000. The experimental temperature shift is in good agre…

Synthesis of SBC, SC and BC block copolymers based on polystyrene (S), polybutadiene (B) and a crystallizable poly(ɛ-caprolactone) (C) block

The sequential anionic polymerization of polystyrene-block-polybutadiene-block-poly(e-caprolactone) (SBC) triblock copolymers as well as polystyrene-block-poly(e-caprolactone) (SC) and polybutadiene-block-poly(e-caprolactone) (BC) diblock copolymers was achieved in benzene. To initiate the polymerization of the highly reactive e-caprolactone, the nucleophilicity of the carbanion has to be reduced. For this purpose 1,1-diphenylethylene (DPE) was used. To avoid inter- and intramolecular transesterification reactions of the growing caprolactone block, the reaction time of this monomer in the block copolymers was strictly controlled. The reaction between polybutadienyl anions and DPE is too slo…

Surface reconstruction of the lamellar morphology in a symmetric poly(styrene-block-butadiene-block-methyl methacrylate) triblock copolymer: A tapping mode scanning force microscope study

The surface morphology of a symmetric poly(styrene-block-butadiene-block-methyl methacrylate) triblock copolymer (PS-b-PB-b-PMMA) with 6 wt % PB has been investigated by tapping mode scanning force microscopy (SFM). The results are compared to the bulk morphology as determined by transmission electron microscopy (TEM). In solvent-cast films PS/PMMA lamellae are formed, which are oriented nearly perpendicular to the free surface. Like in the bulk, also at the free film surface polybutadiene spheres are located at the lamellar PS/PMMA interface. However, contrary to the bulk, the surface morphology includes a large number of defects such as curved lamellar and disclinations, and the lamellar …

Synthesis of block copolymers with poly(methyl methacrylate): P(B-b-MMA), P(EB-b-MMA), P(S-b-B-b-MMA) and P(S-b-EB-b-MMA)

Well-defined diblock copolymers poly(butadiene-b-methyl methacrylate) (=P(B-b-MMA)) and triblock copolymers poly(styrene-b-butadiene-b-methyl methacrylate) (=P(S-b-B-b-MMA)) have been prepared by sequential anionic polymerization in THF. The synthesis of P(B-b-MMA) and P(S-b-B-b-MMA) was most efficient in the presence of lithium alkoxides. By this method side reactions are suppressed and the polymerization can be performed at higher temperatures. The resulting triblock copolymers have narrow molecular weight distribution. The 1,2-PB midblock was quantitatively hydrogenated with tosylhydrazide to enhance thermal stability. Alternatively the hydrogenation can be performed at elevated pressure…

Synthesis and properties of amphiphilic “dumbbell”-shaped grafted block copolymers, 1. Anionic synthesis via a polyfunctional initiator

Two poly(ethylene oxide) stars linked by a long polystyrene chain represent a novel amphiphilic architecture (dumbbell), which is available by anionic grafting of ethylene oxide from a hydroxylated polybutadiene-block-polystyrene-block-polybutadiene triblock copolymer. The short butadiene end-blocks (DPB = 36) of a BSB triblock copolymer with a long styrene middle block (DPS = 650) was first modified by hydroboration and oxidation. A multifunctional alkoxide initiator is thus prepared by titration of the hydroxyl groups of the “polybutadiene” end-block with cumylpotassium. Gelation and precipitation of the polyfunctional initiator in THF could be avoided by complexing the cation (K+) with a…

Junction Dynamics in Telechelic Hydrogen Bonded Polyisobutylene Networks

4-Urazoylbenzoic acid groups are attached to the chain ends of polyisobutylene. The cooperative assembling process of these polar groups is studied by DSC and dielectric and dynamic mechanical spectroscopy. The melting of the ordered clusters occurs in the temperature range 380-390 K. Distortions within the U4A clusters (Σ process) are monitored below the melting temperature T m with dielectric spectroscopy. On a larger length scale, these distortions also lead to stress relaxation which can be probed by dynamic mechanical measurements. Near T m , the relaxation ofU4A multiplets (α* relaxation) is detected with dielectric spectroscopy. In this temperature range, dynamic mechanical measureme…

Spherulite formation in a ?noncrystalline? two-dimensional hydrogen-bond assembly

4-Urazoyl benzoic acid groups 1 are attached as terminal end group to an oligoisobutene. According to wide-angle X-ray scattering the material is amorphous. Differential scanning calorimetry, small-angle X-ray scattering, transmission electron microscopy, and polarizing microscopy show that the polar head groups form ordered two-dimensional assemblies which organize into spherulites. Temperature-dependent SAXS measurements and the d.s.c. analysis give a close insight into the order-disorder (“melting”) process of the two-dimensional clusters which form macroscopic spherulites. The order-disorder transition of the clusters is closely related to the dynamics and order of the polyisobutene cha…

The anionic copolymerization of 5-(N,N-diisopropylamino)isoprene with styrene

The anionic copolymerization of 5-(N,N-diisopropylamino)isoprene (N,N-diisopropyl-2-vinylallylamine) and styrene initiated with alkyllithium compounds is studied. Copolymers obtained from different compositions are characterized by size-exclusion chromatography (SEC), differential scanning calorimetry and by 1 H NMR and 13 C NMR spectroscopy. Under these conditions the dialkylaminoisoprene, similar to butadiene and isoprene, is more reactive than styrene and is incorporated faster into the polymer backbone. The incomplete conversion of the monomers has been attributed to the formation of intra-or intermolecular complexes between the Li + counterion at the chain end and amino groups. Because…

Saccharide modified silica particles by enzymatic grafting

The surface of silica particles has been chemically modified with oligo- or poly-(α,1→4)-D-glucopyranose (amylose) chains of various length by covalently attaching maltoheptaose derivatives to the solid support and enzymatic polymerization of glucose-1-phosphate with a potato phosphorylase as catalyst. The characterization of the products by solid-state NMR spectroscopy showed an interesting dependence of the linewidth with the grafting density of the glucan chains. The modified silica particles showed chiral discrimination in liquid chromatography.

Networks of Partially Hydrogenatedcis-1,4-Polybutadiene and ‘Rigid Rods’

Networks of 'flexible' and 'rigid' chains were synthesized. As 'flexible' component we have used different partially hydrogenated cis-1,4-polybutadiene. The 'rigid' component was synthesized from bis(1,2,4-triazoline-3,5-dione)s and biscyclohexadienes via repetitive Diels-Alder reaction. A slight excess of bis(1,2, 4-triazoline-3,5-dione)s leads to polymers with 1,2,4-triazoline-3,5-dione end groups, which can easily react with the partially hydrogenated cis-1,4-polybutadiene. The influence of the extent of hydrogenation and the amount of crosslinker on the mechanical and thermal behaviour is described.

Hydrogen bonds in unpolar matrix — Comparison of complexation in polymeric and low molecular-weight systems

By ene-reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with double bonds, polar 4-phenyl-1,2,4-triazolidine-3,5-dione (phenyl urazole) groups are introduced into unpolar matrices. Hydrogen-bond complexes are formed between two amide-like units. The temperature dependence of complex formation in dilute hydrocarbon medium is obtained from remperature-dependent IR spectra in the region of the C=O stretching vibration. Results obtained for a low molecular-weight model system are compared with modified polybutadienes, where the groups are attached statistically along the polymer backbone. The enthalpy and the entropy of complex formation (ΔH f =−28.6 kJ/mol; ΔS f =−52 J/mol K−1) obtained for the…

Mechanical and thermal behaviour of networks with “flexible” and “rigid” chains

“Rigid-rod” telechelics were synthesized via repetitive Diels-Alder reaction of biscyclohexadienes and bis(1,2,4-triazoline-3,5-diones). The bistriazolinediones were used in slight excess. The rigidity of the building blocks and the molecular weight were varied. Various amounts of these reactive telechelics are used to crosslink cis-1,4-polybutadiene. The mechanical and the thermal properties of these two-component networks were investigated by stress-strain, differential scanning calorimetry and dynamic-mechanical measurements. The occurrence of microphase separation between the “rigid” and the “flexible” components is discussed to explain the properties of these materials.

A series of copolymers are synthesized by repetitive Diels-Alder polyaddition reaction of bifunctional cyclohepta-1,3,5-trienes with bifunctional 1,2,4-triazoline-3,5-diones. The copolymers of different bistriazolinediones with a bisdiene, or of different biscycloheptatrienes with a dienophile, have good solubility in CH2Cl2 and CHCl3, while the homopolymers are poorly soluble. The copolymers were characterized by standard analytical techniques to test the structural regularity of these systems. Due to the kinetic control, it is possible to apply copolymerization statistics to these systems. Based on a model study, it is concluded that alipatic and aromatic bistriazolinediones have the same…

Behaviour of modified and unmodified polybutadienes in the semidilute regime

Abstract The association behaviour of polybutadiene modified with 4-phenyl-l,2,4-triazoline-3,5-dione was studied in semidilute solution through static (SLS) and dynamic light scattering (DLS). The results were compared with the unmodified polybutadiene, whose behavior in semidilute solution was also studied as function of the molecular weight. At higher concentrations a small-angle excess scattering in SLS and a slow mode motion in DLS were observed both for modified and unmodified polybutadienes suggesting the presence of large clusters. Increasing the polymer concentration, the mass fraction of the slow motion increases up to values near 1, indicating a proximity to the gel point. For po…

The molecular dynamics of thermoreversible networks as studied by broadband dielectric spectroscopy

Polybutadienes modified by a small number of 4-phenyl-1,2,4-triazoline-3,5-dione form thermoreversible networks via hydrogen bonding between the polar stickers. The molecular dynamics of systems with different contents of polar stickers are investigated by broadband dielectric spectroscopy in the frequency regime of 10−1–109 Hz. Unmodified polybutadiene shows two relaxation processes, the α-relaxation which is correlated to the dynamic glass transition of the polybutadiene, and a β-relaxation corresponding to a local relaxation of polybutadiene segments. In the polar functionalized systems, besides these two relaxations, an additional relaxation process (called α*) is observed, which occurs…

Mechanical relaxation in miscible polymer systems: the glass transition regime in poly(vinylmethylether) (PVME)-cross-polystyrene (PS) semi-interpenetrating networks

Abstract Miscible semi-interpenetrating polymer networks (semi-IPN) of varying composition are prepared by crosslinking polystyrene containing few maleic anhydride groups with a diamine in the presence of linear poly(vinylmethylether) (PVME). The resulting PVME-c-P(ScoMA) semi-IPNs are characterized by their thermal and thermomechanical behaviour. Comparison with the corresponding uncrosslinked material proves that weak crosslinking has a negligible effect on the location of the glass transition as measured by d.s.c. Both the Tg data and the temperatures of the loss modulus maximum E″ (at 1 rad/s) show the same non-linear curved composition dependence. Contrary to this the tan δ maximum var…

Microphase separation in ternary ABC block copolymers: Ordering control in molten diblock AB copolymers by attaching a short strongly interacting C block

Some specific features of the microphase separation in molten ternary ABC triblock copolymers (in particular, modifications of the molten AB diblock copolymers by attaching a short third block C strongly incompatible with both A and B blocks) are studied rigorously within the framework of the weak segragation approach. It is shown that via such a modification one can control both the stability as to the microphase separation transition (i.e., the corresponding spinodal temparatures) and the smoothness of such a transition. Two modes of such modifications for every composition are studied in detail:  (i) those resulting in the minimal spinodal temperatures and (ii) those that result in the s…

Studies on the solution behaviour of self-assembling polymeric systems

Functional groups were attached to styrene-butadiene copolymers with different polymeric architectures and a low molecular weight compound. These polar stickers form binary, chelate-like contacts or extended juntion zones depending on their chemical nature. The solution properties of these amphiphilic species in toluene were studied by static light scattering.

Cylindrical morphologies in asymmetric ABC triblock copolymers

In asymmetric ABC triblock copolymers with C being the matrix-forming majority component, the formation of cylindrical morphologies is governed by the sum of the volume fractions of the components A and B (Φ A + Φ B ) as well as by their ratio (Φ B /Φ A ). The paper describes the morphologies of various polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) and polystyrene-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) block copolymers (SEBM) in dependence on these parameters. In addition to previously reported cylinder in cylinder (c i c, core shell) and helical (hel) morphologies, new microphase separated structures as cylinders at cylinder (c a c), undula…

Cooperative self-assembling in statistical copolymers: a new approach to high-temperature thermoplastic elastomers

Based on previous work, where it was shown that 4-urazoylbenzoic acid (U4A) groups, which are attached statistically to polybutadiene, form ordered supramolecular arrays in the unpolar polymer matrix, the present work describes the synthesis of a new molecular building block capable of self-assembling in the unpolar polymer matrix. 5-Urazoylisophthalic acid (U35A) groups attached to 1,4-polybutadiene chains cause the formation of a thermoplastic elastomer of improved properties. The clusters of functional groups show an endothermic transition. The melting temperature increases for low levels of modification from 130°C up to 190°C. The mechanical properties (stress–strain and dynamic mechani…

Linear infrared dichroism by a double modulation technique

In the first part of this paper an experimental setup using Fourier-transform infrared spectroscopy (FTIR) in combination with a photoelastic modulator (PEM) for linear dichroism measurements is described. The second part shows the influence of PEM-amplitude and scan-velocity on the sensitivity of the instrument. The third part deals with the fringe-problem in the baselines of absorbance spectra and its influence on the determination of the linear dichroic ratio.

Chiral helical nanostructures based on amorphous abc-triblock copolymers

So far all lattices of regular microdomain structures reported in the literature, either based on binary AB, ABA or ternary ABC block copolymers, can be described using simple symmetry elements like mirror planes, symmetry centers and rotation axes. The microphase separation in a linear ternary block copolymer consisting of three immiscible components namely polystyrene, polybutadiene and polymethyl methacrylate gives rise to the formation of a chiral supramolecular assembly in which chirality is not defined on a molecular (or macromolecular) level but only by the assembly of the linear triblock copolymer molecules. The polybutadiene (7, 12 wt.-%) phase forms helical strands surrounding the…

Thermal stability of poly(styrene-b-methyl methacrylate) and poly(styrene-b-ethylene-co-1-butene-b-methyl methacrylate)

The thermal stability of poly(styrene-b-methyl methacrylate) diblock copolymers (= P(S-b-MMA)) and poly(styrene-b-ethylene-co-1-butene-b-methyl methacrylate) triblock copolymers (=P(S-b-EB-b-MMA)) was investigated. Well-defined high molecular weight block copolymers with narrow molecular weight distribution (MWD) were molded at different temperatures in vacuum and the alteration of the MWD was sensitively monitored by gel permeation chromatography (GPC). Up to 240°C P(S-b-MMA) shows almost no broadening of the MWD. At higher temperatures low molecular weight polystyrene-rich portions are formed. The number average molecular weight (Mn) is strongly reduced. P(S-b-EB-b-MMA) triblock copolymer…

On the anionic polymerization of dialkylaminoisoprenes, 3. A nuclear magnetic resonance study of the structure of oligo[5-(N,N-diisopropylamino)isoprenyllithium]

The structure of oligo[(5-N,N-diisopropylamino)isoprenyllithium] (number-average degree of polymerization Pn = 1-2) prepared by reaction of alkyllithium with 5-(N,N-diisopropylamino)-isoprene1 in nonpolar (benzene) and polar (tetrahydrofuran) solvents has been studied by 1H and 13C NMR spectroscopy. In tetrahydrofuran, as expected, the negative charge at the terminal chain unit is more delocalized than in benzene and, consequently, the carbon-lithium bond has a more ionic character. In both solvents the living chain end shows a cisoid-4, 1-structure. No cistrans isomerization could be detected. This independence of the carbanion structure of the solvent polarity is explained by the complexa…

Synthesis of new polymers via Diels–Alder reaction. III. Biscyclohexadienephthalimides as dienes

Difunctional cyclohexadienes with dihydrophthalimide central unitsand phenyl side groups to increase solubility are used as bisdienes in repetitive Diels-Alder polyadditions with bis(4-(1,2,4,-triazoline-3,5-dione-4-yl)phenyl)methane as a difunctional dienophile. The polymers show good solubility in CH 2 Cl 2 and CHCl 3 . Non-stoichiometric Diels-Alder polyaddition with slight excess of the bistriazolinedione provides the possibility of synthesizing telechelics with highly reactive triazolinedione end groups

Competitive Adsorption of Functionalized Polymers

The adsorption and desorption of functionalized polystyrene-block-polybutadiene diblock copolymers from dilute solutions in toluene onto silicon wafers are investigated by means of null ellipsometry. The short polybutadiene block is functionalized by a reaction with 4-(3,5-dioxo-1,2,4-triazolidin-4-yl)benzoic acid. On the average there are six functional groups per chain. The polystyrene block does not adsorb on the surface. The adsorption depends on the length of the polystyrene block, and chains with short polystyrene blocks yield higher surface coverage than larger ones. When short and long chains are put together, the short chains displace the long ones in equilibrium conditions nearly …