A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization.

Photopolymerizations, in which the initiation of a chemical-physical reaction occurs by the exposure of photosensitive monomers to a high-intensity light source, have become a well-accepted technology for manufacturing polymers. Providing significant advantages over thermal-initiated polymerizations, including fast and controllable reaction rates, as well as spatial and temporal control over the formation of material, this technology has found a large variety of industrial applications. The reaction mechanisms and kinetics are quite complex as the system moves quickly from a liquid monomer mixture to a solid polymer. Therefore, the study of curing kinetics is of utmost importance for industrial applications, providing both the understanding of the process development and the improvement of the quality of parts manufactured via photopolymerization. Consequently, this review aims at presenting the materials and curing chemistry of such ultrafast crosslinking polymerization reactions as well as the research efforts on theoretical models to reproduce cure kinetics and mechanisms for free-radical and cationic photopolymerizations including diffusion-controlled phenomena and oxygen inhibition reactions in free-radical systems.

Expanding Monomers as Anti-Shrinkage Additives.

Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a (significantly shorter) covalent bond. This volumetric shrinkage can have severe influence on the materials' properties. One strategy to overcome this volumetric shrinkage is the use of expanding monomers that show volumetric expansion during polymerization reactions. Such monomers exhibit cyclic or even oligocyclic structural motifs with a correspondingly dense atomic packing. During the ring-opening reaction of such monomers, linear structures with atomic packing of lower density are formed, which results in volumetric expansion or at least reduced volumetric shrinkage. This review provides a concise overview of expanding monomers with a focus on the elucidation of structure-property relationships. Preceded by a brief introduction of measuring techniques for the quantification of volumetric changes, the most prominent classes of expanding monomers will be presented and discussed, namely cycloalkanes and cycloalkenes, oxacycles, benzoxazines, as well as thiocyclic compounds. Spiroorthoesters, spiroorthocarbonates, cyclic carbonates, and benzoxazines are particularly highlighted.

Dielectric Properties of Shrinkage-Free Poly(2-Oxazoline) Networks from Renewable Resources.

In the course of this study, the dielectric and physicochemical properties of poly(2-oxazoline) (POx) networks from renewable resources were compared with those of fossil-based polyamide 12 (PA 12) networks. POx was synthesized by the energy-efficient, microwave-assisted copolymerization of 2-oxazoline monomers, which were derived from fatty acids of coconut and castor oil. For the preparation of composites, aluminum nitride nanoparticles n-AlN and microparticles µ-AlN as well as hexagonal boron nitride BN submicroparticles were used. Additionally, 0, 15, or 30 wt.% of a spiroorthoester (SOE) were added as an expanding monomer aiming to reduce the formation of shrinkage-related defects. For the crosslinking of the polymers and the SOE as well as the double ring-opening reaction of the SOE, a thermally triggered dual-cure system was developed. The fully-cured blends and composites containing SOEs exhibited lower densities than their fully-cured SOE-free analogues, which was indicative of a lower extent of shrinkage (or even volumetric expansion) during the curing reaction, which is referred to as relative expansion RE. The RE amounted to values in the range of 0.46 to 2.48 for PA 12-based samples and 1.39 to 7.50 vol.% for POx-based samples. At 40 Hz, the "green" POx networks show low loss factors, which are competitive to those of the fossil-based PA 12.

Temperature-Triggered/Switchable Thermal Conductivity of Epoxy Resins.

The pronouncedly low thermal conductivity of polymers in the range of 0.1-0.2 W m-1 K-1 is a limiting factor for their application as an insulating layer in microelectronics that exhibit continuously higher power-to-volume ratios. Two strategies can be applied to increase the thermal conductivity of polymers; that is, compounding with thermally conductive inorganic materials as well as blending with aromatic units arranged by the principle of π-π stacking. In this study, both strategies were investigated and compared on the example of epoxy-amine resins of bisphenol A diglycidyl ether (BADGE) and 1,2,7,8-diepoxyoctane (DEO), respectively. These two diepoxy compounds were cured with mixtures of the diamines isophorone diamine (IPDA) and o-dianisidine (DAN). The epoxy-amine resins were cured without filler and with 5 wt.-% of SiO2 nanoparticles. Enhanced thermal conductivity in the range of 0.4 W·m-1·K-1 was observed exclusively in DEO-based polymer networks that were cured with DAN (and do not contain SiO2 fillers). This observation is argued to originate from π-π stacking of the aromatic units of DAN enabled by the higher flexibility of the aliphatic carbon chain of DEO compared with that of BADGE. The enhanced thermal conductivity occurs only at temperatures above the glass-transition point and only if no inorganic fillers, which disrupt the π-π stacking of the aromatic groups, are present. In summary, it can be argued that the bisphenol-free epoxy-amine resin with an epoxy compound derivable from natural resources shows favorably higher thermal conductivity in comparison with the petrol-based bisphenol-based epoxy/amine resins.

Enhancement of the Insulation Properties of Poly(2-oxazoline)-co-Polyester Networks by the Addition of Nanofillers.

Copoly(2-nonyl-2-oxazoline)-stat-poly(2-dec-9'enyl-2-oxazoline)s can be crosslinked by the thiol-ene reaction with glycol dimercaptoacetate. The copoly(2-oxazoline)-stat-copolyester is tested as dielectric for high-voltage applications, either as unfilled resin or as composite with nanoscaled fillers of silica, alumina, and hexagonal boron nitride. During AC voltage tests, all materials have an average breakdown strength of 45-50 kV mm-1 . For DC voltage tests, samples with SiO2 (hBN) have an average breakdown strength of ≈100 (80) kV mm-1 , while the unfilled copoly(2-oxazoline) has an average breakdown strength of ≈60 kV mm-1 . Permittivity measurements at 20 °C and 50 Hz reveal that all nanocomposites are dielectrics (D = 0.06-0.08), while the unfilled copoly(2-oxazoline)s has a high loss factor of D = 8.43. This phenomenon can be retraced to the phase separation in the crosslinked copolymer, the M-OH functionality of silica and alumina particles, and models of polymer-particle interactions such as the Tanaka model, revealing that the nanofillers reduce the interfacial and dipolar polarizability.

Polyethylene Nanocomposites for Power Cable Insulations.

This review represents a comprehensive study of nanocomposites for power cables insulations based on thermoplastic polymers such as polyethylene congeners like LDPE, HDPE and XLPE, which is complemented by original results. Particular focus lies on the structure-property relationships of nanocomposites and the materials' design with the corresponding electrical properties. The critical factors, which contribute to the degradation or improvement of the electrical performance of such cable insulations, are discussed in detail; in particular, properties such as electrical conductivity, relative permittivity, dielectric losses, partial discharges, space charge, electrical and water tree resistance behavior and electric breakdown of such nanocomposites based on thermoplastic polymers are described and referred to the composites' structures. This review is motivated by the fact that the development of polymer nanocomposites for power cables insulation is based on understanding more closely the aging mechanisms and the behavior of nanocomposites under operating stresses.

Heat Dissipation in Epoxy/Amine-Based Gradient Composites with Alumina Particles: A Critical Evaluation of Thermal Conductivity Measurements.

For the design of the next generation of microelectronic packages, thermal management is one of the key aspects and must be met by the development of polymers with enhanced thermal conductivity. While all polymer classes show a very low thermal conductivity, this shortcoming can be compensated for by the addition of fillers, yielding polymer-based composite materials with high thermal conductivity. The inorganic fillers, however, are often available only in submicron- and micron-scaled dimensions and, consequently, can sediment during the curing reaction of the polymer matrix. In this study, an epoxy/amine resin was filled with nano- and submicron-scaled alumina particles, yielding a gradient composite. It was found that the thermal conductivity according to laser flash analysis of a sliced specimen ranged from 0.25 to 0.45 W·m-1·K-1 at room temperature. If the thermal conductivity of an uncut specimen was measured with a guarded heat flow meter, the 'averaged' thermal conductivity was measured to be only 0.25 W·m-1·K-1. Finite element analysis revealed that the heat dissipation through a gradient composite was of intermediate speed in comparison with homogeneous composites exhibiting a non-gradient thermal conductivity of 0.25 and 0.45 W·m-1·K-1.

UV-mediated thiol-ene click reactions for the synthesis of drug-loadable and degradable gels based on copoly(2-oxazoline)s.

An 80-membered library of gels composed of monofunctional 2-ethyl-2-oxazoline and 2-nonyl-2-oxazoline and one of four selected difunctional 2-oxazolines (containing either ether or ester bonds) were synthesized by microwave-assisted ring-opening polymerizations. The difunctional 2-oxazolines were prepared from the thiol-ene reaction of glycol dimercaptoacetate or 2,2'-(ethylenedioxy)diethanethiol and 2-but-3'-enyl-2-oxazoline or 2-dec-9'-enyl-2-oxazoline. 53 of the gels exhibited glass-transition temperatures, which ranged from -5.9 to 45.3 °C. 13 Derivatives exhibited glass-transition temperatures in the range from 20 to 30 °C, which renders them stiff at room temperature and flexible at body temperature. The gels that did not contain any 2-ethyl-2-oxazoline acted as lipogels, whereas the gels that did not contain any 2-nonyl-2-oxazoline acted as hydrogels; all other gels may be classified as amphigels. The swelling degrees were measured by gravimetry and maximum swelling degrees of 6 (in water) were observed for the gels with the lowest degrees of crosslinking. In a second approach, the synthesis of crosslinked networks had been achieved by performing the polymeranalogous thiol-ene reaction of copoly(2-oxazoline)s containing olefinic side-chains and glycol dimercaptoacetate. This soft strategy enabled the straightforward loading of such gels with active pharmaceutical ingredients without altering them. This method delivered gels with selected composition exhibiting a targeted disc-shape and loaded with active pharmaceutical ingredients from one-step syntheses. The maximum swelling degrees of these specimens were found to be in accordance with the ones from the first route investigated. Preliminary degradation studies were performed at 25 °C; these types of gels were found to be degraded in alkaline media as well as by esterases.

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications.

Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, for which platinum compounds were used in the initial stages. Celebrating the 50th anniversary of hydrosilylations in polymer science and, concomitantly, five decades of continuously growing research, hydrosilylation reactions have advanced to a level that renders them predestined for transfer into commercial products on the large scale. Facing this potential transfer, this review addresses and discusses selected current trends of the scientific research in the area, namely low-cost transition metal catalysts (focusing on iron, cobalt, and nickel complexes), metal-free catalysts, non-thermally triggered hydrosilylation reactions (highlighting stimuli such as (UV-)light), and (potential) industrial applications (highlighting the catalysts used and products manufactured). This review focuses on the hydrosilylation reactions involving alkene reactants.

Effect of Interfacial Polarization and Water Absorption on the Dielectric Properties of Epoxy-Nanocomposites.

Five types of nanofillers, namely, silica, surface-silylated silica, alumina, surface-silylated alumina, and boron nitride, were tested in this study. Nanocomposites composed of an epoxy/amine resin and one of the five types of nanoparticles were tested as dielectrics with a focus on (i) the surface functionalization of the nanoparticles and (ii) the water absorption by the materials. The dispersability of the nanoparticles in the resin correlated with the composition (OH content) of their surfaces. The interfacial polarization of the thoroughly dried samples was found to increase at lowered frequencies and increased temperatures. The ß relaxation, unlike the interfacial polarization, was not significantly increased at elevated temperatures (below the glass-transition temperature). Upon the absorption of water under ambient conditions, the interfacial polarization increased significantly, and the insulating properties decreased or even deteriorated. This effect was most pronounced in the nanocomposite containing silica, and occurred as well in the nanocomposites containing silylated silica or non-functionalized alumina. The alternating current (AC) breakdown strength of all specimens was in the range of 30 to 35 kV·mm-1. In direct current (DC) breakdown tests, the epoxy resin exhibited the lowest strength of 110 kV·mm-1; the nanocomposite containing surface-silylated alumina had a strength of 170 kV·mm-1. In summary, water absorption had the most relevant impact on the dielectric properties of nanocomposites containing nanoparticles, the surfaces of which interacted with the water molecules. Nanocomposites containing silylated alumina particles or boron nitride showed the best dielectric properties in this study.

Interdisciplinary Approaches towards Materials with Enhanced Properties for Electrical Engineering.

The internationally growing demand for electrical energy is one of the most prominent triggers stimulating research these days.[...].

Modification Pathways for Copoly(2-oxazoline)s Enabling Their Application as Antireflective Coatings in Photolithography.

Chromophore-functionalized copoly(2-oxazoline)s are successfully evaluated as bottom antireflective coatings (BARCs) in high-resolution photolithography. With respect to UV light sources used in photolithographic production routines, anthracene is chosen as a chromophore. For application as polymer in BARCs, the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-(3'-(1"-(anthracen-9-ylmethyl)-1",2",3"-triazol-4-yl)propyl)-2-oxazolin)35 can be synthesized by the Huisgen cycloaddition click reaction of the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-pent-4'-inyl-2-oxazolin)35 and the corresponding azide-functionalized anthracenes. These copolymers can be crosslinked by the thermally induced thiol-ene reaction involving the unsaturated C=C bonds of the poly(2-dec-9'-enyl-2-oxazoline) repetition units and a multifunctional thiol as crosslinker. Tests of this BARC in a clean room under production conditions reveal a significant decrease of the swing-curve of a chemically amplified positive photoresist by more than 50%, hence significantly increasing the resolution of the photoresist.

Microwave-Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources.

The copoly(2-oxazoline) pNonOx80 -stat-pDc(=) Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9'-enyl-2-oxazoline Dc(=) Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80 -stat-pDc(=) Ox20 can be used as polymer in a photoresist (resolution of 1 µm) based on UV-induced thiol-ene reactions.

Crosslinked Poly(2-oxazoline)s as "Green" Materials for Electronic Applications.

Poly(2-nonyl-2-oxazoline)80-stat-poly(2-dec-9'-enyl-2-oxazoline)20 and poly(2-dec-9'-enyl-2-oxazoline)100 can be synthesized from the cationic ring-opening polymerization of monomers that can be derived from fatty acids from renewable resources. These (co)poly(2-oxazoline)s can be crosslinked with di- and trifunctional mercapto compounds using the UV-induced thiol-ene reaction. The complex permittivity of the corresponding networks increases with the temperature and decreases with the network density. In a frequency range from 10-2 to 106 Hz and at temperatures ranging from -20 to 40 °C, the changes of the real part of the complex permittivity as well as the loss factor can be explained by interfacial polarization within the material. At a temperature of 20 °C and a frequency of 50 Hz, the permittivity of the crosslinked (co)poly(2-oxazoline)s covers a range from 4.29 to 4.97, and the loss factors are in the range from 0.030 to 0.093. The electrical conductivities of these polymer networks span a range from 5 × 10-12 to 8 × 10-9 S/m, classifying these materials as medium insulators. Notably, the values for the permittivity, loss factor and conductivity of these copoly(2-oxazoline)s are in the same range as for polyamides, and, hence, these copoly(2-oxazoline)-based networks may be referred to as "green" alternatives for polyamides as insulators in electronic applications.

The π-Electron Delocalization in 2-Oxazolines Revisited: Quantification and Comparison with Its Analogue in Esters.

The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed π-electron delocalization along the N-C-O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O-C-O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N-C-O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.97 and 1.10 for the N=C and C-O bonds, and the computed partial charges for the nitrogen and oxygen atoms of -0.43 and -0.44 were almost identical. In the ester group, the bond orders were 1.94 and 1.18 for the C-O bonds, while the partial charges of the oxygen atom are -0.49 and -0.41, which demonstrates the similar electronic structure of the N-C-O and O-C-O segments. In 2-oxazolines, despite the higher electronegativity of the oxygen atom (compared to the nitrogen atom), the charges of the hetero atoms oxygen and nitrogen are equalized due to the delocalization, and it also means that a cationic attack on the nitrogen is possible, enabling regioselectivity during the initiation of the cationic ring-opening polymerization of 2-oxazoline monomers, which is a prerequisite for the synthesis of materials with well-defined structures.

Microwave-assisted cationic ring-opening polymerization of 2-oxazolines.

Unlike any other polymer class, the (co-)poly(2-oxazoline)s have tremendously benefited from the introduction of microwave reactors into chemical laboratories. This review focuses on the research activities in the area of (co-)poly(2-oxazoline)s prepared by microwave-assisted syntheses and, correspondingly, summarizes the current-state-of the-art of the microwave-assisted synthesis of 2-oxazoline monomers and the microwave-assisted ring-opening (co-)polymerization of 2-oxazolines as well as prominent examples of post-polymerization modification of (co-)poly(2-oxazoline)s. Special attention is attributed to the kinetic analysis of the microwave-assisted polymerization of 2-oxazolines and the discussion of non-thermal microwave effects.

Poly(2-oxazoline)-derived contact biocides: contributions to the understanding of antimicrobial activity.

A set of poly(2-oxazoline)-derived (co-)polymers was prepared by microwave-assisted polymerizations and acid-mediated hydrolysis and tested for antimicrobial activity in 50 × 50 × 2 mm PP compound plates containing 5 wt% of the polymers. Antimicrobial activity against gram-negative E. coli and P. aeruginosa as well as C. albicans depended only on the degree of hydrolysis, while antimicrobial activity against gram-positive S. aureus was only observed for hydrolyzed poly(2-nonyl-2-oxazoline)s. The surface energies of the compound plates compared to pure PP were hardly altered, and the compounds can be considered as alternatives for PP. The presence of the biocide additives at the surface of the PP compound plates could be shown by combined ATR-IR, zeta potential, and SEM-EDX measurements. Antimicrobial activity was maintained during double incubation as well as for lowered amounts of the biocide additive of 1% in PP compound plates.

Strategies for the synthesis of poly(2-oxazoline)-based hydrogels.

Poly(2-oxazoline)-based networks currently receive great interest due to their versatile properties that can be tailor made by desktop-planned modifications. This feature summarizes strategies for the preparation of these networks, comprising the in situ cross-linking as well as polymer-analogous cross-linking routines such as (reversible) complex formation, physical processes, and covalent bond formation (involving reactions with olefinic species as well as with epoxides, isocyanates, aldehydes, acids, and their derivatives). Reflecting prominent application examples in the biomedic(in)al sector, poly(2-oxazoline)-co-polyester networks are described in a dedicated section.

Water-developable poly(2-oxazoline)-based negative photoresists.

Copoly(2-oxazoline)-based photoresists are prepared from pEtOx(80) Bu(=) Ox(20) and pPhOx(80) Dc(=) Ox(20) , respectively, a tetrathiol, and a photosensitive initiator. It is possible to prepare copoly(2-oxazoline)s bearing unsaturated side chains in a microwave reactor on a decagram scale in reaction times of 100 min or shorter. UV irradiation of dried polymer films through a quartz mask induces the thiol-ene reaction in the illuminated areas. Subsequent development of the polymer films in halogen-free solvents reproduces the negative pattern of the mask with a resolution of 2 µm. The pEtOx(80) Bu(=) Ox(20) -derived photoresists can also be developed in water.

Anhydrous thallium hydrogen L-glutamate: polymer networks formed by sandwich layers of oxygen-coordinated thallium ions cores shielded by hydrogen L-glutamate counterions.

Anhydrous thallium hydrogen L-glutamate [Tl(L-GluH)] crystallizes from water (space group P2(1)) with a layer structure in which the thallium ions are penta- and hexacoordinated exclusively by the oxygen atoms of the γ-carboxylate group of the hydrogen L-glutamate anions to form a two-dimensional coordination polymer. The thallium-oxygen layer is composed of Tl(2)O(2) and TlCO(2) quadrangles and is only 3 Å high. Only one hemisphere of the thallium ions participates in coordination, indicative of the presence of the 6s(2) lone pair of electrons. The thallium-oxygen assemblies are shielded by the hydrogen l-glutamate anions. Only the carbon atom of the α-carboxylate group deviates from the plane spanned by the thallium ions, the γ-carboxylate groups and the proton bearing carbon atoms, which are in trans conformation. Given the abundance of L-glutamic and L-aspartic acid in biological systems on the one hand and the high toxicity of thallium on the other hand, it is worth mentioning that the dominant structural motifs in the crystal structure of [Tl(L-GluH)] strongly resemble their corresponding analogues in the crystalline phase of [K(L-AspH)(H(2)O)(2)].