Thickening Processes of Lamellar Crystal Monolayers of a Low‐Molecular‐Weight PEO Fraction on a Solid Surface

Using hot‐stage atomic force microscopy, the thickening processes of monolayer crystals of PEO ( = 5 000 g · mol^?1 and = 1.008) from one‐folded (FC1) to extended‐chain (EC) lamellae are experimentally monitored at three temperatures: 50, 52, and 58 °C. At 50 °C some small areas in large FC1 crystals spontaneously thicken into EC crystals. At 52 °C the spontaneously thickened area further expands so as to inductively thicken the entire FC1 lamella into EC lamella. At 58 °C EC crystals first force the adjacent FC1 crystals to melt and then absorb the melted molecules to grow laterally into large EC lamellae till all FC1 lamellae vanish. The three thickening steps express the main thickening process of lamellar crystals from a metastable state to another metastable (or equilibrium) state. The possible mechanisms are discussed in the text.

     

Crystallization Kinetics of Biodegradable Poly(butylene succinate) under Isothermal and Non‐Isothermal Conditions

Crystallization kinetics of the biodegradable and fast crystallizing poly(butylene succinate) is studied, under both isothermal and non‐isothermal conditions. For the isothermal process at temperatures from 75 to 95 °C it is found that the Avrami model successfully describes the transformation kinetics. The non‐isothermal crystallization data obtained at a wide range of cooling rates from 0.1 to 20 °C · min^?1 are treated with several models, which include the modified Avrami, the Ozawa, the combined Avrami‐Ozawa, and the Tobin model. The Lauritzen‐Hoffman parameters are estimated from isothermal and non‐isothermal differential scanning calorimetry data, using different approximations for the growth rate and from the effective activation energy equation proposed by Vyazovkin and Sbirrazzuoli. The multiple‐melting behavior has been interpreted in the context of the melting–recrystallization–remelting phenomena.

     

Amphotropic Ionomers by Attachment of Secondary Amines to a Reactive Ester Polymer

Summary: We report on the synthesis of polyacrylamides that were prepared by the reaction of a reactive ester polymer with a mesogen‐containing secondary amine and N‐methylpiperazine. As the polymers do not form hydrogen bonds near the amide groups, their mobility is significantly higher than that of poly(N‐monoalkylacrylamides). The initially nonionic polymer shows no liquid‐crystalline behavior in bulk and in mixture with ethylene glycol. This is due to the low polarity difference between the different side chains. The polarity difference can be increased by protonation or quarternization of the tertiary amino groups, and liquid‐crystalline behavior is observed. The self‐assembly multilayer build‐up of the polymer with quarternized amino groups, and an anionic polyelectrolyte proceeds regularly.

     

Selective Localization Behavior of Carbon Nanotubes: Effect on Transesterification of Immiscible Polyester Blends

The selective localization of carbon nanotubes (CNTs) in an immiscible polymer blend has attracted much attention. If the two component polymers could react with each other, do selectively located CNTs affect those reactions? Here, an immiscible polyester blend based on polycarbonate/poly(trimethylene terephthalate) (PC/PTT) is studied. CNTs introduced during melt mixing are selectively located in the PTT phase and on the phase interface during the middle stage of melt mixing. The interface‐located CNTs can act as additional substrate to catalyze or even participate in the transesterification themselves, homogenizing the phase morphology of the matrix blend. The degree of randomness of the composite systems is increased, accompanied by a reduced number‐average length of the copolymer sequences.

     

Microwave‐Assisted Synthesis of Poly(L‐lactic acid) via Direct Melt Polycondensation Using Solid Super‐Acids

A microwave‐assisted method of synthesizing high‐molecular‐weight PLA using SSA as green catalyst was developed. Yellowish PLA with above 2.0 × 10⁴ g · mol^?1 was obtained when the reaction was run at 260 °C within 60 min under microwave irradiation with 0.4 wt.‐% SSA. This method used only 10% of the energy consumption necessary for conventional heating, and the catalyst could be used five times without losing catalytic activity. The improvement in and the decrease in the energy consumption under microwave irradiation suggested that selective heating and hot spots effects played a crucial role. The method was shown to be a time‐saving, green and a promising way to lower the cost and spread the application of PLA.

     

Solid‐State Olefin Metathesis: ADMET of Rigid‐Rod Polymers and Ring‐Closing Metathesis

Summary: Solid‐state olefin metathesis of rigid‐rod acyclic diene metathesis (ADMET) polymers and ring‐closing metathesis (RCM) have been investigated. 1,4‐Dipropoxy‐2,5‐divinylbenzene ( 4 ) was synthesized and used in a bulk ADMET polymerization to produce oligomers of dialkoxy poly(phenylene vinylene). The reaction was continued in the solid state, effectively doubling the molecular weight. Solid‐state RCM was investigated with a variety of solid dienes and metathesis catalysts, and demonstrated in low conversions using amide diene 5 with catalysts 9 , 13 , and 14 .

     

Temperature Dependence of the Oxygen Solubility in Acrylates and its Effect on the Induction Period in UV Photopolymerization

Summary: The influence of temperature on the kinetics of the UV photopolymerization of two diacrylates carried out under air was studied by real‐time FTIR‐ATR spectroscopy. In the temperature range up to 100 °C, the rate of polymerization obeys the Arrhenius law. The induction period was found to decrease with increasing temperature. It was shown that this decay is exclusively due to the decreasing solubility of oxygen in the acrylate. Moreover, from the induction period and the oxygen solubility, quantum yields of the α‐cleavage of some photoinitiators were estimated.

Induction period calculated from the solubility of oxygen in TPGDA in comparison with experimental data from RT‐FTIR measurements.     

Structure and Phase Transitions of Poly(heptamethylene p,p′‐bibenzoate): Time‐Resolved Synchrotron WAXS and DSC Studies

Time‐resolved wide‐angle X‐ray scattering (WAXS), as well as differential scanning calorimetry (DSC) and polarisation microscopy studies, were applied to investigate the structure and phase transitions of poly(heptamethylene p,p′‐bibenzoate). Temperature dependencies of several structural parameters were determined. Complete transformation from an isotropic melt to a smectic phase was suggested whereas the transition from a smectic to crystalline phase is only partial (around 30%), although it takes place from the ordered SCA phase. Crystals are formed within the SCA domains with nearly the same coherent length. On the basis of the analysis of the position and the profile of the diffuse wide‐angle X‐ray scattering and mesogenic layer spacing, it was assumed that either crystallisation modifies the smectic structure, or mesophase losses its positional order because of the lack of mobility of the spacers at low temperatures.

WAXS scattering profiles corresponding to P7MB: a) cooling from the isotropic melt at 2 °C · min^?1; b) subsequent melting at 12 °C · min^?1.     

Hyperbranched Poly[bis(alkylene)pyridinium]s

3,5‐Bis(bromomethyl)pyridine hydrobromide and 3,5‐bis(bromobutyl)pyridine hydrobromide were synthesized from commercially available 3,5‐lutidine. The poly(N‐alkylation) of these monomers readily yielded new hyperbranched polyelectrolytes. The progress of reaction was followed by ¹H NMR. A second‐order kinetic scheme fits the experimental data. Rate constants and activation parameters were determined, showing the higher reactivity of 3,5‐bis(bromomethyl)pyridine hydrobromide. This was explained by the electron‐attractive effect of pyridinium groups on the ? CH₂Br end groups. The structures of the hyperbranched poly[3,5‐bis(alkylene)pyridinium]s were investigated by ¹H and ¹³C NMR spectroscopy and a preliminary study of their properties is reported.

     

Synthesis and Characterization of Water Soluble Saccharide Functionalized Polysiloxanes and Their Use as Polymer Surfactants for the Stabilization of Polycaprolactone Nanoparticles

Summary: Monosaccharide functionalized polysiloxanes bearing either terminal or pendant mannose moieties have been obtained starting from the allyloxyethyl glycoside and appropriate H‐containing siloxane compounds, via hydrosilylation reactions. The starting modified monosaccharide was reacted as trimethylsilyl protected derivative and a convenient method for deprotection of the hydroxyl groups was found in order to avoid the degradation of the polysiloxane chains. The reaction products were characterized by IR and NMR spectroscopy. The water solubility of these functionalized polysiloxanes was investigated and critical micelle concentration values were found to be in the range 10⁻⁴–10⁻⁵ M . Some of the water soluble compounds were used as non ionic surfactants for the elaboration of poly(ε‐caprolactone) nanoparticles by nanoprecipitation, and particle sizes of less than 200 nm were observed.

     

A 13C NMR Study of the Products and Mechanism of the Thermal Oxidative Degradation of Poly(ethylene oxide)

The products and mechanism of the thermal oxidative degradation of poly(ethylene oxide) at 150 °C have been analysed using ¹³C NMR spectroscopy. The analysis was assisted by the use of distortionless enhancement by polarisation transfer spectra, longitudinal relaxation time measurements, long-range ¹³C ¹H coupling and chemical shift simulation software. The major result of degradation was chain scission resulting in two formate ester chain ends. Minor products were in-chain esters, peroxy groups, oxymethylene links and hydroxy and methoxy chain ends.

Initial steps for the mechanism of chain scission.     

Insights into the Ring‐Expansion Polymerization of Thiiranes with 2,4‐Thiazolidinedione

The behavior of the ring‐expansion homopolymerization of 2 (phenoxymethyl)thiirane (PMT) and propylene sulfide (PS), respectively, with thiazolidine‐2,4‐dione (TZD) as a cyclic initiator is investigated. The polymerizations show steadily growing molar masses with increasing monomer conversions. In addition, reversible merging reactions between rings are observed, with up to six merged macrocycles formed. The degree of merging is strongly dependent on the initial monomer concentration, whereas temperature has only a small impact. Under optimized conditions, ring‐poly(PMT) polymer with values of M _n up to 50 250 g mol^?1 and dispersities down to 1.11 can be synthesized. DSC and ESI‐MS measurements of the novel ring‐poly(PS) prove the formation of ring polymer having topological purity above 95%.

     

A Low Temperature Polycondensation for the Preparation of Highly Fluorinated Poly(arylene ether sulfone)s Containing Crosslinkable Pentafluorostyrene Moieties

Summary: The polycondensation of pentafluorophenyl sulfone (PPSO) with hexafluorobisphenol A (6F‐BPA), or a model compound, 4‐phenoxylphenol (POPOH), has been studied in order to find optimized reaction conditions for the preparation of fluorinated poly(arylene ether sulfone)s (FPAESs). It was found that PPSO had a very high reactivity in N,N‐dimethylacetamide (DMAc), allowing the reaction to occur at temperatures as low as 22 °C, even in the absence of any catalyst. This reaction was promoted by the addition of a trace amount of potassium fluoride (KF). Increasing the amount of KF to 1.05 equiv enhanced the conversion and allowed the reaction to be completed in a short time. Under this reaction condition, KF acted as a catalyst to activate the phenol group and also acted as a base to absorb the HF, which was a by‐product of the polycondensation, to produce high molecular weight polymer. The use of calcium hydride (CaH₂) instead of KF as a base in this reaction produced a similar effect with a slightly lower reaction rate. Both base systems were also applicable to the reaction of pentafluorostyrene (FSt) with 6F‐BPA. However, a much higher reaction temperature (125 °C) was required due to the low reactivity of FSt. Reacting FSt with an excess of 6F‐BPA produced a mixture of mono‐ and di‐substituted products of FSt with a controllable ratio, which could further react with PPSO to produce a polymer containing crosslinkable FSt moieties both as end‐capping groups and inserting units. This structure allowed the molecular weight of the polymer and the content of FSt to be adjusted independently. Crosslinked films of this polymer demonstrated an excellent processability and performance in waveguide applications, having refractive indices of 1.5061 (TE) and 1.5038 (TM), and a straight waveguide loss of 0.7 dB · cm⁻¹.

Reaction scheme for the preparation of fluorinated poly(arylene ether sulfone)s.     

Relationship between Architecture and Adhesive Properties of Macromolecular Materials, 1

This study deals with the preparation of polyurethane‐graft‐poly(n‐butyl acrylate)s copolymers by polymerization of diphenyl‐methane‐4,4‐di‐isocyanate (MDI) with α,α′‐di‐hydroxyl‐poly(n‐butyl acrylate)s of different sizes as macromonomers. The polyaddition has been studied on the basis of kinetic measurements, and the comb‐like structure of the resulting polymer has been well‐established. Such grafted copolymers display specific adhesive properties in connection with their comb‐like architecture.

     

Thermal Properties of Poly(ester amide)s with Isolated,Two Adjacent and Three Adjacent Amide Groups within a Polyester Chain

Differential scanning calorimetry (DSC) was employed to investigate the thermal properties of segmented aliphatic poly(ester amide)s (PEA)s. Three different series of PEAs were synthesized, each containing amide blocks of defined lengths which are randomly placed in the poly(butylene adipate) (PBA) backbone. Thus, the defined amide blocks consist of isolated amide groups, two adjacent amide groups or three adjacent amide groups. The PEAs show glass transition temperatures between ?63 and 1 °C, melting temperatures between 28 and 183 °C and crystallization temperatures lie between ?0.2 and 148 °C. The types of groups participating in the crystallization process and the length of the amide segments have an influence on the morphology of these polymers.

     

Novel Aromatic Polymer Electrolyte with Comb‐like Structure: Synthesis and Properties

Summary: A novel aromatic polymer electrolyte with pendant sulfodecyloxy groups was synthesized. The monomer 4 , bis[2‐(10′‐sulfodecyloxy)‐5‐chlorophenyl]sulfone, was synthesized from bis(2‐hydroxy‐5‐chlorophenyl)sulfide via bromoalkylation, oxidation, and sulfonation, and then polymerized via Ni‐catalyzed C C coupling polymerization to afford the title polymer electrolyte 6 . The polymer 6 was isolated as a brown powder with molecular weight of = 12 000. The high decomposition temperature of 6 (200 °C) was confirmed by TG/DTA‐MS measurement. Proton conductivity of 6 was measured using porous polyimide membrane as a supporting substrate. The pore‐filled membrane showed 1 × 10⁻⁵ S · cm⁻¹ of the proton conductivity at 80 °C and 90% RH.

Synthesis of aromatic polymer electrolyte having sulfodecyloxy groups via nickel‐catalyzed C C coupling polymerization.     

Evaluation of the Isoconversional Approach to Estimating the Hoffman‐Lauritzen Parameters from the Overall Rates of Non‐Isothermal Crystallization of Polymers

Summary: The isoconversional approach proposed by Vyazovkin for evaluating the Hoffman‐Lauritzen parameters from overall rates of non‐isothermal crystallization was critically applied to two new and fast crystallizing polymers, poly(propylene terephthalate) and poly(butylene naphthalate), which are used for the production of fibers. Non‐isothermal crystallization data were corrected for the effect of the thermal lag and the effective activation energy as a function of temperature was calculated using the method of Friedman. The estimated Hoffman‐Lauritzen parameters, U* and K_g, were consistent with corresponding values from isothermal crystallization experiments obtained either from DSC measurements or using polarized optical microscopy (POM). It was found that the proposed method could simulate the experimental data very well, and the temperature interval under consideration did not allow the detection of any critical breakpoints denoting regime transitions.

Dependence of the effective activation energy on average temperature for PPT.     

Novel Triaromatic Ester Mesogenic Liquid Crystalline Epoxy Resin Containing Both Methyl Substituent and Ethoxy Flexible Spacer: Synthesis and Curing

A novel triaromatic ester liquid crystalline epoxy resin (LCER) that contains both a methyl substituent and an ethoxy flexible spacer, p‐methylphenylene di{4‐[(2,3‐epoxypropoxy)ethoxy]benzoate} (MPEPEB), has been synthesized. The mesotropic property has been investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (POM). MPEPEB shows a lower melting temperature at 78.7 °C and a broad nematic mesophase temperature range of about 55 °C. Meanwhile MPEPEB shows a mesophase to ?50 °C upon cooling. The curing behavior of MPEPEB with 2,6‐diamino‐3,5‐diethyltoluene (DAE) has been investigated by means of DSC and POM during isothermal and dynamic processes. Although there is little difference between the activation energies obtained from the kinetic data, a marked difference is found between the isothermal and dynamic investigation. The curing reaction in the isothermal investigation roughly obeys n‐th order kinetics, while two exothermal peaks appear in the dynamic DSC curves of MPEPEB/DAE. A comparison of the isothermal and dynamic data shows that the curing rate is not a unique function of temperature and curing degree. The cured networks have lower glass temperatures and show a mesophase at room temperature which disappears at about 86–88 °C.

     

Gas‐Phase Assisted Surface Polymerization of Vinyl Monomers with Fe‐Based Initiating Systems

Summary: Gas‐phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) and styrene (St) was investigated with Fe‐based radical initiating systems, FeCl₂/2,2′‐bipyridine (Bpy)/methyl α‐bromophenylacetate (MBPA), etc. GASP with these initiating systems proceeded to produce corresponding polymers on substrate surfaces. The resulting PMMA had very high PDI values, suggesting an uncontrolled reaction. In an attempt to control the GASP, polymerization with a simple initiating system, Fe(0)/MBPA, was examined on Fe(0)‐metal surfaces, resulting in significant polymerization activity to produce high‐molecular‐weight PMMA. The results of time‐course tests on GASP of MMA and St suggested that a change had taken place to produce physically controlled propagation sites on the Fe(0) powder surfaces.

GASP schemes with a simple initiating system Fe(0)/MBPA.     

Cascade Reactions in Polymeric Nanoreactors: Mono (Rh)‐ and Bimetallic (Rh/Ir) Micellar Catalysis in the Hydroaminomethylation of 1‐Octene

The concept of micellar catalysis was transferred to the hydroaminomethylation of 1‐octene with N,N‐dimethylamine. In the first series of experiments a rhodium(I ) complex with amphiphilic triphenylphosphane functionalized poly(2‐oxazoline)s as macroligand was applied as catalyst. Results obtained under standard hydroformylation conditions (T = 100 °C, p = 50 bar) were not satisfying with regard to activities and selectivities of the hydroaminomethylation reaction. Rising the temperature to 150 °C increased the yield of amine to 22% with a corresponding n/iso selectivity of 7.5 and a TOF number of 461 h^?1. Best results were obtained by applying a dual Rh/Ir catalyst within the polymeric micelles leading at lower temperature of 130 °C to an amine yield of 24% with a corresponding n/iso selectivity of 11 and TOF numbers of about 600 h^?1.