Development of wood protective polyurethane coatings from mahua oil-based polyetheramide polyol: a renewable approach

The present work reports the preparation of wood protective polyurethane (PU) from mahua oil-based polyetheramide polyol and its performance evaluation. The synthesis of polyetheramide polyol was carried out in two steps: the first step deals with the synthesis of mahua oil fatty amide (MFA) from mahua oil by base catalyzed aminolysis reaction and the second step deals with the synthesis of polyetheramide polyol from diglycidyl ether of bisphenol-A (DGEBA) and MFA. The structure of the synthesized polyetheramide polyol was confirmed by the Attenuated total reflection fourier transform infrared (ATR-FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopy. The synthesized polyetheramide polyol was used as a precursor for the wood protective PU coatings. The performance of the prepared wood protective PU coatings was evaluated by the measurements of the various performance properties. The results reveal that mechanical, thermal, and microbial properties of the prepared PUs are satisfactory compared to other literature reported vegetable oil-based PUs; whereas, water, solvent, and chemical resistance of the prepared PUs are quite good. The study concludes that mahua oil-based polyetheramide polyol is a suitable precursor for the preparation of wood protective PU.     

Polyurethane (urea)/polyacrylates interpenetrating polymer network (IPN) adhesives for low surface energy materials

On the basis of the polymerization of the acrylate phase catalyzed by the oxidation of trialkylborane at room temperature, a series of polyurethane (urea)/polyacrylates adhesives with interpenetrating polymer network structure (IPNS) was synthesized. The crosslinking polyurethane (urea) phase was synthesized by the reaction between polymer diamine or triol and isocyanate. The resulting IPN adhesives as a function of the polyurethane (urea) or 2‐hydroxylethyl acrylate terminated polyurethane (HEA‐PU) (crosslinking agent of acrylate phase) content were explored. The adhesive morphology took on the IPNS that manifested as a finely dispersed polyurethane (urea) phase in the acrylate phase. Excellent adhesion to low surface energy materials was achieved within a wide range of polyurethane (urea) contents. The IPN adhesives also displayed better flexibility than polyacrylate adhesives with HEA‐PU as a crosslinking agent. Copyright © 2011 John Wiley & Sons, Ltd.     

Rheological properties of polyurethane adhesives containing silica as filler: influence of the nature and surface chemistry of silica

Four silicas, two fumed silicas (one hydrophilic and one hydrophobic) and two precipitated silicas (one hydrophilic and one hydrophobic), were added as filler to solvent‐based polyurethane (PU) adhesive formulations. In general, the addition of silica increased the viscosity, the storage and loss moduli of the PU adhesives but only the hydrophilic fumed silica exhibited pseudoplasticity and thixotropy. The rheological properties imparted by adding filmed silicas to PU adhesive solutions were more noticeable than that of precipitated silicas. Interactions between the hydrophilic fumed silica, the polyurethane and/or the solvent seemed to be responsible for the improved rheological properties of filled PU adhesives.     

Recycling of polyurethane wastes using different carboxylic acids via acidolysis to produce wood adhesives

This study aims to provide further understanding on the depolymerization of polyurethanes (PU) via acidolysis. Therefore, polyurethane foams scraps are chemical recycled using different dicarboxylic acids, namely succinic and phthalic dicarboxylic acids, being the reaction products identified using Fourier-transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The results obtained show that succinic acid has higher efficiency as cleavage agent, as a result, the succinic acid ensuing recovered polyol (RP) presents higher hydroxyl value and lower viscosity. Additionally, from the oxidative-induction time measurements, it is observed that the RP is considerably more thermally stable, than the petroleum-based polyol, due to the higher content of aromatic moieties. Afterwards, the RP is used as substitute of petroleum-based polyol in the production of polyurethane adhesives (PUA) and compared with conventional polyol based PUA. Due to the higher content of aromatic moieties, higher bonding strength is achieved using the RP. Overall, further understanding on the acidolysis is obtained, proving the suitability of this method for the recycling of PU.     

Effect of nanosilica on the kinetics of cure reaction and thermal degradation of epoxy resin

Nanocomposites from nanoscale silica particles(NS),diglycidylether of bisphenol-A based epoxy(DGEBA),and 3,5-diamino-N-(4-(quinolin-8-yloxy) phenyl) benzamide(DQPB) as curing agent were obtained from direct blending of these materials.The effect of nanosilica(NS) particles as catalyst on the cure reaction of DGEBA/DQPB system was studied by using non-isothermal DSC technique.The activation energy(E_a) was obtained by using Kissinger and Ozawa equations. The E_a value of curing of DGEBA/DQPB/10%NS system showed a decrease of about 10 kJ/mol indicating the catalytic effect of NS particles on the cure reaction.The E_a values of thermal degradation of the cured samples of both systems were 148 kJ/mol and 160 kJ/mol,respectively.The addition of 10%of NS to the curing mixture did not have much effect on the initial decomposition temperature(T_i) but increased the char residues from 20%to 28%at 650℃.     

Biobased polyurethane adhesive over petroleum based adhesive: Use of renewable resource

This review article is based on the recent trends and development of biobased polyurethane (PU) adhesives from vegetable oil. A detail discussion has been reported about the PU adhesive starting from petroleum based to biobased source. Special attention has been given towards the utilization of castor oil based PU in adhesive technology, due to the wide range of castor oil among all vegetable oil. The appreciable adhesion, mechanical, thermal properties of vegetable oil based PU adhesives were compared with petroleum based PU adhesive, which were utilized to meet the specific application in adhesion industry.     

Modification of the rheological properties of polyurethanes by adding fumed silica: influence of the preparation procedure

The way of addition of fumed silica determined the rheological properties of polyurethane (PU) adhesives. The higher the shear rate during preparation of fumed silica containingPU adhesives, the higher viscosity and improved plasticity and thixotropy in the solutions. The improved properties of these adhesive solutions were ascribed to the creation of interactions between the silanol groups on the fumed silica, the polar groups in the soft segments of the polyurethane and/or the solvent. However, the way of incorporate the fumed silica in the polyurethane did not affect the rheological properties of fumed silica-PU composites (obtained by solvent removal from the solutions), indicating the key role of the solvent in the rheology of PU adhesive solutions.     

Preparation of Silver Nanoparticles Incorporated Electrospun Polyurethane Nano-fibrous Mat for Wound Dressing

Polyurethane foam is currently used as an exudate absorptive wound dressing material. In this study silver (Ag) nanoparticles were incorporated into electrospun polyurethane (PU) nanofiber to enhance the antibacterial as well as wound healing properties. The electrospinning parameters were optimized for PU with and without silver nanoparticles. Silver nanoparticles were synthesized by aqueous and organic methods. The water absorption, antibacterial and cytocompatibility of the PU-Ag nanofibers were studied and compared to that of conventional PU foam. The results indicated that the PU-Ag nanofibers could be used for wound dressing applications.     

Polymeric Nanocomposites of Polyurethane Block Copolymers and Functionalized Multi‐Walled Carbon Nanotubes as Crosslinkers

Summary: We report on a new route to synthesize polymeric carbon nanotube‐polyurethane (PU) nanocomposites. Multi‐walled carbon nanotubes (MWNTs) functionalized by chemical modification were incorporated as a crosslinker in prepolymer, which was prepared from a reaction of 4,4′‐methylene bis(phenylisocyanate) and poly(ε‐caprolactone)diol. The reinforcing effect of carbon nanotubes in crosslinked MWNT‐PU nanocomposites was more pronounced as compared to that in conventional MWNT‐PU nanocomposites. The optimum content of chemically modified MWNTs for crosslinking with polyurethane was determined to be approximately 4 wt.‐% in our samples, based on observation of a NCO peak in FT‐IR spectroscopy. MWNT‐crosslinked polyurethane containing 4 wt.‐% modified MWNTs showed the highest modulus and tensile strength among the composites and pure PU. The presence of functionalized MWNTs in the polymeric nanocomposite yielded enhancement in the thermal stability due to crosslinking of the MWNTs with PU.

Possible configuration for MWNT‐PU nanocomposite molecules and FT‐IR spectra of samples obtained during reaction of prepolymer with functionalized MWNTs (second step).     

Improvement in fracture behaviors of epoxy resins toughened with sulfonated poly(ether sulfone)

The sulfonated poly(ether sulfone) (SPES) was successfully prepared using chlorosulfonic acid as a sulfonating agent. Diglycidylether of bisphenol-A (DGEBA) epoxy resins were modified with different contents of SPES, and the thermal and mechanical interfacial properties of DGEBA/SPES blends were investigated. As a result, the surface free energy of the blends was increased by the addition of SPES. DSC measurements revealed that the curing reaction was delayed with the increase of SPES content. Whereas, the thermal stabilities of the blends were slightly decreased as the SPES content increased. Meanwhile, the glass transition temperature and fracture toughness of the blends were increased with increasing SPES content, due to the improved intermolecular interactions, such as hydrogen bonding, between the hydroxyl group of DGEBA and the sulfonic group of SPES in the blends. The agreement could be observed by SEM which revealed phase separated morphology of DGEBA/SPES blends.     

Epoxy as a reactive plasticizer for improving polycarbonate processibility

An oligomer of a diepoxy (diglycidyl ether of bisphenol-A, DGEBA) and an aromatic diamine (MCDEA) have been used as reactive plasticizers for polycarbonate (PC). A small amount of PC chain scission occurred during this blending process, probably due to transesterification of the PC carbonate group by the hydroxyl group of the DGEBA oligomer. Addition of DGEBA to PC was found to greatly reduce the T_g and processing temperature. Dynamic rheology measurements showed that the added epoxy can very effectively reduce the viscosity, but that the addition of epoxy also accelerated the crystallisation rate of the PC, which was confirmed by XRD, optical transmission microscopy and DMTA. The DMTA results of cured blends also showed that this crystallization of the PC enhanced their heat resistance properties. Sol–gel studies of the cured samples showed that some of the PC was grafted to the crosslinked epoxy network. Studies of the rubbery behaviour, solvent resistance of the cured blend and SEM images suggest that PC is the main continuous phase in the matrix and that the epoxy phase is mainly dispersed as sub-micron particles in the matrix.     

Synthesis and properties of silanized waterborne polyurethane/graphene nanocomposites

A series of silanized waterborne polyurethane (WPU)/graphene oxide (GO) chemical hybrids were synthesized from polycaprolactone diol, isophorone diisocyanate, dimethylol butanoic acid, and (3-aminopropyl) triethoxysilane with GO as multifunctional crosslink as well as reinforcing filler. With the addition of GO, dispersion size greatly decreased due to the increased water phase viscosity, while it increased after chain extension reaction due to the migration of GO into the PU particles. The GO covalently bonded to WPU via the sol–gel type reaction augmented contact angle, glass transition temperature (Tg), hardness, and Young’s modulus of the cast film up to 1 %. However, the effects were less pronounced at high content (1.5 %) due to the agglomeration of GO particles.     

AFM approach toward understanding morphologies in toughened thermosetting matrices

Atomic force microscopy, AFM, has been used for determining the microstructure of thermosetting matrices toughened by incorporation of core-shell particles and high-performance thermoplastics. A variety of systems has been considered in this work: one group is based on diglycidyl ether of bisphenol-A (DGEBA) epoxy matrix, and the other group is based on bisphenol-A dicyanate (DCBA) matrix. The studied epoxy systems were: DGEBA cured with an aromatic hardener, diamino diphenyl sulfone (DDS), and modified with polymethylmethacrylate (PMMA), or cured with a cycloaliphatic hardener, diamino dimethyl cyclohexylmethane (3DCM), and modified with core-shell particles of polystyrene-co-butylacrylate (PS-co-Bu). The DCBA-based matrices have been modified with polysulfone of bisphenol-A (PSU) or with polyetherimide (PEI). The influence of the modifiers and the curing conditions on the generated morphologies is reported as analysed by AFM in contact and tapping modes.     

聚丙烯-g-聚氨酯共聚物组成对其结晶行为的影响

接枝共聚物;聚丙烯-g-聚氨酯共聚物组成对其结晶行为的影响     

Composites of UHMWPE fiber reinforced PU/epoxy grafted interpenetrating polymer networks

Several polyurethane-modified epoxy resins (PU/DGEBA-g-IPNs) were synthesized and characterized through a series tests, including differential scanning calorimetry and mechanical property measurements, such as tensile, Izod, bending and shear strengths were investigated in the study. The PU/DGEBA-g-IPNs and neat DGEBA as matrices for UHMWPE fiber-reinforced and aramid fiber-reinforced composites were prepared for comparison of their mechanical properties. The degree of plasma treatment, the polyurethane content, and the type of polyol in the polyurethane within the matrix of the composite were investigated through mechanical and bulletproof testing.     

Properties of solvent based polyurethane adhesives containing fumed silicas

Five hydrophilic and two hydrophobic fumed silicas of different surface area and particle size were added to solvent based polyurethane adhesives. Silica addition produced a noticeable increase in the adhesive viscosity, imparted negative thixotropy, increased the storage modulus (G') and improved the green adhesion of chlorinated rubber/PU adhesive/chlorinated rubber joints. Those modifications were more pronounced in the adhesives which contain hydrophilic silicas.     

Novel urethane/epoxy resin hybrid materials using a moisture‐curing system

Novel curing systems of a urethane/epoxy resin [diglycidyl ether of bisphenol A (DGEBA)] alloy using the moisture‐latent hardener ketimine (K‐systems) were investigated on the DGEBA‐rich side and were compared with aromatic diamine curing systems (A‐systems). Almost all the added DGEBA was separated from the polyurethane matrix and dispersed as 2–10‐μm‐diameter particles after curing in the A‐systems. Therefore, DGEBA did not act as a reinforcing agent for the polyurethane matrix. However, 50% of the added DGEBA was dispersed as particles with a diameter of 1–4 μm, and the other 50% was incorporated into the polyurethane matrix in the novel K‐systems. Therefore, the polyurethane matrix in the K‐systems should be reinforced effectively by both incorporated and finely dispersed DGEBA and should result in significant improvements in the stress–strain properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1137–1144, 2004     

Surface-enhanced Raman scattering from bilayers of polystyrene,diglycidyl ether of bisphenol-A,poly(4-vinyl pyridine), and poly(4-styrene sulfonate)

Surface-enhanced Raman scattering (SERS) has been observed from thin films of polystyrene (PS), diglycidyl ether of bisphenol-A (DGEBA), and poly(4-vinyl pyridine) (PVP) deposited on silver island films Degradation of the polymers occurred rapidly during laser irradiation and was accompanied by the appearance of strong bands near 1375 and 1575 cm-1. These bands were attributed to the formation of graphite-like species by the silver-catalyzed thermal oxidation of the polymers induced by localized laser heating of the substrate. When the thin films of PS, DGEBA, or PVP were overcoated with much thicker films of a second polymer such as polystyrene sulfonate (PSS), the degradation was greatly reduced, and excellent SERS spectra of the PS, DGEBA, and PVP films were obtained. Overlayers reduced degradation within the first films deposited on silver island films by restricting the availability of oxygen at the interface to its solubility in the overlayer polymer or by altering the adsorption of oxygen onto the substrate. SERS was observed for the PS, DGEBA, and PVP films and the PSS overlayers when the films were deposited from relatively dilute solutions. When the PS, DGEBA, and PVP films were deposited from more concentrated solutions, SERS was not observed from the PSS overlayers. It was suggested that most of the SERS was due to a short-range, charge-transfer mechanism associated with sites of atomic scale roughness and that SERS was observed from the overlayer when the first film failed to occupy all of the sites.     

Use of calcium carbonate – fumed silica mixtures as filler in polyurethane adhesives

Natural ultramicronized calcium carbonate and mixtures of fumed silica‐natural ultramicronized calcium carbonate are proposed as fillers of solvent based polyurethane (PU) adhesives. PU adhesive containing only calcium carbonate shows similar rheological, thermal, mechanical, surface and adhesion properties than the PU adhesive without filler. Addition of 90 wt% fumed silica +10 wt% calcium carbonate mixture to PU adhesive produced a similar performance than the PU adhesive containing only famed silica. The increase in the amount of natural calcium carbonate in respect to fumed silica in the filler mixture produced detrimental effect on the rheological and mechanical properties of the PU adhesives (in respect to those provided by the PU adhesive only containing fumed silica), although the surface and adhesion properties were not noticeably modified.     

网络间含离子键的聚氨酯/接枝乙烯基酯树脂互穿聚合物网络 研究

分别以双酚-A型环氧树脂E-51和聚醚型环氧树脂E-46为原料合成了两种二乙胺-环氧树脂和加成多元醇(分别命名为AE-51,AE-46),将其和甲基丙烯酸一起用于合成聚氨酯/接枝乙烯基酯树脂(PU/接枝VER)互穿聚合物网络(IPN),使之在两个网络间形成离子键。实验结果表明,这类新型的IPN材料中两个网络间的互穿程度与相容性进一步提高,从而导致刚性的接枝VER对弹性的PU网络有更好的增强效果。DSC和FTIR的测定结果表明,在含AE-51的IPN中,由于离子键的作用使PU网络硬段的有序结构遭到很大程度的破坏,与AE-51和PU网络中的硬段以及VER网络有较好的相容性有关,因此这类IPN材料具有较好的力学性能。