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Since extraction of the naturally occurring mussel-foot proteins is expensive and time-consuming, routes towards synthetic analogues are continuously being explored. Often, these methods involve se ...

For the stabilization of complex bone fractures, tissue adhesives are an attractive alternative to conventional implants, often consisting of metal plates and screws whose fixation may impose additional trauma on the already fractured bone. This study reports on the synthesis and evaluation of activated dopamine derivatives as primers for fiber-reinforced-adhesive patches in bone-fracture stabilization strategies. The performance of synthesized dopamine derivatives are evaluated with regard to the adhesive shear strength of formed bone patches, as well as cell viability and surface properties. Dopamine-derived primers with methacrylamide, allyl, and thiol functional groups were found to significantly increase the adhesive shear strength of adhesive patches. Furthermore, deprotonation of the primer solution was determined to be essential in order to achieve good adhesion. In conclusion, the primer solutions that were found to give the best adhesion were the once where dopa-thiol was used in combination with either dopa-methacrylamide or dopa-allyl, resulting in shear bond strengths of 0.29 MPa.

By combining ATRP, dendrimer chemistry and ‘click’ reactions, a library of novel linear dendritic block copolymers (hybrids) was successfully synthesized. The isolated polymers displayed hydrophilic alkyne groups and Tg's ranging from 14 °C to 67 °C. A Tg threshold of 39 °C was found necessary for straightforward porous membrane fabrication via the breath figure method. Exploiting the copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction, a robust and benign protocol was identified enabling surface functionalization under aqueous conditions. Such manipulations included the introduction of fluorescent rhodamine for thorough assessment by confocal fluorescence microscopy as well as polyethylene glycol chains or perfluorinated groups for tuning the membrane wettability. Finally, with the initial indication of being nontoxic to human dermal fibroblasts (hDF) and osteoblast-like MG63, the porous membranes can potentially find use in the field of controlled cell culture such as patterning of cell growth.

Itaconic acid is a platform compound for bio-based renewable materials. This study employs itaconic anhydride (IAn) as a novel monomer for lipase-catalyzed ring-opening addition condensation polyme ...

Radical copolymerization based on acrylonitrile (AN) and 2,2,2-Trifluoroethyl acrylate (ATRIF) initited by AIBN was investigated in acetonitrile solution. The resulting pol- y(AN-co-ATRIF) copolymers were characterized by 1 H, 13 C, and 19 F NMR and IR spectroscopy, and size exclusion chromatogra- phy (SEC). Their compositions were assessed by 1 H NMR. The kinetics of radical copolymerization of AN with ATRIF was investigated from sereval experiments achieved at 70 � C from initial (AN)0/(ATRIF)0 molar ratios ranging between 20/80 and 80/20 and was enabled to determine the reactivity ratios of both comonomers. From the monomer—polymer copolymer- ization curve, the Fineman-Ross and Kelen-T€ laws enabled to assess the reactivity ratios (rAN5 r1 5 1.25 6 0.04 and rATRIF 5 r2 5 0.93 6 0.05 at 70 � C) while the revised pat- terns scheme led to r12 5 rAN 5 1.03, and r21 5 rATRIF 5 0.78 at 70 � C. In all cases, rAN x rATRIF product was close to unity, which indicates that poly(AN-co-ATRIF) copolymers exhibit a random structure. This was also confirmed by the Igarashi's and Pyun's laws which revealed the presence of AN-ATRIF, AN-AN, and ATRIF-ATRIF dyads. The Q and e values for ATRIF were also assessed (Q2 5 0.62 and e2 5 0.93). The glass transi- tion temperature values, Tg, of these copolymers increased from 17 to 61 � C as the molar percentage of ATRIF decreased from 77 to 16% in the copolymer. Thermogravimetry analysis of poly(AN-co-ATRIF) copolymers showed a good thermal sta- bility compared to that of poly(ATRIF) homopolymer due to incorporation of AN comonomer. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3856-3866

Functionalization of thermally expandable microspheres (TEMs) with a conjugated polymer is explored. These functionalized thermally expandable microspheres were prepared by grafting 3-n-dodecylthiophene via oxidative polymerization from a thiophene modified TEM. The thiophene modified TEM to 3-n-dodecylthiophene ratio was varied during grafting and the resulting poly(3-n-dodecylthiophene) grafted TEM were characterized by FT-IR spectroscopy, Thermal Gravimetric Analysis, Scanning Electron Microscopy, Thermo-Mechanical Analysis and X-ray diffraction. The particles were approximately 30 μm in diameter and upon heating, the functionalized microspheres expanded up to 50 times. This expansion property was related to the poly(3-n-dodecylthiophene) content, where the increase in poly(3-n-dodecylthiophene) on microsphere decreased the thermal expansion. The X-ray diffraction shows a sharpening of the poly(3-n-dodecylthiophene) (1 0 0) diffraction peak upon expansion. Grafting conjugated polymers to thermally expandable microspheres provides robust functional photo- and electro-active TEMs.

Emerging dendritic-linear-dendritic (DLD) hybrids that possess synergetic properties of linear and highly functional branched dendritic polymers are becoming important macromolecular scaffolds in f ...

Four sets comprising a total of 16 sequential interpenetrating network (SeqIPN) hydrogels were efficiently fabricated via UV initiated thiol-ene coupling chemistry and from 2 kDa or 8 kDa primary p ...

Poly(ethylene glycol) (PEG)-diallyls, ranging from 2 to 8 kDa, were successfully reacted with a trifunctional thiol crosslinker via thiol–ene coupling reaction to construct four different primary P ...

Considering the large number of applications for hydrogels, a better understanding of the relation between molecular structure and mechanical properties for well-defined hydrogel is essential. A ne ...

Aiming to develop new dielectric polymers containing CN and F groups with strong dipole moments, a novel copolymer of acrylonitrile (AN) and 2,2,2-trifluoroethyl acrylate (ATRIF) was synthesized in acetonitrile by free radical process as well as the respective homopolymer (poly(ATRIF)). The copolymer’s composition and microstructure were analyzed by FTIR, 1 H and 13 C NMR spectroscopy and SEC. The molar incorporation of AN determined in the copolymer by NMR was 58 mol%. Thermogravimetric analysis of poly(AN- co -ATRIF) copolymer showed good thermal stability comparatively to the fluorinated homopolymer. Both copolymer, poly(AN- co -ATRIF), and homopolymer, poly(ATRIF), were dielectrically characterized over a frequency range from 10 −1 to 10 6 Hz, and in a temperature range from 223 to 393 K. The dominating relaxation process detected in both materials is the α-relaxation, associated with the dynamic glass transition. A VFTH temperature dependence of the relaxation times ( τ ) was found for both materials, as characteristic of cooperative processes, from which the respective glass transition temperatures ( T g ( τ = 100 s)) were estimated, which differ ∼40 K, the one of the copolymer being higher (307 K) in accordance to the calorimetric analysis. This effect was attributed to a higher stiffness of the backbone in the copolymer originated by the inclusion of the acrylonitrile groups. Both relaxation functions have the same breath of relaxation times allowing constructing a single master curve, indicating similar non-exponential character. A less fragile behavior was found for the copolymer. This was rationalized in a more straightforward way by the free volume approach instead from a correlation between fragility and intermolecular coupling. It was found that in the copolymer the free volume increases at a lower rate with the temperature increase. It was inferred from the VFTH temperature dependence of the dc conductivity and low values of the decoupling index that ion motion is significantly influenced by the dynamics of the α-process.

In the last decades, the fabrication of ordered nano- and microporous structures has attracted increasing interest due to their specific properties and multiple possible applications in electronics, as templates or in the biological field. The development of such materials has been favored by the introduction of the simple breath-figure templating method in the 1990’s. In order to fully exploit the potential of these porous materials, the use of advanced functional molecules as precursors is essential. One suitable class of molecules is the well-defined linear-dendritic hybrids (LD hybrids) family. The structural variations, multiple end-groups and possible amphiphilicity of these molecules are significant advantages that could lead to highly sophisticated functional materials with potential usage in biology. Therefore, this project was directed towards the synthesis of advanced LD hybrids and the evaluation of their ability to form ordered functional porous films.A degradation and toxicity study was initially conducted on polyester-based 2,2-bis(methylol)propionic acid (bis-MPA) dendrimers under physiological conditions to support the potential usage of these molecules for biological purposes. The materials were found to undergo a relatively fast depolymerization process at pH 7.5. Moreover, the initial dendrimer and its decomposition products were proven to be non-toxic for immune competent cells, allowing for the utilization of these molecules for biological applications.A linear-dendritic-linear hybrid library was successfully synthesized from biocompatible poly(ethylene glycol) (PEG), poly(e-caprolactone) (PCL) and bis-MPA building blocks using a combination of ring-opening polymerization (ROP)and copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The materials, consisting of one long PEG block connected to the focal point of the dendron and several PCL arms attached at its periphery, were used to construct ordered porous films using the breath figure method. The polymeric architecture strongly affected the ordering of the films with a more regular morphology obtained from a more flexible polymer. Changing the semi-crystalline PCL to amorphous polylactide (PLA) also permitted the formation of porous arrays. Interestingly, films obtained from inverted structures possessing one long PCL block and several short PEG chains, also presented a regular morphology. Moreover they could be activated to exhibit multiple surface hydroxyl groups.To increase the number of orthogonal synthetic methodologies available for the preparation of advanced macromolecules, high molecular weight dendritic macrothiols were synthesized. These molecules were efficiently coupled to a number of core molecules via thiol-ene coupling, generating a comprehensive library of dendritic materials. This approach represents an attractive alternative to the commonly used, but potentially toxic, CuAAC.Exploiting the obtained results, a final LD hybrid was synthesized from atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA) derivatives and thiol-ene coupling (TEC) with macrothiols. This macromolecule was successfully utilized to form functional ordered porous arrays and the availability of peripheral alkyne functional groups was demonstrated by efficient coupling with fluorescent Rhodamine-B. The HEMA-backbone allowed for the introduction of cross-linkable azide groups that were used to significantly improve the thermal stability of the films from 50 °C to 200 °C. These materials have the potential to be used in applications such as catalysis, in medicine and as sensors.

In the present work, microfibrillated cellulose (MFC) made from bleached sulfite softwood dissolving pulp was utilized to reinforce a poly(ε-caprolactone) (PCL) biopolymer matrix. To improve the dispersibility of the hydrophilic MFC in the nonpolar matrix and the interfacial adhesion in the composite material, we covalently grafted the MFC with PCL via ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). To be able to investigate the effect of the PCL graft length on the mechanical properties of the composite material, we performed ROP to different molecular weights of the grafts. Bionanocomposites containing 0, 3, and 10 wt % MFC were prepared via hot pressing using both unmodified and PCL grafted MFC (MFC-g-PCL) as reinforcement. PCL grafting resulted in improved dispersion of the MFC in a nonpolar solvent and in the PCL matrix. The mechanical testing of the biocomposites showed an improvement in the mechanical properties for the PCL grafted MFC in comparison to ungrafted MFC. It was also shown that there was an impact on the mechanical properties with respect to the PCL graft lengths, and the strongest biocomposites were obtained after reinforcement with MFC grafted with the longest PCL graft length.

Rigid nanoscale polymer rods were prepared by grafting preformed amine-terminated poly(styrene) and poly(tert-butyl acrylate) onto oxidized cellulose microcrystals. Low polydispersity polymers, grown using atom transfer radical polymerization, were characterized and purified prior to cellulose attachment. Oxidation of the cellulose microcrystal led to the formation of carboxylic acids on the surface of the microcrystals. Covalent attachment of the polymers onto the cellulose microcrystals was achieved via a carbodiimide-mediated amidation reaction. The length and diameter of the polymer-cellulose composites increased upon surface modification. Typically, polymer-cellulose composites are synthesized by a grafting-from method because it can be difficult to obtain sufficient graft density using a grafting-to preparation. However, the composites reported here comprised 60-64% grafted polymer by mass. This degree of grafting-to allowed the composite to form stable suspensions in organic solvents.

Interfacial adhesion between immiscible cellulose–polymer interfaces is a crucial property for fibrous biocomposites. To tailor the interfacial adhesion, the grafting of polymers from cellulose films was studied using ring-opening polymerization of e-caprolactone. The poly(e-caprolactone) (PCL) grafted cellulose was analyzed with FTIR, AFM and via water CA measurements. The graft length was varied by the addition of a free initiator, enabling tailoring of the interfacial toughness. Films of microfibrillated cellulose were grafted with PCL and hot-pressed together with a PCL-film to form a bilayer laminate. Interfacial peeling toughness correlates very strongly with PCL degree of polymerization (DP). PCL grafts form physical entanglements in the PCL matrix and promote significant plastic deformation in the PCL bulk, thus increasing interfacial peeling energy.

Linear dendritic hybrid materials enable a range of architectural variations which offers novel possibilities in the tailoring of polymeric materials. In this study dendrons based on the 2,2-bis(methylol)propionic acid (bis-MPA) building block, bearing click chemistry moieties in the core and peripheral hydroxyl functionalities, have been used as macroinitiators for ring opening polymerization of e-caprolactone. A library of star branched polymers with poly(e-caprolactone) chains was initially constructed using dendrons up to 4th generation. In a second step, the popular CuAAC or thiol–ene click reaction was efficiently used to attach poly(ethylene glycol) chains of different lengths to the core. Potential applications of the resulted amphiphilic linear dendritic hybrids were investigated. Both self-assembled micelles loaded with doxorubicin anticancer drug and ordered honeycomb membranes with enhanced surface area were successfully fabricated and characterized.

The introduction of a nanoscopic reinforcing phase to a polymer matrix offers great possibilities of obtaining improved properties, enabling applications outside the boundaries of traditional composites. The majority of the work in this thesis has been devoted to polymer/clay nanocomposites in coating applications, using the hydroxyl-functional hyperbranched polyester Boltorn® as matrix and montmorillonite clay as nanofiller. Nanocomposites with a high degree of exfoliation were readily prepared using the straightforward solution-intercalation method with water as solvent. Hard and scratch-resistant coatings with preserved flexibility and transparency were obtained, and acrylate functionalization of Boltorn® rendered a UV-curable system with similar property improvements. In order to elucidate the effect of the dendritic architecture on the exfoliation process, a comparative study on the hyperbranched polyester Boltorn® and a linear analogue of this polymer was performed. X-ray diffraction and transmission electron microscopy confirmed the superior efficiency of the hyperbranched polymer in the preparation of this type of nanocomposites. Additionally, an objective of this thesis was to investigate how cellulose nanofibers can be utilized in high performance polymer nanocomposites. A reactive cellulose “nanopaper” template was combined with a hydrophilic hyperbranched thermoset matrix, resulting in a unique nanocomposite with significantly enhanced properties. Moreover, in order to fully utilize the great potential of cellulose nanofibers as reinforcement in hydrophobic polymer matrices, the hydrophilic surface of cellulose needs to be modified in order to improve the compatibility. For this, a grafting-from approach was explored, using ring-opening polymerization of e-caprolactone (CL) from microfibrillated cellulose (MFC), resulting in PCL-modified MFC. It was found that the hydrophobicity of the cellulose surfaces increased with longer graft lengths, and that polymer grafting rendered a smoother surface morphology. Subsequently, PCL-grafted MFC film/PCL film bilayer laminates were prepared in order to investigate the interfacial adhesion. Peel tests demonstrated a gradual increase in the interfacial adhesion with increasing graft lengths.

Hydrophobic isoporous membranes were fabricated using the "breath figure" method from polystyrene stars synthesized via ATRP. The living polymer chain ends at the surface of the films were then used, without further modification, in a "grafting-from" approach to grow surface-linked polyglycidyl methacrylate chains under conditions that maintained the regular honeycomb structure. This versatile functional surface was then used as a platform to build a small library of surfaces using a variety of simple chemistries: (i) the acid hydrolysis of the epoxide to form bis-alcohol groups and (ii) utilizing the "click-like" epoxide-amine reaction to functionalize the surface with a model biomolecule-(biotinamido)pentylamine. The successful modifications were confirmed by a combination of spectroscopic and biological means. Changes in the growth characteristics of nonmotile Psychrobacter sp. strain, SW5, on the honeycomb films, provided further evidence confirming changes in the hydrophobicity of the surface upon grafting.

In this contribution, the influence of abstractable hydrogen on the kinetics of photopolymerized vinyl ether/maleate monomer formulations is reported. The effects of chain transfer on the polymeriz ...

By taking advantage of the orthogonal nature of thiol−ene coupling and anhydride based esterification reactions, a facile and chemoselective strategy to dendritic macromolecules has been developed. The ability to interchange growth steps based on thiol−ene and anhydride chemistry allows the synthesis of fifth-generation dendrimers in only five steps and under benign reaction conditions. In addition, the presented coupling chemistries eliminate the traditional need for protection/deprotection steps and afford dendrimers in high yield and purity. The modularity of this strategy coupled with the latent reactivity of the alkene/hydroxyl chain ends was demonstrated by using different cores (alkene and hydroxyl functional), various AB2 and CD2 monomers and a range of chain end groups. As a result, three dendritic libraries were prepared which exhibited tunability of both the chemical functionality and physical properties including the fabrication of PEG hydrogels.

The combination of hardness, scratch resistance, and flexibility is a highly desired feature in many coating applications. The aim of this study is to achieve this through the introduction of an unmodified nanoclay, montmorillonite (Na(+)MMT), in a polymer resin based on the hyperbranched polyester Boltorn H30. Smooth and transparent films were prepared from both the neat and the nanoparticle-filled hyperbranched resins. X-ray diffraction (XRD) and transmission electron microscopy (TEM) corroborated a mainly exfoliated structure in the nanocomposite films, which was also supported by results from dynamic mechanical analysis (DMA). Furthermore, DMA measurements showed a 9-16 degrees C increase in Tg and a higher storage modulus-above and below the T(g)-both indications of a more cross-linked network, for the clay-containing film. Thermogravimetric analysis (TGA) demonstrated the influence of the nanofiller on the thermal properties of the nanocomposites, where a shift upward of the decomposition temperature in oxygen atmosphere is attributed to the improved barrier properties of the nanoparticle-filled materials. Conventional coating characterization methods demonstrated an increase in the surface hardness, scratch resistance and flexibility, with the introduction of clay, and all coatings exhibited excellent chemical resistance and adhesion.

Superhydrophobic and self-cleaning cellulose surfaces have been obtained via surface-confined grafting of glycidyl methacrylate using atom transfer radical polymerization combined with postmodification reactions. Both linear and branched graft-on-graft architectures were used for the postmodification reactions to obtain highly hydrophobic bio-fiber surfaces by functionalization of the grafts with either poly(dimethylsiloxane), perfluorinated chains, or alkyl chains, respectively. Postfunctionalization using alkyl chains yielded results similar to those of surfaces modified by perfluorination, in terms of superhydrophobicity, self-cleaning properties, and the stability of these properties over time. In addition, highly oleophobic surfaces have been obtained when modification with perfluorinated chains was performed.

In cellulose nanocomposites, the surface of the nanocellulosic phase is critical with respect to nanocellulose dispersion, network formation and nanocomposite properties. Microfibrillated cellulose ...

Novel thermo-responsive cellulose (filter paper) surfaces of N-isopropylacrylamide (NIPAAm) and pH-responsive cellulose surfaces of 4-vinylpyridine (4VP) have been achieved via surface-initiated ATRP. Dual-responsive (pH and temperature) cellulose surfaces were also obtained through the synthesis of block-copolymer brushes of PNIPAAm and P4VP. With changes in pH and temperature, these "intelligent" surfaces showed a reversible response to both individual triggers, as indicated by the changes in wettability from highly hydrophilic to highly hydrophobic observed by water contact angle measurements. Adjusting the composition of the grafted block-copolymer brushes allowed for further tuning of the wettability of these "intelligent" cellulose surfaces.

Presently, the majority of reports deal with combining chemical reactions, in a stepwise fashion, to obtain well-defined polymers. In the future, chemists need to address new challenges such as increase in the range of available efficient reactions, developing libraries of compatible one-pot reactions, and the application of obtained materials in key industries. Indeed, the rising importance of the click concept has now devised robust synthetic approaches in various fields of research. The unique selectivity of the click reaction is today a new found toolbox for scientists to investigate one-pot multi-step systems. Several accelerated protocols have elegantly been reported to obtain a library of advanced polymers.

A series of lanthanide (Eu3+) cored fluorinated dendrimers of generations 1 through 4 (G1–G4) have been studied with respect to their film-forming properties at the air–water surface. All dendrimers studied here formed stable films at the air–water surface. At the air–water surface, the dendrimers are likely to adopt asymmetric “funnel-like” conformations wherein the lanthanide core is directed towards the water surface and the fluorinated phenyl groups are directed away from the bulk phase. This hypothesis was further tested by addition of an electrolyte (0.01 M MgSO4) to the subphase. The added electrolyte was found to (i) advance the onset of network formation, as well as completion of monolayers, and (ii) increase the collapse pressure. Both features support the asymmetric conformation hypothesis, in that addition of an electrolyte promotes further conformational changes and shields electrostatic repulsion between lanthanide cores, thus allowing for closer packing of the molecules.

Immobilizing liquid crystalline polymers on cellulose generates new possibilities of accomplishing addressable/responsive bio-based substrates. In this paper we report on our first steps to combine the electro-optic properties of liquid crystals with the versatility of paper as a displaying substrate. Electric current or magnetic fields can be used to manipulate the orientation of liquid crystals and thereby change the appearance and the properties of the material. Atom transfer radical polymerization (ATRP) can be used successfully to graft polymers from solid substrates in a controlled manner. In this study it is shown that the grafting of a liquid crystalline monomer, 11-(4'-cyanophenyl-4″-phenoxy)undecyl acrylate, onto cellulose by ATRP is possible, and that thicker films can be obtained by using PMA as a spacer in between the cellulose and the liquid crystalline block. The cellulose fibers become highly hydrophobic subsequent to grafting and the liquid crystalline polymer possesses mesophases accessible for further processing.

The preparation and characterization of a series of first to fourth generation dendronized poly-(norbornene)s are presented. The monomers were synthesized in a divergent fashion from 5-norbornene-2 ...

The present study involves the synthesis of sulfonated poly(3-ethyl-3-(hydroxymethyl)oxetane), sPTMPO, by end-capping the hydroxy-groups in the PTMPO with 1,4-butane sultone. A series of the polymer with different degrees of substitution was investigated. Furthermore, the subsequent use of the sulfonated PTMPO as the acidic component in proton conducting membranes was explored. The membranes were prepared by either a) mixing the partly sulfonated PTMPO with hexamethoxymethyl melamine (HMMM) to form cross-links by ether formation between the methylol groups on HMMM and the remaining hydroxyl groups on the hyperbranched polyether or b) using the sulfonated polyether in conjunction with a pyridine functionalised polysulfone, PSU-pyridine, to produce acid–base blend membranes. Membrane properties such as proton conductivity, water uptake and mechanical properties are discussed.

Nanoparticles have been used to reinforce polymer matrices since the late 1980s, with promising results. Hyperbranched polymers are densely branched molecules with a globular structure, leading to ...

Four generations of dendronized polymers with a methacrylate backbone and hydroxy-functionalized aliphatic polyester dendrons based on 2,2-bis(methylol)propionic acid were studied in solutions by ...

Thermosetting resins based on semi-crystalline poly(dimethyl trimethylene carbonate) (PDTC) were synthesised and characterised. Polymers with linear and branched architectures were synthesised thro ...

Organic-inorganic hybrid materials consisting of nanosized silica particles with surface grafted PS or PS-b-PMMA were synthesized using ATRP. These hybrid materials were used in the fabrication of ...

Eu3+-. Tb3+- and Er3+-cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer f ...

Dendronized polymers with a methacrylate backbone bearing pendant aliphatic polyester dendrons based on 2,2-bis(methylol)propionic acid have been investigated by rheological measurements, different ...

A series of polymers tethered with bis-MPA dendrons was synthesized by a combination of divergent growth and atom transfer radical polymerization (ATRP). Macromonomers of first and second generatio ...

Summary: Branched aliphatic polycarbonates were synthesized by ring opening polymerization of 5,5-dimethyl-1,3-dioxane-2-one (NPC) initiated from polyfunctional alcohols and a commercial hyperbranched polyester (BOLTORN®). Polymerizations in the presence of fumaric acid under bulk conditions allowed high conversion (80%) without gelation. The synthesis of polymers with long chain branches was confirmed by size exclusion chromatography and universal calibration. The Mark–Houwink exponent decreased, indicating an increased density, while increasing the number of arms. The star polymers with up to four arms showed thermal properties Tg (20–30 °C) and Tm (100–110 °C) similar to linear PNPC. Boltorn™ hyperbranched polymer with radial polycarbonate grafts.

The synthesis and characterization of dendron-coated porphyrins up to the fifth generation are described. Both free base and zinc-cored tetraphenylporphyrin (TPPH2 and TPPZn) were used, from which the dendrons were divergently grown using the anhydride of acetonide-protected bis-MPA (acetonide-2,2-bis(methoxy)propanoic anhydride). It is shown that a spacer must be attached to the porphyrin to increase the hydrolytic stability and allow synthesis of higher generations. Direct coupling of dendrons to the porphyrins was also investigated but failed to give full substitution of the porphyrin core. The absorption and fluorescence emission data for the TPPZn dendrimers indicate that the porphyrin configuration may change at higher generations. The hydrodynamic volume of the dendrimers is calculated from the polarization anisotropy decay data. It is shown that these bis-MPA dendrimers are significantly smaller than the same generation Frechet-type benzyl ether TPP dendrimer.

Three sets of aliphatic polyester dendrimers based on 2,2-bis(methylol)propionic acid (bis-MPA) were synthesized. Two of the sets had benzylidene terminal groups and either a trimethylolpropane or ...

Thermosetting resins with semi-crystalline grafts have been synthesized. An amorphous resin with epoxide groups was first functionalized with hydroxyl groups using 2,2-bis(methylol) propionic acid, ...

An increased demand for new and improved coating systems, both due to environmental as well as performance reasons, have appeared during the last decades. Techniques such low temperature curing powder coatings, radiation curable systems, and high solids have gained an increased interest and obtained significant market shares. Although improved in many aspects, these systems still have limited use in certain applications due to technical reasons. One way to change the properties of thermoset resins that has obtained significant interest during the last decade is by changing the molecular architecture of the resin. An example of polymers which exhibit different properties compared to conventional linear structures are highly branched, dendritic, polymers [1-3]. These polymers, for example, exhibit a higher solubility and lower melt viscosity compared to their linear counterparts. They can also be tailored with respect to functionality and polarity to adjust the properties for certain applications. Coating resins based on hyperbranched polymers have been described both for liquid UV-curable systems as well as powder coatings [4-6]. This presentation will focus on how properties of resins based on dendritic polymers can be tailored and how this can applied to coating systems such as powder coatings, radiation curable resins and no-solvent liquid systems. The correlation between resin structure and its properties both before and after cure will be discussed.

Ductile polymer coatings were investigated in terms of their response to uniaxial deformation and contact deformation with respect to indentation and scratching. The effects of pigmentation, contact geometry, load and speed on the mechanical response were studied. The materials have been tested with extended spherical contacts deep into the coating layer and concentrated conical contacts close to the surface. The residual deformation pattern was examined with optical microscopy, white-light interferometry and atomic force microscopy. In the case of extended spherical contacts, corresponding to small effective strains, there was a correlation between the magnitude of residual deformation and the tensile strength. In the case of concentrated conical contacts, corresponding to larger strains, the materials were ranked differently. Reproducible failure transitions were detected with increased scratch load for the conical contacts. These failure transitions could not be directly linked to uniaxial break parameters. Stratification appears to be an issue in pigmented coatings. The effect of pigmentation was increased tensile stiffness and improved scratch resistance.

The scope of this work has been to investigate storage and recovery processes in ductile polymer coatings. The effects of storage have been measured in terms of variations in mechanical response with time. The use of contact tests in combination with sophisticated surface imaging tools offered unique possibilities to monitor deformation recovery over long periods of time. The kinetics of the recovery processes has been monitored. Polyurethane coatings were found to recover in a similar fashion to a viscous liquid. By comparing the time scale of the recovery with transient tests, it was evident that this was not a viscoelastic effect. The effect of exposure to water and humidity on deformation response and recovery was significant for polyurethane coatings. In addition, high amounts of pigmentation had a great effect on recovery processes. Surface-, bulk-, and interfacial-properties were greatly affected by storage time.

A series of 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) hyperbranched aliphatic polyesters with different molecular weights (generations) is analysed for the first time by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The main negative and positive low-mass fragments are identified in the fingerprint part of the spectra (m/z < 400) and are principally assigned to fragmentation of the Bis-MPA repeating units. In addition, it is shown that the fragmentation pattern is highly affected by the functional end-groups. This is illustrated for a phthalic acid end-capped hyperbranched polymer and for an acetonide-terminated dendrimer analog. Also, typical fragments assigned to the ethoxylated pentaerythritol core molecule are detected. These ions show decreasing intensities with increasing molecular weight. This intensity dependency on the generation is used to calibrate the molecular weight of hyperbranched polyesters on the surface. To obtain quantitative information, a principal component analysis WCA) multivariate statistical method is applied to the ToF-SIMS data. The influence of different normalization procedures prior to PCA calculation is tested, e.g. normalization to the total intensity, to the intensities of ions assigned to the Bis-MPA repeating unit or to intensities of fragments due to the core molecule. It is shown that only one principal component (PC1) is needed to describe most of the variance between the samples. In addition, PC1 takes into account the generation effect. However, different relationships between the PC1 scores and the hyperbranched mass average molecular weights are observed depending on the normalization procedure used. Normalization of data set ion intensities by ion intensities from the core molecule allows linearization of the SIMS intensities versus the molecular weight and allows the hyperbranched polymers to be discriminated up to the highest generations. In addition, PCA applied to ToF-SIMS data provides an extended interpretation of the spectra leading to further identification of the correlated mass peaks, such as those of the Bis-MPA repeating unit (terminal, dendritic and linear) and those of the core molecule. Finally, the work presented demonstrates the extreme potential of the static ToF-SIMS and PCA techniques in the analysis of dendritic molecules on solid surfaces.

Two ductile coating ma-terials were subjected to a combined indentation and scratch test procedure de-signed to screen a predetermined pattern of many small sample surfaces in a limited time. The screening of 50 surface spots ordered in a matrix pattern on the surface was carried out in 4.5 hr. The test provides reproducible data in terms of indentation modulus, elastic recovery, scratch penetration depth, and scratch residual depth, and also offers the possibility of detecting critical mechanical transitions such as rupture. The presented procedure produces sufficient data in a limited time scale to fulfill the requirements for a fast method to screen coating compositions.

The viscoelasticity of two thermally crosslinked polymer coatings was examined in terms of relaxation of the applied stress after a sudden strain. Two different transient methods were utilized: flat-ended cylindrical indentation testing of polymer film on a rigid substrate and tensile testing of a corresponding free-standing polymer film. The correlation between tensile and indentation tests was studied. The mechanical response of a viscoelastic layer deposited on a rigid substrate was investigated as a function of indentation depth. there was good agreement between the results of the tensile and indentation tests for thick film layers at moderate indentation depths. The findings indicate that the substrate influences the coating performance by reducing the viscous contribution to the stress response hand amplifying the magnitude of the equilibrium modulus for large indentation depths. The indentation method utilized here was shown to be a potentially suitable tool for the determination of Poisson's ratio of polymer films.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is utilized to study dendrons, dendrimers and hyperbranched derivatives prepared from the 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) or ...

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was utilized to study dendritic macromolecules with various architectures, such as dendrons, dendrimers and hyperbranched polyesters prepared from bis-(hydroxymethyl)propionic acid (Bis-MPA) and a series of hyperbranched polyethers based on 3-ethyl-3(hydroxymethyl)oxetane. The measurements were performed on spin-coated thin films of the branched molecules (D) onto silicon, chemically etched copper foil and silver-coated wafers. They showed weak signatures of molecular ions by proton capture (D + H) + in the high mass range of the spectra (m/z > 400). On the contrary, cationization of the intact molecules with alkali or transition metal ions such as Na + , Cu + or Ag + was observed. High-intensity quasi-molecular ions (D + M) + (with M = Na + , Cu + or Ag + ) allowed the studied polymers to be identified. The whole molecular species were observed for Bis-MPA dendrons and dendrimers up to 3000 Da for hydroxyl or acetonide-terminated derivatives. The success of the so-called cationization experiments with metal substrates compared with analysis of molecular adsorbates on silicon is highlighted. The ToF-SIMS sensitivity appeared useful to provide information about the molecular end-groups or to highlight incomplete reaction occurring during some deprotection step of the synthesis. Only uncationized fragments of low masses were detected for the hyperbranched polyesters. This result suggested the effect of molecular asymmetry and/or flattening of the molecules on the substrates, which hampered the molecule lift-off efficiency. Nevertheless, the hyperbranched polyethers were characterized based on the peak distribution of intensities, which allowed estimation of their molecular weight average. This work was intended to illustrate the capabilities of ToF-SIMS to analyse dendritic polymers on surfaces.

The use and interpretation of contact scratch tests on polymer coatings has been investigated. The influences from test parameters such as scratch speed, contact geometry and load on the deformation response were examined. Two ductile polymer coatings of commercial grade tailored for pre-painted steel applications were used as model systems. The residual deformation pattern was examined with optical microscopy, white-light interferometry, and atomic force microscopy. Free-standing coating films were also subjected to static, transient and dynamic tensile testing to find a correlation between the intrinsic coating properties and the scratch behavior. The results indicate that the use of a single set of contact parameters is insufficient to reflect the overall response of a coating material to real contact conditions. A well-designed scratch test will however give a substantial amount of useful information.

Fluorinated hyperbranched polymers and dendrimers with low optical losses and functionality to modify refractive index and add a cross-linking unit were developed. The results of refractive index measurements indicate a tunability of the refractive index between approximately 1.5 and 1.6, and optical losses below 0.5 dB/cm at 1550 nm. Dendrimers with similar surface group structure and possibility to surface functionalization were prepared using a lanthanide cation as focal point. Results on luminescent properties in the NIR and IR regions were measured for lanthanide ions such as Nd3+ and Er3+, showing characteristic emission bands at 1.06, 1.3 and 1.5 μm. The associated absorption and excitation spectra were found similar to those of the corresponding ions in optical glasses.