Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

Improvement of Chromatic Aberration of the Plastic Rod‐Lens Array, 2

Summary: We propose in this paper a new plastic rod‐lens with low chromatic aberration. Since a plastic rod‐lens has a parabolic refractive index distribution, it usually also shows a distribution of Abbe number. This Abbe number distribution is thought to cause the chromatic aberration of the plastic rod‐lens array. We have studied novel materials for a new plastic rod‐lens with low chromatic aberration and have provided new transparent polymer blends consisting of two polymers with different refractive indices and with almost equal Abbe numbers by using a fabrication process based on photopolymerization of methacrylate monomer(s) in the presence of other methacrylic polymers. The process can give new transparent polymer blends which cannot be formed using conventional techniques for polymer blend formation. In this work, tricyclo[5,2,1,0^2,6]deca‐8‐yl methacrylate is used as a high refractive index monomer and tert‐butyl methacrylate is used as a low refractive index one. By using polymer blends including these monomer units, we have created a plastic rod‐lens with lower chromatic aberration.

Molecular structures of comonomers in the study.     

Novel Phenol‐Formaldehyde Resins, 2. Resols Prepared Using Reactive Solvents

New results on the method of preparation of phenol‐formaldehyde resins from phenol and multihydroxymethyl derivatives of some ketones are presented. The latter, known as the reactive solvents of melamine, were prepared by reacting acetone and methyl ethyl ketone with excess of formaldehyde. A novel group of resins of resol type has been obtained. The structure of products is discussed and compared to that of classical resols. The fragments of ketones have been found incorporated into the structure of resins.

Temperature dependence of viscosity of a classical resol and of the resols modified with reactive solvents.     

A Reactive Flame Retardant as a Poly(propylene)‐Sized Glass Adhesion Promoter

Summary: Contact‐mode AFM adhesion strength measurements were employed in order to investigate the capability of PBBMA FR as an adhesion promoter in PP composites. The reactive FR exhibited superior coupling properties in comparison to conventional coupling agents such as PP‐g‐ma introduced in reinforced PP composites.

AFM image showing the recess carved out by the AFM tip in a PBBMA layer deposited on glass treated with APS.     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐Poly(ε‐caprolactone) by Reactive Extrusion, 2 – Parameter Analysis

EVOH‐g‐PCL were prepared by a solvent‐free reactive extrusion process using a co‐rotating twin screw extruder. Kinetic simulations were made of selected reaction conditions at 185 °C. Changes in the screw rotation rate resulted in evolution of the residence time distribution and slightly changed the monomer conversion. An increase of the [OH]₀/[Cl]₀ ratio made the reactive system more viscous and decreased the overall pumping capacities of the extruder. Increase of the mean residence time, combined with a positive kinetic effect of [OH]₀ increase, leaded to an important increase in conversion. For all the conducted experiments, equivalent distribution dispersions and good agreements between calculated conversion and those measured were obtained. An increase in temperature from 185 to 200 °C resulted in total conversion.

     

Synthesis of Poly(methyl methacrylate)‐Grafted Poly(ethylene‐co‐1‐octene) Copolymers by a “Grafting from” Melt Process

Graft copolymers with a poly(ethylene‐co‐1‐octene) backbone and poly(methyl methacrylate) random polymer branches are successfully synthesized by the grafting‐from technique in the molten state. The in situ radical polymerization of methyl methacrylate from the polyolefin backbone is investigated with two different peroxide initiators at 135 and 150 °C, respectively. The number of PMMA grafts per polyolefin chain is varied from 0.08 to 1.07 with PMMA polymerization degrees of 500 and 18, respectively, depending on the experimental conditions. The effect of a nitroxyl‐based radical scavenger (i.e., DEPN) on competition between the grafting of PMMA from the polyolefin backbone and MMA homopolymerization is also explored.

     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐poly(ε‐caprolactone) Synthesis by Reactive Extrusion, 1 ‐ Structural and Kinetic Study

Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. ¹H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct₂) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.

     

An NMR‐MOUSE® for Analysis of Thin Objects

A special unilateral NMR sensor has been designed for investigations of thin samples with a thickness of less than 1 mm and of surface effects of polymers. For use with the bar‐magnet NMR‐MOUSE®, the so‐called “crazy coil” is introduced with a low penetration depth. It is a flat meander coil etched on a printed circuit board with wiggles in the conductors. The design of the new coil and FEM simulations of the B ₁ field are presented. Different applications are discussed by means of illustrative examples. They are the detection of surface damage in rubber samples, the swelling and drying of a latex membrane exposed to cyclohexane vapor mimicking a chemical sensor, and the drying of a thin sprayed adhesive layer.

Bar‐magnet NMR‐MOUSE® with crazy coil.     

Onium Salts of Amino Acids as Co‐Initiators in Photoinduced Free‐Radical Polymerization

Summary: The onium salts of selected aliphatic and aromatic amino acids were investigated as electron donors in photoinduced free radical polymerization, in conjunction with either DIBF or BP as sensitizer. The laser flash photolysis experiments unmistakably documented that the free radical formation occurs via an electron transfer reaction from the amino acid salt to the chromophore triplet state. The kinetic studies clearly showed that either the DIBF or BP onium salts of selected aliphatic and aromatic sulfur‐containing amino acids exhibit a significant increase in the efficiency of free‐radical polymerization of TMPTA as compared to non‐sulfur‐containing co‐initiators and that the efficiency of all tested electron donors is only slightly dependent on the cation type coupled with co‐initiators tested.

Possible mechanism for the free radical photoinitiated polymerization.     

Chemical Structures Formed in Electron Beam Irradiated Poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP)

Summary: The perfluorinated copolymer poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) was electron beam irradiated under vacuum at various temperatures ranging from room temperature to a temperature above the melting temperature of FEP. Changes of the chemical structure were analyzed by ¹⁹F solid‐state NMR and IR spectroscopy. Trifluoromethyl end groups were generated as a result of main chain scission at all irradiation temperatures studied. In addition, trifluoromethyl side groups in various environments and double bond structures were formed. Quantitative analysis showed that long‐chain branches were formed at irradiation temperatures above 200 °C. Furthermore, the hexafluoropropylene (HFP) units in FEP were found to be less sensitive to radiation than the perfluoropropyl vinyl ether (PPVE) units in poly[tetrafluoroethylene‐co‐(perfluoropropyl vinyl ether)] (PFA).

¹⁹F solid‐state NMR spectra of FEP.     

The Effect of the Degree of Branching in Hyperbranched Polyesters Used as Reactive Modifiers in Epoxy Thermosets

The effect of the degree of branching (DB) of a hyperbranched polyester (GBPEX) added as a modifier of new thermosets obtained from diglycidylether of bisphenol A has been studied. The use of ytterbium triflate as cationic initiator allows the hydroxyl chain‐ends in the GBPEX to become covalently linked to the matrix through the monomer activated propagation mechanism. The curing process has been studied by DSC and rheology. The DB of the modifier does not affect appreciably the thermal stability and the chemical reworkability but shrinkage exhibits a significant reduction on increasing the DB. Thermomechanical characteristics are also improved with increasing the DB of the modifier.

     

Morphological and Physical Properties of Triblock Copolymers of Methyl Methacrylate and 2‐Ethylhexyl Methacrylate

Summary: Triblock copolymers of methyl methacrylate (MMA) and 2‐ethylhexyl methacrylate (EHMA) [that is, poly(MMA–EHMA–MMA)] were prepared by an emulsion atom‐transfer radical polymerization. The relationships of their structural, morphological, and physical properties were investigated. The latex particles had core‐shell morphologies and the block copolymers experienced phase separation. Small latex particles with a low number of cores could deform and wet silicon‐wafer surfaces, but the deformation of large latex particles was restricted by the internal two‐phase morphology of the particles. Latex casting produced continuous pinhole‐free films, in which hard poly(MMA) (PMMA) cores of different latex particles merged and provided interparticle connections. The morphology of solution‐cast films depended on block composition, solvent type, and film thickness. For all the prepared polymer samples, thick films cast in toluene had poly(EHMA) (PEHMA) materials at air surface, whereas those cast in tetrahydrofuran had a sponge‐like PMMA surface structure. Thin toluene‐cast films from P(MMA–EHMA–MMA) with the block degrees of polymerization ( ) 200–930–200 showed spherical PMMA domains and those from 380–930–380 yielded a protruded worm‐like PMMA structure. The copolymer materials were coated on a glass surface for peeling tests. The films gave good hot‐melt adhesion properties when the of the PEHMA block was over 600. The peeling strength depended on the lengths of both PEHMA and PMMA blocks. The P(MMA–EHMA–MMA) sample with of 310–930–310 yielded the highest peeling strength of 7.4 kgf · inch^?1. The developed material is demonstrated to be a good candidate for a solvent‐free, hot‐melt, pressure‐sensitive adhesives for special‐purpose applications such as medical tapes and labels.

     

The Importance of Crosslinking and Glass Transition Temperature for the Mechanical Strength of Nanofibers Obtained by Green Electrospinning

Crosslinked particles containing butyl acrylate, methyl methacrylate, and allyl methacrylate are prepared by free‐radical emulsion polymerization. The glass transition temperatures of the polymers are varied by the crosslinking densities in the latex particles. Aqueous acrylate dispersions with polymers of different glass transition temperatures are electrospun with PVA as the matrix polymer. The effects of crosslinking density and T_g on the structure and mechanical properties of the fibers are studied. Crosslinking of unreacted allyl groups is induced by UV irradiation to stabilize the fibers by interparticle crosslinking. Both the ability to undergo interparticle crosslinking and the E modulus depend on the merging of the particles during the electrospinning process.

     

Low‐Stress Hyperbranched Polymer/Silica Nanostructures Produced by UV Curing,Sol/Gel Processing and Nanoimprint Lithography

Nanocomposite materials based on a HBP and silica are produced using either a dual‐cure sol/gel and photopolymerization process or by mixing silica nanoparticles with the HBP. In both cases the conversion of the HBP is independent of composition and obeys a time‐intensity superposition with power‐law dependence on UV intensity. Optimization of the dual‐cure process leads to transparent sol/gel composites with ultrafine structures. These materials systematically outperform the particulate composites, including an increase of the glass transition temperature of 63 °C and a process‐induced internal stress as low as 2.5 MPa. Nano‐sized gratings are produced from the sol/gel composites by low‐pressure UV nanoimprint lithography.

     

Preparation and Characterization of Polyurethane Hybrids from Reactive Polyhedral Oligomeric Silsesquioxanes

Summary: Hybrid polyester resins containing polyhedral oligomeric silsesquioxanes (POSS), and their polyurethanes were prepared using reactive POSS as a substitution for partial diol monomer. They were investigated by FT‐IR, rheometry, dynamic mechanical analysis, wide‐angle X‐ray diffraction, contact‐angle measurement, atomic force microscopy, and thermogravimetric analysis, respectively. The results showed that the hybrid polyester‐POSS resins had a shear thinning behavior, and the more the POSS was embedded, the stronger the shear thinning behavior, and the higher the viscosity. Incorporation of POSS could increase the glass transition temperature and thermal stability and decrease the surface free energy of the polyurethanes. When the POSS content was relatively high, the POSS molecules in hybrid polyurethane‐POSS had a strong self‐assembling ability to form nanocrystalline domains.

Loss tangent curves of polyurethanes.     

Catalyzed Solid‐State Polyamidation

Summary: The current study is focused on key experiments on catalyzed SSP, examining the effect of selected phosphonates on the overall process rate. Catalyst incorporation was achieved through melt blending in a single screw extruder, providing a suitable and homogenous starting material for the reaction in the solid phase. More specifically, the post‐polycondensation runs were performed in a fixed bed reactor under flowing nitrogen at 160 and 200 °C. The additives used were found to catalyze the reaction in the solid phase, resulting even in tripling the solution relative viscosity after 4 h of SSP. Differences in the catalytic performance of the added materials were observed and correlated to the catalysts properties and morphology. An indicative potential catalysis mechanism is suggested, in which reactivity enhancement through partial attachment of the phosphorus compounds on the polyamide chain is the key step. Finally, the kinetics of the process were examined based on a power‐law rate expression, which was further modified so as to relate the apparent SSP rate constant with the phosphorus concentration.

SSP rate constants as a function of catalyst content.     

Preparation of Novel Fluoroalkyl End‐Capped Oligomer/Hydroxyapatite Nanocomposites

Novel fluoroalkyl end‐capped oligomer/hydroxyapatite nanocomposites have been easily prepared by the reaction of disodium hydrogenphosphate and calcium chloride in the presence of self‐assembled molecular aggregates formed by fluoroalkyl end‐capped oligomers in aqueous media. The fluorinated hydroxyapatite nanocomposites thus obtained were found to exhibit a good dispersibility in a variety of media, and were applied to the surface modification of glass.

     

Injection Moulding Difficult Nanopatterns with Hybrid Polymer Inlays

Hybrid polymeric inlays, patterned by nanoimprint lithography, are used to rapidly mass replicate pillar‐like nanostructures by injection moulding. This is difficult to achieve with traditional nickel inlays due to the rapid heat transfer of the metal, which results in premature cooling of the molten polymer and improper filling of nanoscale features. Using hybrid inlays, nanopillars can reliably be stretched by up to 40% of their designed height by adjusting moulding parameters. Hybrid inlays display longevity of more than 2000 cycles and can rapidly be fabricated to firmly establish injection moulding as an exceptionally useful tool for the high volume prototyping and production of nanopatterned polymeric devices.

     

Cover Image,Volume 92, Issue 1

The cover image, by Marco Rito‐Palomares et al., is based on the Perspective Monolithic chromatography: insights and practical perspectives, DOI: 10.1002/jctb.5040 .

     

Synthesis,Characterization and Properties of Novel Poly(urethane‐imide) Networks as Electrical Insulators with Improved Thermal Stability

Summary: A new series of thermoplastic poly(urethane‐imide)s (TPUI1‐4) containing hydroxyl groups in the backbone was synthesized from the reaction of epoxy‐terminated polyurethane prepolymers (EPU1‐4) and an imide containing diacid (DIDA) chain extender under optimized reaction conditions. EPU1‐4 was prepared through end‐functionalization of NCO‐terminated polyurethanes based on polyester polyol (CAPA) and hexamethylene diisocyanate with glycidol. A blocked isocyanate (BIC) was made from the reaction of trimethylol propane (TMP), toluene diisocyanate (TDI) and N‐methylaniline (NMA). Polymer networks were prepared from the reaction of librated isocyanate groups of BIC with hydroxyl groups of TPUIs. The starting materials and polymers were characterized by conventional spectroscopic methods and the physical, thermal and electrical properties of crosslinked networks were studied. Investigation of the recorded properties for these samples showed considerable improvement in thermal and electrical properties in comparison to common polyurethanes.

Synthetic route for preparation of TPUIs.