Thermal degradation studies of polyurethane/POSS nanohybrid elastomers

Reported here is the synthesis of a series of polyurethane/POSS nanohybrid elastomers, the characterisation of their thermal stability and degradation behaviour at elevated temperatures using a combination of thermogravimetric Analysis (TGA) and thermal volatilisation analysis (TVA). A series of PU elastomer systems have been formulated incorporating varying levels of 1,2-propanediol-heptaisobutyl-POSS (PHIPOSS) as a chain extender unit, replacing butane diol. The bulk thermal stability of the nanohybrid systems has been characterised using TGA. Results indicate that covalent incorporation of POSS into the PU elastomer network increases the non-oxidative thermal stability of the systems. TVA analysis of the thermal degradation of the POSS/PU hybrid elastomers have demonstrated that the hybrid systems are indeed more thermally stable when compared to the unmodified PU matrix; evolving significantly reduced levels of volatile degradation products and exhibiting a ∼30 °C increase in onset degradation temperature. Furthermore, characterisation of the distribution of degradation products from both unmodified and hybrid systems indicate that the inclusion of POSS in the PU network is directly influencing the degradation pathways of both the soft and hard-block components of the elastomers: The POSS/PU hybrid systems show reduced levels of CO, CO₂, water and increased levels of THF as products of thermal degradation.     

苯基笼状倍半硅氧烷(TSP-POSS)改性聚氨酯的分子模拟和热性能研究

采用分子力学及分子动力学方法,构建了质量百分比分别为0 wt%、3.06 wt%、6.56 wt%、10.13wt%、12.11 wt%、15.36 wt%和19.87 wt%共7种TSP-POSS杂化聚氨酯的分子结构模型,通过对均方位移、径向分布函数、XRD衍射图谱的分析,在分子水平上研究了半笼型TSP-POSS的引入对聚氨酯分子链结构及热性能的影响.结果表明,当TSP-POSS含量低于12.11 wt%时,随着TSP-POSS质量分数的增加,分子链之间的平均距离增大,分子间相互作用减小,聚合物分子链的运动性增强;当TSP-POSS含量高于12.11 wt%时,TSP-POSS自身会团聚成晶簇,降低了聚合物分子链的运动能力并由无定形聚集状态转变为层状半结晶结构.通过对7种体系的体积-温度函数分析,证明TSP-POSS的引入在一定程度上能显著提高聚氨酯杂化材料的玻璃化转变温度,在一定程度上增强其热稳定性.     

用于抑制海洋微生物附着的过渡金属配合物研究进展

许多金属配合物具有杀菌、抗病毒和抗癌的活性,在医疗卫生等领域占有重要地位,其生物活性机理也得到了较深入系统的研究.虽然一些过渡金属配合物也在防止海洋微生物附着方面得到应用,但是专门从配位化学和生物无机化学的角度对其进行总结分析的研究还未见报道.以配体的不同类型对这类过渡金属配合物进行分类,简介了其用于防海洋微生物附着的实验室研究和实际应用情况,并对未来研究前景进行了展望.     

Antibiotic enhanced dopamine polymerization for engineering antifouling and antimicrobial membranes

In this work,we adopt a new tobramycin(TOB)-dopamine coating system to endow thin film composite membranes with excellent antifouling and antimicrobial properties.Combining the hydrophilic and antibiofouling properties of both TOB and polydopamine,the TOB-dopamine modified membrane exhibits improved antifouling and antimicrobial properties compared with the conventional dopamine modified and unmodified membranes.The TOB-dopamine system has two advantages over the conventional modification with dopamine and tris buffer solution.First,TOB-dopamine modification is more efficient than the conventional dopamine modification due to the accelerating effect of TOB on dopamine polymerization.Second,the TOB-dopamine modified membranes exhibit better hydrophilicity,and enhanced antifouling and antimicrobial properties than the conventional dopamine modified membrane.Beyond engineering membranes,the proposed TOB-dopamine system can also be extended for wider surface hydrophilic and antimicrobial modifications.     

Structures and antifouling properties of low surface energy non-toxic antifouling coatings modified by nano-SiO_2 powder

Antifouling coatings are used to improve the speed and energy efficiency of ships by preventing or- ganisms, such as barnacles and weed, building up on the underwater hull and helping the ships movement through the water. Typically, marine coatings are tributyltin self-polishing copolymer paints containing toxic molecules called biocides. They have been the most successful in combating bio- fouling on ships, but their widespread use has caused severe pollution in the marine ecosystem. The low surface energy marine coating is an entirely non-toxic alternative, which reduces the adhesion strength of marine organisms, facilitating their hydrodynamic removal at high speeds. In this paper, the novel low surface energy non-toxic marine antifouling coatings were prepared with modified acrylic resin, nano-SiO2, and other pigments. The effects of nano-SiO2 on the surface structure and elastic modulus of coating films have been studied, and the seawater test has been carried out in the Dalian Bay. The results showed that micro-nano layered structures on the coating films and the lowest surface energy and elastic modulus could be obtained when an appropriate mass ratio of resin, nano-SiO2, and other pigments in coatings approached. The seawater exposure test has shown that the lower the sur- face energy and elastic modulus of coatings are, the less the marine biofouling adheres on the coating films.     

Improving hydrophilicity and protein antifouling of electrospun poly(vinylidenefluoride-hexafluoropropylene) nanofiber membranes

<正>Poly(vinylidenefluoride-hexafluoropropylene)(PVDF-HFP) nanofiber membranes with improved hydrophilicity and protein fouling resistance via surface graft copolymerization of hydrophilic monomers were prepared.The surface modification involves atmospheric pressure glow discharge plasma(APGDP) pretreatment followed by graft copolymerization of poly(ethylene glycol) methyl ether methacrylate(PEGMA).The success of the graft modification with PEGMA on the PVDF-HFP fibrous membrane is ascertained by X-ray photoelectron spectroscopy(XPS) and attenuated total reflectance Fourier transform infrared measurements(ATR-FTIR).The hydrophilic property of the nanofiber membranes is assessed by water contact angle measurements.The results show that the PEGMA grafted PVDF-HFP nanofiber membrane has a water contact angle of 0°compared with the pristine value of 132°.The protein adsorption was effectively reduced after PEGMA grafting on the PVDF-HFP nanofiber membrane surface.The PEGMA polymer grafting density on the PVDF-HFP membrane surface is measured by the gravimetric method,and the filtration performance is characterized by the measurement of water flux.The results indicate that the water flux of the grafted PVDF-HFP fibrous membrane increases significantly with the increase of the PEGMA grafting density.     

A modified polyvinylchloride surface with antibacterial and antifouling functions

Surfaces with antibacterial and hydrophilic properties are very attractive to cardiovascular applications. The objective of this study was to synthesize and immobilize a novel antibacterial and hydrophilic polymer onto surface of polyvinylchloride via an effective and mild surface coating technique. The surface coated with a terpolymer constructed with N‐vinylpyrrolidone, 3,4‐dichloro‐5‐hydroxy‐2(5H)‐furanone derivative, and succinimide residue was evaluated with cell adhesion, bacterial adhesion, and bacterial viability. 3T3 mouse fibroblast cells and two bacteria species were used to evaluate surface adhesion and antibacterial activity. Results showed that the polymer‐modified polyvinylchloride surface exhibited not only significantly decreased 3T3 fibroblast cell adhesion with a 66% to 87% reduction but also significantly decreased bacterial adhesion with 69% to 87% and 52% to 74% reduction of Pseudomonas aeruginosa and Staphylococcus aureus attachment, respectively, as compared with original polyvinylchloride. Furthermore, the modified polyvinylchloride surfaces exhibited significant antibacterial functions by inhibiting bacterial growth (75%‐84% and 78–94% inhibition of P aeruginosa and S aureus, respectively, as compared to original polyvinylchloride) and killing bacteria. These results demonstrate that covalent polymer attachment conferred antifouling and antibacterial properties to the polyvinylchloride surface.     

Non-linear dielectric spectroscopy: antifouling and stabilisation of electrodes by a polymer coating

Non-linear dielectric spectroscopy (NLDS) has previously been shown to produce quantitative information that is indicative of the metabolic state of various organisms, by modeling the non-linear effects of their membranous enzymes on an applied oscillating electromagnetic field using supervised multivariate analysis methods. However, the instability of the characteristics of the measuring apparatus rendered the process temperamental at best in the laboratory and impractical for field use. The main practical problem, of the non-stationarity of the electrode-solution interface and the ease with which the electrode surfaces are subject to protein fouling. It is addressed by applying a thin, electrically transparent antifouling coat to the electrodes. This reduces the interminable cleaning procedures previously required to prepare the electrodes for use, increases their usable lifetime before recleaning, and also improves the precision and linearity of multivariate models on NLDS data.     

Preparation and thermal properties of a novel UV‐cured star polyurethane acrylate coating

A novel star polyurethane acrylate (SPUA) used for UV‐curable coating was prepared from 2,4‐toluene diisocyanate, 2‐hydroxyethyl arcylate, and hexakis(2‐hydroxyethyl)melamine, and characterized using FTIR, ¹H‐NMR, and elemental analysis. Its UV curing behaviors investigated via FTIR clearly indicated that this monomer could be cured rapidly at air atmosphere. The conversion of the unsaturated bond of the cured monomer sample is near to 72% after exposed under UV light for 40 sec. The hardness, flexibility, and mechanical properties of the cured film were also investigated. The thermal stability of the cured film was studied using thermogravimetric analysis (TGA) and real time Fourier transform infrared (RTFTIR). Results showed that this oligomer has some superior properties and can be used for UV curing coating. Copyright © 2007 John Wiley & Sons, Ltd.     

Migration and surface modification in polypropylene (PP)/polyhedral oligomeric silsequioxane (POSS) nanocomposites

This paper reports on the migration of POSS‐based nanocomposites both by annealing the melt and by heating the solid blend in the microwave oven. The migration proceeds to all surfaces of the sample as verified by ATR‐FTIR spectra of the bottom and top surfaces. Concentrations of POSS on the surface, exceeding 50%, are obtained. Polarity of the matrix increases POSS migration. During annealing at 190°C, a sublimation of POSS from the upper surface occurs. In air, sublimation is decreased by oxidizing the organic side groups of POSS and the PP to non‐volatile moieties. No sublimation occurs below 100°C. The AFM and SEM‐EDAX verified the high POSS concentration on the surface and indicated very pronounced roughness of the surface of the sample. The static contact angle measurements reveal very high hydrophobicity as well as low surface free energy (SFE) of the surface of the sample, which is close to that of Teflon and of pristine POSS. The migration of POSS is due to its lower surface tension, the entropy considerations, its lower cohesive energy with the matrix chains as compared to the cohesion energy between the chains, and the density and temperature fluctuations of the matrix chains which upon relaxation repulse and propel POSS to the surfaces. Copyright © 2008 John Wiley & Sons, Ltd.     

Long lasting marine antifouling polyurethane coating chemically bonded with poly(hexamethylene guanidine)

In order to protect the marine environment, traditional marine antifouling coatings such as tributyltin (TBT)-based antifouling coatings have been phased out. There is an urgent need to develop environmentally friendly marine antifouling coatings. In this work, the antibacterial poly(hexamethylene guanidine) (PHMG) was introduced into polyurethane (PU) through chemical bond to prepare a green environmentally friendly marine antifouling coating (PU-PHMG). The morphology, antimicrobial properties, mechanical properties and thermostability of the PU-PHMG films were investigated. The antimicrobial rates of PU-PHMG films against E. coli and S. aureus were both more than 99.9% when PHMG content in the films reached 1.0 wt%. The excellent antimicrobial activities can be maintained for more than 90 days due to the non-leaching characteristic of PHMG. The growth of algae was also inhibited on the surface of PU-PHMG films. The PU-PHMG coating is promising for the applications in marine antifouling field.     

Preparation of an environmentally friendly antifouling degradable polyurethane coating material based on medium-length fluorinated diols

A novel medium-length fluorinated diols and poly(L-lactide) (PLLA) were synthesized via Michael addition reaction and ring-opening polymerization, respectively. Subsequently, Synthetic medium-length fluorinated diols and PLLA were combined to prepare new polyurethane composites with degradability and low surface energy. The compositional analysis and structural characterization of synthetic materials were characterized by using fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance spectra (¹HNMR). Thermogravimetric analysis(TGA) indicated that the introduction of medium-length fluorinated diols improved the thermal stability of the polyurethane. The biodegradation and low surface energy of the polyurethane were investigated by static hydrolysis experiment and water contact angle test. It was found that the degradation rate of the polyurethane increased as measurement time went on when the PLLA content was under 40%, and the water contact angle increased from 71.12° to 108.24° with the increase of fluorine content, which indicated that the degradable and low surface energy polyurethane has a potential as a coating material for a marine antifouling coating application.     

Reversible adhesion surface coating proppant

Proppant is a key material in the hydraulic fracturing process,which has been widely used in unconventional oil exploitation.Normal proppants are easy to sedimentate and accumulate at the entrance of shale fracture,which will block the diversion of water,oil and gas.Coated proppants(CPs) are fabricated by coating resin on normal ceramic proppants through a simple method,which is dramatically enhanced the supporting properties in shale fracture and easy to scale up.Compared with uncoated ceramic proppants,the self-suspension ability of CPs is ~11 times higher,which are able to migrate and distribute farther and deeper inside the fracture.At the same time,Coating enhanced the 23.7% of adhesive force in maximum,which makes the CPs easier to adhere on the fracture surface to supportthe shale fracture.Besides,the liquid conductivity of CPs is 60% higher than uncoated ceramic proppants at13.6 MPa pressure.This method is expected to fabricated varieties of proppantsfor shale fracture supporting to improve the exploration of unconventional oil and gas resources.     

Assessment of corrosion protection and performance of bio-based polyurethane acrylate incorporated with nano zinc oxide coating

In this study, a series of UV-curable anticorrosive PUA coatings embedded with varying concentrations of inorganic ZnO fillers have been successfully prepared from jatropha-based polyol. The electrochemical impedance spectroscopy (EIS) and Tafel polarisation analysis revealed that increasing fillers composition lead to the improvement of the anticorrosive property of the hybrid coatings. Meanwhile, the salt spray test results were found to correlate with the EIS of C_c (F cm⁻²) was 2.71 × 10⁻⁹, Bode plot - 10⁶ Ω cm² and Tafel polarisation results 7.56 × 10⁻⁶ MPY at 3 wt% of ZnO. Physical properties of 3 wt% loading of ZnO fillers in hardness test obtained 6H which was strongly attributed to the low interfacial interaction and poor dispersion of the fillers within the polymer matrix.     

Surface-modified carbon nanotubes and the effect of their addition on the tribological behavior of a polyurethane coating

The toluene-2,4-diisocyanate (TDI) treatment was used to bind isocyanate functional groups (OCN-) on the surface of multi-walled carbon nanotubes (MWCNTs), after which the TDI modified MWCNTs and unmodified MWCNTs were added to the polyurethane (PU) to produce composite coatings with improved wear properties. When the modified MWCNTs were added to the PU binder, the grafting TDI can take part in the curing of the PU binder so that chemical bonding was established between the MWCNTs and the matrix. Friction and wear tests indicated that modified MWCNT reinforced PU composite coating has the highest coefficient of friction and the highest wear resistance of the examined composite coating. Furthermore, the effects of sliding speed and applied load on the friction and wear behavior of the PU coating filled with MWCNTs or MWCNTs-TDI were also studied. The results showed that the coefficient of friction decreased with increasing sliding speed and applied load, and the anti-wear behavior of the PU coating filled with MWCNTs-TDI was the best under 320 N at a speed of 3.0 m s⁻¹.     

Thermoresponsive oligo(ethylene glycol) methacrylate colloids with antifouling surface properties

Thermoresponsive polymeric colloids attract great attention in several biotechnological applications owing to their ability to manipulate drug release characteristics in a controlled manner. Majority of these applications utilized N‐isopropylacrylamide (NIPAM)‐based particles for controlled drug release. Despite its advantages, such as easy chemical modification and well‐documented literature, a potentially important bottleneck for NIPAM in biological applications is its tendency for nonspecific protein adsorption. Herein, we report a simple way to prepare novel thermoresponsive colloids composed of oligo(ethylene glycol) side chains via precipitation polymerization technique. In addition to displaying highly reversible thermal response, these particles also have considerably low nonspecific protein adsorption when compared with NIPAM counterparts. These crosslinked poly(ethylene glycol) ethyl ether methacrylate particles were characterized using dynamic light scattering and transmission electron microscopy. The effects of co‐monomer, crosslinker and initiator on particle characteristics were investigated. Finally, particle toxicity studies were carried out using 3T3 fibroblast cell lines in MTT cytotoxicity assay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A study on phase morphology and surface properties of polyurethane/organoclay nanocomposite

In this study, polyurethane/organically modified layered silicate (organoclay) nanocomposites were prepared through in situ polymerization in the presence of organoclay. Phase morphology of the polyurethane/organoclay nanocomposite was investigated by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). The results suggest that the inter-domain repeat distance decreased with the introduction of organoclay. The organoclay has a more significant effect on the inter-domain repeat distance at a low hard segment content. Also with the increase of the hard segment, the inter-domain repeat distance and domain size increased markedly. The size of hard domain of the polyurethane was found to be in the range of 12-32 nm in this case, and it keeps nearly unchanged with the clay content. It is suggested by AFM phase imaging technique that the hard domain can self-organize further to form spherical aggregates. The introduction of clay into the polyurethane matrix resulted in the decrease in the size of the spherical aggregates from ∼800 nm to ∼500 nm, indicating clay has an important effect on the aggregation behavior of hard domains. The effect of clay on the surface energy was examined by means of AFM and goniometry techniques. The results obtained by two methods are consistent, i.e., with the increase of clay content, the surface energy decreased due to the effect of organic modifier.     

Structures and antifouling properties of low surface energy non-toxic antifouling coatings modified by nano-SiO<Subscript>2</Subscript> powder

Antifouling coatings are used to improve the speed and energy efficiency of ships by preventing organisms, such as barnacles and weed, building up on the underwater hull and helping the ships movement through the water. Typically, marine coatings are tributyltin self-polishing copolymer paints containing toxic molecules called biocides. They have been the most successful in combating biofouling on ships, but their widespread use has caused severe pollution in the marine ecosystem. The low surface energy marine coating is an entirely non-toxic alternative, which reduces the adhesion strength of marine organisms, facilitating their hydrodynamic removal at high speeds. In this paper, the novel low surface energy non-toxic marine antifouling coatings were prepared with modified acrylic resin, nano-SiO₂, and other pigments. The effects of nano-SiO₂ on the surface structure and elastic modulus of coating films have been studied, and the seawater test has been carried out in the Dalian Bay. The results showed that micro-nano layered structures on the coating films and the lowest surface energy and elastic modulus could be obtained when an appropriate mass ratio of resin, nano-SiO₂, and other pigments in coatings approached. The seawater exposure test has shown that the lower the surface energy and elastic modulus of coatings are, the less the marine biofouling adheres on the coating films. Supported by High-Tech Research and Development Program of China (Grant No. 2004AA001520)     

POSS‐nylon 6 nanocomposites: Influence of POSS structure on surface and bulk properties

Hybrid organic/inorganic nanocomposites based on polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals and nylon 6 were prepared via melt mixing. Two structurally and chemically different POSS molecules, a closed cage, nonpolar octaisobutyl POSS (Oib‐POSS) and an open cage, polar trisilanolphenyl POSS (Tsp‐POSS) with differing predicted solubility parameters were evaluated in the nylon matrix. Surface analysis, including quasi‐static and dynamic nanoindentation and nanotribological techniques, revealed exceptional improvements in modulus and hardness along with significant reductions in friction. Additionally, surface wetting characteristics of the nylon were reversed, with POSS incorporation yielding low surface energy, highly hydrophobic surfaces. AFM, TEM/EDAX, spectroscopic techniques and thermomechanical analysis were used to evaluate nanoscale dispersion and bulk properties of the composites. Both POSS molecules exhibit preferential surface segregation behavior in the nylon matrix. Tsp‐POSS, with its higher predicted solubility in nylon, exhibited enhanced dispersion and tribomechanical properties at both nano and bulk scale. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1088–1102, 2009     

Reactivity differences between molecular and surface silanols in the preparation of homogeneous and heterogeneous olefin metathesis catalysts

The reaction of Mo(N)(CH₂tBu)₃ (1) and SiO_2-(700) generates (SiO)Mo(NH)(CHtBu)(CH₂tBu) (2) when performed in C₆H₆ (material [1/SiO_2-(700)]_C6H6). The grafting occurs presumably by protonation of the nitrido ligand to form an intermediate (SiO)Mo(NH)(CH₂tBu)₃ (3), a pentacoordinated complex, which decomposes into 2 and 2,2-dimethylpropane. While [1/SiO_2-(700)]_C6H6 is highly active in olefin metathesis, [1/SiO_2-(700)]_CH2Cl2 and [1/SiO_2-(700)]_THF are poorly active or inactive catalysts respectively. In contrast, when Mo(N)(CH₂tBu)₃ reacts with a molecular silanol derivative, a soluble model of the surface of SiO_2-(700), it yields a very stable complex, (c-C₅H₉)₇Si₇O₁₂SiO-Mo(NH)(CH₂tBu)₃ (3m), which does not spontaneously generate 2,2-dimethylpropane and an alkylidene complex in contrast to the surface complex. Moreover, 3m does not catalyse olefin metathesis at room temperature as it does not already contain the initiating carbene ligand, and it is necessary to heat up the reaction mixture to 110 °C to obtain low catalytic activity. Nevertheless, the complex 3m generates well-defined metallocarbenes when heated in the presence of PMe₃: (c-C₅H₉)₇Si₇O₁₂SiO-Mo(N)(CHtBu)(P(CH₃)₃)₂ (4m) as a 10:1 mixture of its syn and anti rotamers with the loss of 2 equiv. of 2,2-dimethylpropane.