Chemische Methoden zur Analyse von Netzwerken

The chemical investigation of the network structure of crosslinked polymers requires the defined splitting of the polymer chains by inequivocal reactions. From nature and amount of the reaction products conclusions can be drawn on the network structure. The present possibilities and limits of the chemical analysis of crosslinked polymers are discussed on some examples of crosslinking polyreactions and subsequent crosslinking of macromolecules.     

The influence of loose and semianchored siloxane polymer chains on the tack of crosslinked silicone rubber

The influence of addition of nonreactive silicone oil or semianchored silicone polymer on crosslinked poly(dimethylsiloxane) (PDMS) rubber–rubber adhesion was studied. The additives can be considered either a tackifier, or connector molecules, able to cross the interface and entangle. In both cases, it influences the tack of the elastomers. An additional variable is the molecular weight of the additive, which affects the reptation of the polymer chains. Polymer–polymer demixing, which is the result of thermodynamic incompatibility of mixed polymers is another factor that influences tack. It causes the free chains to appear at the surface forming a layer of oil, which actually destroys the tack of the PDMS samples. The resulting tack phenomena as a function of oil, respectively semianchored silicone polymer chains, are very much dependent on the transient nature of the polymer reptation: in many cases the polymers need very long time periods to obtain equilibrium in interphase crossing, or oil sweats out of the crosslinked polymers, forming a liquid layer between the two phases resulting in a low tack value, due to hydrodynamic wetting alone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of shape memory polymer networks based on carboxylated telechelic poly(ɛ-caprolactone)/epoxidized natural rubber blends

Shape memory polymer networks were prepared from blends of end-carboxylated telechelic poly(?-caprolactone) (XPCL) and epoxidized natural rubber (ENR). The XPCL/ENR blends can form cross linked structure via interchain reaction between the reactive groups of each polymer during molding at high temperature. Degree of crosslinking of the blend network and their thermomechanical properties were characterized by gel content measurement, DSC and DMA. We found that the degree of crosslinking and crystalline melting transition temperatures was dependent upon the blend compositions as well as the molecular weight of the XPCL segment in the blends. The blends showed a good shape memory behavior such as good shape fixity as well as a high final recovery rate when they exhibit crystalline melting transition with a sufficiently high degree of crosslinking. And the response temperature of the recovery was well matched with T_m of the samples.     

Molecular dynamics study of the mechanical properties of polydisperse pressure-sensitive adhesives

Amorphous polymers are one of the primary materials used in pressure sensitive adhesives (PSAs). Their design can be aided by a better understanding of the mechanisms governing the molecular and mesoscopic scale behavior. This work presents a molecular dynamics study of the toughness and failure modes of a coarse-grained polydisperse PSA model in probe peel tests, achieved by varying the crosslinking density and locations. Generally, the toughness of polydisperse PSAs increases at a crosslinking density of 0.5%, compared to the non-crosslinked structure, and declines at higher crosslinking densities, which also changes the failure mode from cohesive to adhesive. The performance is affected by the length of the polymer chains that form crosslinks, although high crosslinking densities make the system less sensitive to effects related to its polydispersity. The results herewith presented display an optimal performance when 35–45% of the particles in the system belong to the giant component of the PSA network. This is achieved at crosslinking densities of 0.5–1.0%, depending on the length of the chains that are allowed to crosslink.     

The effect of polymer molecular weight and crosslinking reactions on the adhesion properties of microsphere water-based acrylic pressure-sensitive adhesives

In this work, the effect of polymer molecular weight and crosslinking reactions on the end-use properties of the microsphere water-based acrylic pressure-sensitive adhesives (PSA) is presented. Polymer molecular weight and polymer microstructure were regulated using different chain transfer agent (CTA) concentrations and by addition of a diacrylic monomer (MM). The adhesion properties of the synthesized PSAs were characterized via measurements of tack, peel adhesion and shear strength. The results of experiments have shown that the kinetics of suspension polymerization is relatively independent on the amount of CTA and MM. The amount of gel phase in the adhesive was reduced with increasing amount of CTA agent, and gel phase amount may be considered as a function of polymer molecular weight. With a combination of CTA and MM was possible to regulate the amount of formed gel phase in the adhesive, as well sol phase molecular weight. All of the measured adhesion properties strongly depend on molecular weight of the synthesized polymer and on the amount of gel phase. For adhesives synthesized solely with addition of CTA, tack decreased with lower polymer molecular weight and consecutively also with lower amount of gel phase. The same trend was also observed for peel strength measurements, whereas a cohesive failure was observed for adhesives with low amount of gel phase. A maximum value for tack and shear strength was observed at 80 wt% of gel phase. In case of syntheses with a combination of CTA and MM (amount of gel phase in range from 70 to 80 wt%), tack values were distributed in quite narrow range. On the other hand, peel strength values decreased in comparison with adhesives synthesized only with CTA, regardless to the equal amount of gel phase. Poor shear strength was observed for all adhesives synthesized by combination of CTA and MM.     

PH-induced structure change of poly(vinyl alcohol) hydrogel crosslinked with poly(acrylic acid)

The structure of the hydrogel of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was investigated by small angle X-ray scattering (SAXS) of synchrotron radiation. A physically crosslinked blend gel, which was prepared by repetitive freezing and thawing of an aqueous solution of PVA and PAA, could be chemically crosslinked by esterfication of PVA with PAA even in the hydrogel state. The chemical crosslinking induced the destruction of physical crosslinks into a folded structure, indicating that the chemical crosslinking proceeds at the sites around the physical crosslinks that contain PVA and PAA in much higher concentration than other portion of the gel. The pH-induced structure changes of the PVA hydrogels, chemically crosslinked with poly(acrylic acid) (PAA) were investigated by SAXS on the samples of various chemical crosslinking time. The gels were shrunk at pH4, and swollen at pH8. The results of SAXS showed, that the Porod slope changed with chemical crosslinking time from -3.5 to ?2.9 at pH4, and from ?2.9 to ?2.4 at pH8. The results suggest that a folded structure as a structural domain, which is characterized by fractally rough interface, tends to change into the structure that corresponds to percolation cluster, particularly at pH8. The gels immersed in pH8 showed a remarkable structure change accompanying swelling. The results revealed that a conformational change of PAA chains, induced by the pH change, can be explained by the presence of a structural domain in the gel network, where both PVA chains and PAA chains get entangled and partially form a interpenetrating polymer network(IPN).     

Synthesis of telechelic polyacrylates with unsaturated end-groups

A convenient, one-pot synthesis of telechelic and semi-telechelic polyacrylates with unsaturated end-groups has been developed. Atom transfer radical polymerization of methyl or n-butyl acrylate was initiated with either ethyl α-bromomethylacrylate or methyl dichloroacetate, as a monofunctional or difunctional initiator, respectively, and mediated with various Cu/amine complexes. Addition of excess ethyl 2-bromomethylacrylate was found to not only immediately quench the polymerization but also installed 2-carbethoxyallyl moieties on the ends of the polymer chains. The telechelic polymers were found to undergo thermally or photochemically induced crosslinking reactions.     

Secondary dispersion‐based reactive pressure‐sensitive adhesives with improved tack

Reactive pressure‐sensitive adhesives (PSA) have to meet the requirements for sufficient tack prior to crosslinking but also high shear after crosslinking. This article examines the use of secondary acrylic dispersions with reactive groups and epoxy resin dispersions for such PSA. Long‐term stable secondary PSA dispersions with high tack after film formation were obtained. Tack was dependent on the amount of carboxylic acid groups in the polymer as well as the base used for partial neutralization of the solvent‐borne copolymers. Reactive PSA were prepared by mixing a secondary dispersion with high amounts of carboxylic acid groups with an epoxy resin dispersion providing no tack. Variation of mixing ratio gave reactive PSA with sufficient tack, peel, and shear prior to crosslinking. Crosslinking of these reactive PSA at elevated temperatures led to high shear which was limited by incomplete molecular mixing of both phases. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46315.     

Hydrosilylation crosslinking of silicone rubber catalyzed by bis (1,5-cyclooctadiene) di-μ,μ′-chlorodirhodium

Hydrosilylation vulcanization of addition silicone rubber catalyzed by bis (1,5-cyclooctadiene) di-μ,μ′-chlorodirhodium at 150° was studied. The course of vulcanization, rubber network density, and mechanical properties of the vulcanizate are discussed with respect to the structure and molecular weight of the reactive groups of telechelic and internal vinylmethylpolysiloxanes and crosslinking methyl (hydrogen) dimethyl siloxane copolymers. Molecular weights of the polysiloxane components as well as the ration of unsaturated and Si—H groups were optimized. The results are in agreement with the theory of rubber elasticity of polymer networks and show wide application possibilities of the catalyst used.     

The synthesis and characterization of novel carboxyl telechelic microspheres

A series of novel carboxyl telechelic microspheres (CTMs) with different length of oligo-caprolactone telechelic chains are readily prepared via a three-step approach involving: (1) the hydrolytic oligomerization of ε-caprolactone, (2) the esterification of oligo-caprolactone with maleic anhydride, and (3) the suspension polymerization of maleic acid polycaprolactone ester acid (MAPCLA) with divinylbenzene. The CTMs, which are water swellable, spherical, and porous, contain carboxyl functionalities of 1.0 to 4.2 mEq/g (dry), which are found to be lower swelling change (during conversion of ionic form) and higher exchange efficiencies than those of the Emerk. IV resin. The intermediate products, oligo-caprolacton, and MAPCLA are characterized by the acid–base titration, hydroxyl value titration, and infrared and ¹H nuclear magnetic resonance analysis, respectively. The morphology and porous of CTMs are also tested by scanning electron microscopy and Brunauer-Emett-Teller technology. The effects of the length of the telechelic chains and the degree of crosslinking (divinylbenzene), as well as the amount of porogen (toluene), on the physical and chemical parameters of the CTMs are also described. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:205–216, 1998     

Crosslinking of isocyanate functional acrylic latex with telechelic polybutadiene. I. Synthesis and characterization

An ambient curable isocyanate functional acrylic latex was synthesized by incorporating dimethyl meta-isopropenyl benzyl isocyanate (TMI®), an isocyanate monomer, into styrene/n-butyl acrylate copolymer. An artificial latex of amino-terminated telechelic polybutadiene was prepared and blended with the acrylic latex as a curing agent. The isocyanate content in the blended latex was determined by titration and FTIR measurements. The latex blend properties, in terms of particle size and latex viscosity, and the latex film properties, in terms of stress–strain behavior and solvent swelling behavior, showed no significant change after 30 days' storage of the latex blend at 50°C. The good storage stability was attributed to the stable nature of the latex blend in which there was little chance for the isocyanate-containing particles to come into contact with the curing agent particles, thus preventing premature contact of the acrylic chains with the telechelic chains. The reactivity of different functional groups in the telechelic polymer was studied; the amino group was found to be the most reactive toward the TMI. In addition, a shorter chain telechelic crosslinker was found to result in a higher degree of crosslinking, but this was more intraparticle than interparticle in nature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 965–975, 1998     

UV-initiated crosslinking of photoreactive acrylic pressure-sensitive adhesives using excimer-laser

UV-initiated crosslinking technology is well established in the market and allows the production of a wide range of ultraviolet (UV)-crosslinkable pressure-sensitive adhesives (PSA) with interesting features. The balance between such properties as adhesive and cohesive strengths within the crosslinked self-adhesive coatings is critical for their performance. The UV crosslinking of acrylic PSA, especially for following properties: tack, peel adhesion, and shear strength of self-adhesive polymer layers, has been investigated using UV excimer-laser and UV lamp as UV sources. It was observed that after UV crosslinking of acrylic PSA using excimer-laser in comparison with typical UV lamp, high-quality PSA products with excellent properties, such as tack, peel adhesion, shear strength, and shrinkage were received.     

Computer-Aided Design of Crosslinked Polymer Membrane Using Machine Learning and Molecular Dynamics

The formation of crosslinking network between polymer chains has significant influence on polymer properties. In particular, the crosslinked structure of ionic networks like proton exchange membrane affects the conductivity performance. To further develop in this area, a framework for polymer membrane design based on the developed quantitative prediction model of the properties of crosslinked polymer is proposed. First, polymers with different crosslinking degrees are constructed by a crosslinking algorithm. Next, molecular dynamics is used to calculate the properties of crosslinked polymers. Then, the quantitative relationship between crosslinked polymer structures and macroscopical properties is developed. Subsequently, computer-aided polymer design method is integrated with the developed quantitative predict model. The crosslinked polymer design problem is expressed as an optimization problem to obtain the optimal crosslinking degree. Bayesian optimization strategy is used to solve the established optimization model. Finally, two case studies of perfluoro sulfonic acid and perfluoro imide acid design are given to illustrate the application of the proposed polymer design framework.     

Novel flexible network polymers consisting of oligomeric primary polymer chains originated in the mechanistic discussion of multiallyl crosslinking polymerization

Summary It is well known that allyl monomers polymerize only with difficulty and yield polymers having low molecular weights, i.e., oligomers. Inevitably, free-radical multiallyl crosslinking polymerization provides network polymers consisting of oligomeric primary polymer chains, i.e., having abundant dangling chains. This led to the development of novel flexible network polymers such as amphiphilic network polymers (I) consisting of short primary polymer chains and long crosslink units with opposite polarities, simultaneous interpenetrating networks (II) consisting of both polyurethane (PU) and polymethacrylate (PM) networks with oligomeric primary polymer chains, and network polymers (III) consisting of centipede-type primary polymer chains. Thus, the solution copolymerizations of benzyl methacrylate with tricosaethylene glycol dimethacrylate in the presence of lauryl mercaptan yielded I consisting of nonpolar, short primary polymer chains and polar, long crosslink units. The opposite type of I was prepared by the copolymerization of 2-hydroxyethyl methacrylate, a polar monomer having a hydroxyl group, with heneicosapropylene glycol dimethacrylate, a nonpolar monomer having a poly(oxypropylene) unit. The equimolar polyaddition crosslinking reaction of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with tri(oxytetramethylene) glycol, leading to PU networks, and the free-radical crosslinking copolymerization of methyl methacrylate with tri(oxytetramethylene) dimethacrylate in the presence of CBr₄, leading to PM networks, were progressed simultaneously, providing II formed via the topological crosslink between PU and PM network structures. The post-copolymerizations of oligomeric allyl methacrylate/alkyl methacrylate precopolymers, having different amounts of pendant allyl groups and different molecular weights, with allyl benzoate/vinyl benzoate monomer mixtures were conducted to give III.     

Molecular design and synthesis of crosslinked polyimides using radical isomerization of vinylcyclopropane with thiols

Reactive polyimides bearing a vinylcyclopropane (VCP) moiety in the main chain were successfully synthesized from the corresponding diamine with the VCP moiety. Their radical crosslinking using a dithiol proceeded with the radical ring-opening reaction (RROR) of the VCP moiety to afford the corresponding crosslinked polyimides with the CC bonds in crosslinking moieties. Thermal properties of those crosslinked polyimides were evaluated by thermal gravimetry and differential scanning calorimetry. As a result, the increase of the crosslinking degree in the crosslinked polymer exhibited great residual weight at 600°C. In contrast, the tendency of the glass transition temperature was inverse because the increase in the amount of dithiol unit as a crosslinker would enhance the mitigation of the polymer packing structure and activates the mobility of polymer chains.     

Correlation between network structure and brittleness of triallyl isocyanurate resins as compared with diallyl phthalate resins

It is not possible to improve the toughness of triallyl isocyanurate (TAIC) resins by applying the procedures useful for diallyl phthalate (DAP) resins as typical allyl resins. The results obtained are discussed in connection with the network structure of TAIC resin. Thus, the polymerization of TAIC would provide a homogeneous network accompanied by the incomplete occurrence of intermolecular crosslinking reactions caused by the rigidity of polymer chains, although DAP resins would consist of the microheterogeneous networks as the agglomerate of colloidal particles.     

Concentration of elastically active network chains and cyclisation in networks obtained by alternating stepwise polyaddition

The crosslinking statistics for the post-gel stage of a stepwise alternating polyaddition of a bi- and tri-functional component has been developed. The treatment includes formation of elastically inactive cycles and their activation resulting in formation of elastically active network chains (EANCs). Model calculations have shown that in networks formed from telechelic polymers the fraction of bonds wasted in elastically inactive cycles amounts only to several percent, but their effect on lowering the concentration of EANCs is rather important. The effect of cyclisation on the concentration of EANCs can be strongly reduced if the concentration of EANCs is compared at the same relative conversion with respect to that at the gel point or at the same gel fraction. The concentration is rather sensitive to incompleteness of the reaction or to deviations from the stoichiometrically equivalent ratio of the functional groups.     

UV crosslinkable microsphere pressure sensitive adhesives—influence on adhesive properties

In the following study, a synthesis and characterization of UV crosslinkable acrylic pressure sensitive adhesives are presented. Different amounts of unsaturated photoinitiator 4-acryloyloxy benzophenone (4-ABF) were added in t-butyl acrylate/2-ethylhexyl acrylate monomer mixture and then polymerized using a suspension polymerization technique. The adhesive suspension was coated on a pilot coating machine, dried by application of IR and subsequently crosslinked under UV light. The copolymerized 4-ABF photoinitiator will produce reactive radicals upon absorption of UV light, which are capable of initiating a rapid chain reaction with neighboring C-H positions of polymer side chains, what leads to formation of crosslinked polymer structures. UV crosslinking process was monitored by ATR-FTIR spectroscopic technique. Adhesion properties of the synthesized materials were determined using standard measurements of tack, peel and shear strength. Results have shown that all adhesive properties are strongly influenced by the degree of crosslinking of the microspheres, which increased with higher amounts of added 4-ABF photoinitiator. All the three measured adhesive properties showed a substantial decrease even at small amounts of added 4-ABF. The decrease in adhesion may be correlated with higher crosslinking density, what also resulted in higher gel phase amounts. Determination of glass transition temperature showed minor difference between adhesive coatings.     

Influence of borate amount on the swelling and rheological properties of the Scleroglucan/borax system

Scleroglucan is a fungal polysaccharide that, when dispersed in water, assumes a very stable triple helix structure. It has numerous industrial applications in different fields, such as food industry, cosmetics, and pharmaceutics. In the presence of borate ions, this polymer forms weak gels that, after freeze‐drying and compaction, show an anisotropic swelling behavior, related to the borate/polymer ratio. By monitoring the evolution of the elastic and viscous moduli it was possible to follow the gel formation kinetics. The rheological properties of the network were studied as a function of crosslinking agent concentration and the corresponding flow curves and mechanical spectra were recorded. The kinetics of the crosslinking reaction was monitored by following the time evolution of the storage and loss moduli, after the addition of borate ions to the Scleroglucan system. Creep‐recovery experiments allowed acquiring recoverable strain values and those of the critical stress above which a very high compliance of the sample is reached. Obtained results are to be related to the specific type of bonds between the polysaccharide chains and the crosslinking agent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42860.     

Preparation,morphology, and mechanical properties of elastomers based on α,ω‐dihydroxy‐polydimethylsiloxane/polystyrene blends

α,ω‐Dihydroxy‐polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by the solution polymerization of styrene (St) in the presence of α,ω ‐dihydroxy‐polydimethylsiloxane (PDMS), using toluene as solvent and benzoyl peroxide (BPO) as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, which were vulcanized to elastomers at room temperature with methyl‐triethoxysilicane (MTES). The use level of MTES was far more than the necessary amount used to end‐link hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Investigations were carried out on the elastomeric materials by extraction measurement, swelling measurement, and scanning electron microscopy. The extraction data show that at each composition the amount of soluble fraction is less than expected and the difference between experimental and theoretical values becomes more and more significant as PS content increases. This is mainly due to the grafting of PS onto PDMS and the entanglement of PS in the interpenetrating polymer network (IPN), which consists of either directly linked PDMS chains or chains linked via PS grafts and is formed by free radical crosslinking of PDMS during the radical polymerization of St. PS grafted on PDMS is insoluble and PS entangled in the IPN is difficult to extract. Both render the soluble fraction to be less than expected. As the St content in preparing PDMS/PS blends increases, the probability of grafting PS onto PDMS also increases, which may subsequently produce a higher crosslinking level of PDMS networks that linked via PS grafts by radical crosslinking. As a result, not only the amount of insoluble PS increases but also PS entangled in the IPN is more difficult to extract. Scanning electron microscopy demonstrates that the elastomer system has a microphase‐separated structure and a certain amount of PS remains in the PDMS networks after extraction, which is in accordance with the extraction data. Moreover, the mechanical properties of the elastormeric materials have been studied in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3542–3548, 2004