Functional Acrylic Resins Prepared via Photo-Induced Telomerization Using Tetrabromomethane as Telogen.

Novel method of obtaining functional acrylic resins (FARs) containing carboxyl- and benzophenone groups (in-chain functionalization) and terminal Br atoms was verified. Acrylic oligomers were prepared by a solution-free, UV-initiated telomerization process of basic monomer (n-butyl acrylate) and functional monomers (acrylic acid and 4-acrylooxybenzophenone) in the presence of radical photoinitiator and different amount of tetrabromomethane (CBr4) as telogen. The effect of telogen content on UV-telomerization kinetics as well as physicochemical and thermal (Tg) properties of FARs was investigated. A telogen content higher than 5 wt. parts does not affect the UV-telomerization rate (photo-DSC), the molecular weights of telomers (GPC), or their glass transition temperature (DSC), but it significantly increases the conversion of monomers (up to 88%) and lowers the viscosity of FARs (approx. 6 Pa·s). NMR studies confirmed the inclusion of CBr4 in the structure of functional acrylic telomers.

Influence of Methacrylate and Vinyl Monomers on Radical Bulk Photopolymerization Process and Properties of Epoxy-Acrylate Structural Adhesives.

In this paper, epoxy-acrylate structural adhesives tapes (SATs) were obtained from Bisphenol A-based liquid epoxy resin and epoxy acrylic resins (EARs). A new method of EARs preparation, i.e., the free radical bulk photopolymerization process (FRBP), was studied in detail. The influence of methacrylic monomers (methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, (2-acetoacetoxy)ethyl methacrylate) and vinyl monomers (N-vinylpyrrolidone and styrene) on the FRBP process of base monomers (i.e., butyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate) was investigated. The kinetics of photopolymerization process was monitored by photo-differential scanning calorimetry method. The properties of the obtained EARs (viscosity and average molecular weights), as well as monomers conversion using 1H NMR, were determined. It was revealed that styrene significantly decreases the photopolymerization rate and increases the final monomers conversion (+27%). However, the resulting tetrapolymers BA-co-GMA-co-HEA-co-STY have low molecular weights and low polydispersity (2.2). Methacrylate monomers with shorter aliphatic chains (

Multiblock Elastomers TPEAA and TPEEA: Physical Structure and Properties.

A three series of terpolymers composed of the blocks PTMO (MPTMO = 1000 g/mol) or DLAol (MDLAol = 540 g/mol), PA12 (MPA12 = 2000 g/mol) and xGT (DPxGT = 2) with various chemical compositions of ester block were obtained. The series differ in the chemical structure of the flexible block and weight content of the soft phase. The effect of the number of carbons dividing the terephthalate groups on the synthesis, structure and properties of these elastomers has been investigated. To confirm assumed chemical structure Carbon-13 (13C NMR) and Proton (1H NMR) Nuclear Magnetic Resonance and Fourier-transform Infrared Spectroscopy (FT-IR) were used. The influence of chemical compositions of ester block on the thermal properties and the phase separation of obtained systems were defined by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA) and Wide Angle X-ray Scattering (WAXS). The mechanical and elastic properties were evaluated.

The Effect of Type-I Photoinitiators on the Kinetics of the UV-Induced Cotelomerization Process of Acrylate Monomers and Properties of Obtained Pressure-Sensitive Adhesives.

A new method of solvent-free acrylic pressure-sensitive adhesives (PSAs) based on UV-induced cotelomerization products was presented. The key acrylic monomers (i.e., n-butyl acrylate and acrylic acid) with copolymerizable photoinitiator 4-acrylooxybenzophenone in the presence of a selected chain transfer agent (tetrabromomethane, TBM) were used in the UV-cotelomerization process. Moreover, two kinds of UV-photoinitiators (α-hydroxyalkylphenones, HPs and acylphosphine oxides, APOs) were tested. Photo-DSC, viscosity, thermogravimetric, and GPC measurements for cotelomers were performed. The kinetics study revealed that the systems with APOs, especially Omnirad 819 and Omnirad TPO, were characterized by a much higher reaction rate and greater initiation efficiency than HPs systems were. Additionally, the APO-based syrups exhibited a higher solid content (ca. 60-96 wt%), a higher dynamic viscosity (5-185 Pa·s), but slightly lower molecular weights (Mn and Mw) compared to HP syrups. However, better self-adhesive features (i.e., adhesion and tack) were observed for PSAs based on cotelomers syrups obtained using APOs with lower solid contents (55-80 wt%). It was found that as the solids content (i.e., monomers conversion) increased the adhesion, the tack and glass transition temperature decreased and the type and amount of photoinitiator had no effect on polydispersity. Most of the obtained PSAs were characterized by excellent cohesion, both at 20 °C and 70 °C.

E-Beam Effects on Poly(Xylitol Dicarboxylate-co-diol Dicarboxylate) Elastomers Tailored by Adjusting Monomer Chain Length.

Poly(xylitol dicarboxylate-co-diol dicarboxylate) elastomers can by synthesized using wide variety of monomers with different chain lengths. Obtained materials are all biodegradable, thermally stable elastomers, but their specific properties like glass transition temperature, degradation susceptibility, and mechanical moduli can be tailored for a specific application. Therefore, we synthesized eight elastomers using a combination of two dicarboxylic acids, namely suberic and sebacic acid, and four different diols, namely ethanediol, 1,3-propanediol, 1,4-buanediol, and 1,5-pentanediol. Materials were further modified by e-beam treatment with a dose of 100 kGy. Materials both before and after radiation modification were tested using tensile tests, gel fraction determination, 1H NMR, and 13C NMR. Thermal properties were tested by Differential Scanning Calorimetry (DSC), Dynamic Thermomechanical Analysis (DMTA) and Thermogravimetric Analysis (TGA). Degradation susceptibility to both enzymatic and hydrolytic degradation was also determined.

Synthesis and Characterization of Novel Hybrid Flocculants Based on Potato Starch Copolymers with Hollow Carbon Spheres.

Novel carbon nanofiller-based starch-g-polyacrylamide hybrid flocculation materials (St-PAM-CS) were in situ prepared using potato starch (St), acrylamide (AM), and hollow mesoporous carbon spheres (CSs; diameters of 300-400 nm). Structures of different St-PAM-CS systems were characterized by Fourier transform infrared (FTIR) spectroscopy, X-Ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), laser scanning microscopy (LSM), and particle size analysis. The flocculation tests were evaluated by removing high turbidity kaolin suspension-initial absorbance 1.84. The effect of the St to AM molar ratio, doses, and content of CSs in hybrids on flocculation efficiency were examined. Satisfactory flocculation efficiency was obtained for all hybrids with 1 wt.% of the CS component. The highest reduction of the kaolin suspension absorbance (to 0.06) was observed for a 3 mL dose of the starch hybrid with the highest AM content. Additionally, St-PAM-CS showed a reduction in the sludge volume in time. The hybrids reached better flocculation efficiency in relation to the reference systems without CSs. The proposed flocculation mechanism (considering bridging, patching, and formation of hydrogen bonds) has been confirmed by the recorded results.

Physical Effects of Radiation Modification of Biodegradable Xylitol-Based Materials Synthesized Using a Combination of Different Monomers.

There is a possibility of obtaining xylitol-based elastomers sharing common characteristics of biodegradability, thermal stability, and elastomeric behavior by using monomers with different chain-lengths. Therefore, we have synthesized eight elastomers using a combination of four different diols (ethanediol, 1.3-propanediol, 1.4-buanediol, and 1.5-pentanediol) and two different dicarboxylic acids (succinic acid and adipic acid). The obtained materials were further modified by performing e-beam treatment with a dose of 100 kGy. Materials both before and after radiation modification were tested by DSC, DMTA, TGA, tensile tests, gel fraction determination, hydrolytic and enzymatic degradation tests, 1H NMR and 13C NMR and FTIR.

Epoxy-Based Structural Self-Adhesive Tapes Modified with Acrylic Syrups Prepared via a Free Radical Photopolymerization Process.

New modifiers (i.e., acrylic syrups; ASs) of epoxy-resin-based thermally curable structural self-adhesive tapes (SATs) were prepared via a free radical bulk polymerization (FRBP) of n-butyl acrylate, butyl methacrylate, glycidyl methacrylate, and hydroxybutyl acrylate. In the process, two kinds of UV-photoinitiators (i.e., monoacylphosphine oxide/Omnirad TPO and bisacylphosphine oxide/Omnirad 819) and various mixing speed of the monomers mixture (200-1000 rpm) were applied. The TPO-based syrups exhibited a lower copolymers content (10-24 wt%), dynamic viscosity (<0.1 Pa·s), molecular weights (Mn and Mw, and polydispersity (1.9-2.5) than these with Omnirad 819. Additionally, the higher mixing speed significantly reduced monomers conversion and viscosity of ASs as well as molecular weights of the acrylate copolymers. These parameters influenced the properties of thermally uncured (e.g., adhesion) and thermally cured SATs (shear strength of aluminum/SAT/aluminum overlap joints). Better self-adhesive features were observed for SATs-TPO (based on ASs with lower monomers conversion, Mn and Mw); however, a slightly higher shear strength was noted for the thermally cured SAT-819 (ASs with higher monomers conversion, Mn and Mw). An impact of polydispersity of the acrylate copolymers as well as crosslinking degree of thermally cured SATs on the mechanical strength was also revealed.

Influence of Acrylic Acid on Kinetics of UV-Induced Cotelomerization Process and Properties of Obtained Pressure-Sensitive Adhesives.

A new environmentally friendly method of photoreactive pressure-sensitive adhesives (PSAs) preparation was demonstrated. PSAs based on n-butyl acrylate (BA), acrylic acid (AA) and 4-acryloyloxy benxophenone (ABP) were prepared via the UV-induced cotelomerization process in the presence of a radical photoinitiator (acylphosphine oxide) and telogen (tetrabromomethane). Hydroxyterminated polybutadiene was used as a crosslinking agent. Influence of AA concentration (0-10 wt %) on kinetics of the cotelomerization process was investigated using a photodifferential scanning calorimetry method, selected physicochemical features of obtained photoreactive BA/AA/ABP cotelomers (molecular masses, polydispersity, monomers conversion and dynamic viscosity) and self-adhesive properties of obtained PSAs (adhesion, tack and cohesion) were studied, as well. It turned out that AA content is the important factor that influences monomers conversion (thereby the volatile parts content in prepolymer) and PSAs' properties. As the acrylic acid content increases, the reaction rate increases, but the total monomers conversion and the solid content of the prepolymer decreases. Additionally, the adhesion and cohesion of PSAs were grown up, and their tackiness decreased. However, the AA content has no effect on molecular weights (Mw and Mn) and polydispersity (c.a. 1.5) of photoreactive cotelomers. The optimal AA content necessary to obtain a prepolymer with low volatile parts content and good PSA properties was determined.

Preparation and Characterization of Potato Starch Copolymers with a High Natural Polymer Content for the Removal of Cu(II) and Fe(III) from Solutions.

Cross-linked potato starch (StMBA) and starch-g-polyacrylamide materials with a high content of natural polymer from 60 to 90 wt.% (St60-St90) were synthesized by double chemical-chemical modification (grafting and cross-linking). Eco-friendly starch absorbents were tested for removal of Cu2+ and Fe3+ from aqueous solutions. The characteristics of the obtained materials (Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermal analysis (TGA), X-Ray Diffraction (XRD) and laser scanning microscopy (LSM)) confirmed their diversity in terms of composition and structure. The effect of N,N'-Methylenebisacrylamide (MBA) and polyacrylamide (PAM) content in the starch graft copolymers, treatment time and concentration of metal ions on adsorption efficiency were investigated. The adsorption efficiency for StMBA was 14.0 mg Cu2+/g and 2.9 mg Fe3+/g, regardless of the initial concentration of ions, whereas for starch graft copolymer St60 it was 23.0 mg Cu2+/g and 21.2 mg Fe3+/g. Absorption of Fe(III) was persisted even after 2 days. Pseudo-second order model was used to investigate the adsorption mechanisms. It was found that in addition to the chemical adsorption of ions on the surface, there is sorption inside the polymer network and chelating mechanism may dominate. Satisfactory results were attributed to the adequate grafting of PAM onto starch, the ability to form complexes with metal cations and changes in material structure.

Effect of the B:Zn:H2O Molar Ratio on the Properties of Poly(Vinyl Acetate) and Zinc Borate-Based Intumescent Coating Materials Exposed to a Quasi-Real Cellulosic Fire.

In order to investigate an influence of the B:Zn:H2O molar ratio on the fire protection efficiency of poly(vinyl acetate)-based thermoplastic intumescent coating materials (ICs), systems containing ammonium polyphosphate, melamine, pentaerythritol and different types of zinc borates (ZBs) were tested in a vertical position in quasi-real fire conditions. 3ZnO·2B2O3·6H2O (ZB6), 2ZnO·3B2O3·3.5H2O (ZB3.5) or 3ZnO·2B2O3 (ZB0) were added in amounts of 1-10 wt. parts/100 wt. parts of the other coating components mixture. Char formation processes and thermal insulation features were investigated using an open-flame furnace heated according to the cellulosic fire curve. Thermogravimetric features (DTG), chemical structures (FTIR) and mechanical strength of the ICs and the chars were analyzed as well. It was revealed that the type and dose of the ZBs significantly affect thermal insulation time (TIT) (up to 450 °C of a steel substrate) and sagging (SI) of the fire-heated coatings as well as the compressive strength of the created chars. The highest TIT value (+89%) was noted for the sample with 2.5 wt. parts of ZB3.5 while the lowest SI (-65%) was observed for the coatings containing 10 wt. parts of the hydrated borates (i.e., ZB3.5 or ZB6). The best mechanical strength was registered for the sample filled with the anhydrous modifier (3 wt. parts of ZB0). The presented results show that the ICs with the proper ZBs can be used for effective fire protection of vertically positioned steel elements.

Hydrophilic Films Based on Carboxymethylated Derivatives of Starch and Cellulose.

The carboxymethylated derivatives of starch (CMS) and cellulose (CMC) were used for film preparation. The infrared spectroscopy revealed that crosslinking via ester bridges with citric acid occurred between the two polysaccharide derivatives. The effect of polysaccharide derivatives ratio on physicochemical properties of prepared films was evaluated. Generally, the values of tested parameters (moisture absorption, surface roughness, and mechanical and thermal properties) were between the values noted for neat CMS or CMC-based films. However, the physicochemical properties of the system with equal CMS/CMC weight ratio diverged from this trend, i.e., the highest tensile strength, the highest Young's modulus (ca. 3.4 MPa and ca. 4.9 MPa, respectively), with simultaneously the lowest moisture absorption (18.5% after 72 h) have been noted. Such systems could potentially find application in agriculture or pharmacy.

Free-Radical Bulk-Photopolymerization Process as a Method of Obtaining Thermally Curable Structural Self-Adhesive Tapes and Effect of Used Type I Photoinitiators.

A new fabrication method for thin (120 µm) thermally curable structural self-adhesive tapes (SATs) was demonstrated by utilizing a series of acrylic syrups (ASs) modified using Bisphenol A-based liquid epoxy resin. The acrylic syrups containing poly(butyl acrylate-co-butyl methacrylate-co-glycidyl methacrylate-co-2-hydroxyetyl acrylate-co-4-acryloyloxy benzophenone) were synthesized via free-radical bulk-photopolymerization (FRBP) process. Influence of different type I radical photoinitiators (PIs), i.e., α-hydroxyalkylphenones (HPs), acylphosphine oxides (APOs) and its mixtures (HPs/APOs and APO/APO) on selected physico-chemical features of obtained ASs was studied. It turned out that APO-type PIs are more effective in the FRBP process (NMR studies). Self-adhesive tests of SATs revealed that the monomers' conversion in ASs have a significant influence on adhesion and tack. Moreover, the polymer structures formed at the UV cross-linking stage of SATs significantly affect the cross-linking degree of SATs during thermal curing (differential scanning calorimetry method). The highest values of overlap shear strength were achieved by SATs based on ASs with monomers' conversion on the level 50-60%.

Investigation of particle-based and monolithic columns for cation exchange protein displacement chromatography using poly(diallyl-dimethylammonium chloride) as displacer.

The overall topic of the investigation was the separation of basic proteins by cation exchange displacement chromatography. For this purpose two principal column morphologies were compared for the separation of ribonuclease A and alpha-chymotrypsinogen, two proteins found in the bovine pancreas. These were a column packed with porous particles (Macro-Prep S, 10 microm, 1000 A) and a monolithic column (UNO S1). Both columns are strong cation exchangers, carrying -SO3(-)-groups linked to a hydrophilic polymer support. Poly(diallyl-dimethylammonium chloride) (PDADMAC), a linear cationic polyelectrolyte composed of 100-200 quaternary pyrrolidinium rings, was used as displacer. The steric mass action (SMA) model and, in particular, the operating regime and dynamic affinity plots were used to aid method development. To date the SMA model has been applied primarily to simulate non-linear displacement chromatography of proteins using low molar mass displacers. Here, the model is applied to polyelectrolytes with a molar mass below 20000 g mol(-1), which corresponds to a degree of polymerization below 125 and an average contour length of less than 60 nm. The columns were characterized in terms of the adsorption isotherms (affinity, capacity) of the investigated proteins and the displacer.