Adhesion of Technical Lignin-Based Non-Isocyanate Polyurethane Adhesives for Wood Bonding

Lignin is the most abundant aromatic natural polymer,and receiving great attention in replacing various petro-leum-based polymers.The aim of this study is to investigate the feasibility of technical lignin as a polyol for the synthesis of non-isocyanate polyurethane(NIPU)adhesives to substitute current polyurethane(PU)adhesives that have been synthesized with toxic isocyanate and polyols.Crude hardwood kraft lignin(C-HKL)was extracted from black liquor from a pulp mill followed by acetone fractionation to obtain acetone soluble-HKL(AS-HKL).Then,C-HKL,AS-HKL,and softwood sodium lignosulfonate(LS)were used for the synthesis of technical lignin-based NIPU adhesives through carbonation and polyamination and silane as a cross-linker.Their adhesion per-formance was determined for plywood.FTIR spectra showed the formation of urethane bonds and the reaction between lignin and silane.The NIPU adhesives prepared with C-HKL showed the highest adhesion strength among the three lignin-based NIPU adhesives.As the silane addition level increased,the adhesion strength of NIPU adhesives increased whereas formaldehyde emission decreased for all NIPU adhesives prepared.These results indicate that NIPU adhesives based on technical kraft lignin have a great potential as polyol for the synth-esis of bio-based NIPU adhesives for wood bonding.

Polyurethane Hybrid-Based Wood Adhesive: Review

Based on commercially available polyvinyl alcohol (PVA) stabilised polyvinyl acetate (PVAc), emulsion adhesives are neither heat nor moisture-resistant and show weak strength at high relative humidity and high temperatures. Pre- or post-crosslinking is another method used to manufacture a conventional vinyl-based homopolymers or copolymers system with improved water resistance. Vinyl neodecanoate (VeoVa), N-methylolacrylamide (NMA), Methacrylamide, methacrylic acid (MAA), and other self-crosslinking comonomers are typically inserted to produce highly water-resistant vinyl based homopolymers or copolymers. Additionally, organic crosslinkers like glyoxal, glutaraldehyde, citric acid, tartaric acid, and the like, as well as inorganic crosslinkers like acidic metal salts like aluminium chloride, aluminium nitrate, boric acid, and the like, can be used to prepare the highly water-resistant vinyl based homopolymers or copolymers. It is also possible to combine the self-crosslinking comonomers with the organic crosslinkers. Recently, a different hybrid chemistry has been developed that improves lap shear strength, has outstanding water resistance, good durability, and doesn’t require any additional crosslinker agents. Two distinct polymers were combined to develop hybrid polymers. They usually involve mixing an organic polymer with a polymer. There are many capping agents that are used for polyurethanes to produce acrylics that are capped with polyurethane and used as an oligomer in PVAc wood glue. Here, in this paper, we reviewed the different hybrid chemistry based on polyurethane chemistry for wood bonding applications.

Universal Encapsulation Adhesive for Lead Sedimentation and Attachable Perovskite Solar Cells with Enhanced Performance

In this work,a modified polyurethane adhesive(PUA)was prepared to realize a convenient encapsulation strategy for lead sedimentation and attachable perovskite solar cells(A-PSCs).The modified PUA can completely self-heal within 45 min at room temperature with an efficient lead ion-blocking rate of 99.3%.The PUA film can be coated on a metal electrode with slight efficiency improvement from 23.96%to 24.15%.The thermal stability at 65℃and the humidity stability at 55%relative humidity(RH)are superior to the devices encapsulated with polyisobutylene.The PUA film has strong adhesion to the flexible substrate and the initial efficiency of the flexible perovskite module(17.2%)encapsulated by PUA remains 92.6%within 1825 h.These results suggest that PUA encapsulation is universal for rigid and flexible PSCs with enhanced stability and low lead hazards.Moreover,it was found that flexible PSCs can be well attached to various substrates with PUA,providing a facile route for the A-PSCs in various scenarios without additional encapsulation and installation.

The Aging Behavior of Polyurethane Adhesive in Medium

The aging behavior of polyurethane adhesive in medium was investigated and compared by means of scanning electronic microscopy（SEM）, infrared spectroscopy（IR）, interface analysis and shearing strength test. The experimental results show that the shear strength of polyurethane adhesive in salt water is decreased more quickly than that in water. Na^＋ and Cl^- ions could make the polyurethane adhesive age faster and the interface metal corrosion. The high temperature accelerates the diffusion of water molecule, Na^＋ and Cl^- ions and the degradation of the giant molecule.

A feasibility study of using two-component polyurethane adhesive in constructing wooden structures

This investigation was conducted to determine the feasibility of using a two-component polyurethane （PUR） adhesive, with special waterproof properties, in constructing wooden structures. We designed and conducted tests to compare the shear strength and adhesion performance of PUR with polyvinyl acetate （PVAc） adhesive on block-shear specimens constructed of oriental beech （Fagus orientalis L.）, fir （Abies alba Mill.）, poplar （Populus deltoides Bartr.）, white oak （Quercus alba L.）, sycamore （Platanus orientalis L.） and white walnut （Juglans cinerea L.）. The values of the percentage of wood failure were also determined in specimens constructed with each adhesive. The highest shear strength values of both adhesives were obtained in specimens constructed of beech, while the lowest shear strength values were obtained in fir and poplar specimens. Average shear strength of the PUR adhesive was 16.5% higher than that of the PVAc adhesive. Specimens constructed of fir, poplar and sycamore were characterised by the highest percentages of wood failure, whereas the lowest average percentages of wood failure were obtained in beech and oak specimens. With the exception of oak specimens, there was no statistically significant difference between percentage of wood failure among the PUR and PVAc adhesives. Generally, the PUR adhesive showed an acceptable adhesion performance on wood materials used in our study.

Soy Protein Isolate Non-Isocyanates Polyurethanes(NIPU)Wood Adhesives

Soy-protein isolate(SPI)was used to prepare non-isocyanate polyurethane(NIPU)thermosetting adhesives for wood panels by reacting it with dimethyl carbonate(DMC)and hexamethylene diamine.Both linear as well as branched oligomers were obtained and identified,indicating how such oligomer structures could further cross-link to form a hardened network.Unusual structures were observed,namely carbamic acid-derived urethane linkages coupled with lactam structures.The curing of the adhesive was followed by thermomechanical analysis(TMA).It appeared to follow a two stages process:First,at a lower temperature(maximum 130℃),the growth of linear oligomers occurred,finally forming a physically entangled network.This appeared to collapse and disentangle,causing a decrease of MOE,as the temperature increases.This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature.Second,chemical cross-linking of the chains appeared to ensue,forming a hardened network.This was shown by the thermomechanical analysis(TMA)showing two distinct MOE maxima peaks,one around 130℃ and the other around 220℃,with a very marked MOE decrease between the two.Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented.The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards,showing to be suitable for interior grade plywood panels.It did not pass the requirements for wet tests.However,addition of 15%of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.

Liquefaction of Banana Pseudo-stem and Preparation of Polyurethane Adhesive from Liquefied Products

Banana pseudo-stem was liquefied in the mixture of polyhydric alcohols of polyethylene glycol(PEG400) and glycerol. Hydroxyl value of liquefied products ranged from 294.8 to 370.2 mg KOH/g and M_n was about 430. Liquefied products(LBPP) could be used as raw materials for polyurethane by reacting with 4, 4'-diphenylmethane diisocyanate(4, 4'-MDI) and PEG400 to synthesize liquefied product-based polyurethane(LBPP-PU) adhesive. To analyze in depth the creation of urethane linkage among LBPP, PEG400 and 4, 4'-MDI, factors which had effects on the residue content were all investigated. They were characterized by FT-IR and TG. The shear strength of LBPP-PU adhesive was improved when decreasing the percentage of the substitution of PEG400 by LBPP. The adhesive strength was obtained from T-peel of aspen/polyurethane adhesive joints, and the maximum lap shear strength(4.40 MPa) was obtained when 16.70% of LBPP was added to the LBPP & PEG400 system.

Preparation and Performance of Graphene Oxide Modified Polyurethane Thermal Conductive Insulating Adhesive

A novel graphene oxide (GO) modified polyurethane thermal conductive insulating adhesive with small addition and excellent insulation properties was prepared by in-situ polymerization using GO as thermal conductive filler.The effects of GO content on the mechanical performance,thermal conductivity,thermal stability and insulation properties of the modified polyurethane adhesive were studied.The results showed that the tensile strength and elongation at break of polyurethane adhesive increased at first and then decreased with the increase of GO content.The thermal conductivity and thermal decomposition temperature of GO/PU composite adhesive can be effectively improved by adding appropriate amount of GO.The tensile strength,thermal conductivity and thermal decomposition temperature of polyurethane adhesive reached the maximum when GO content was 1.5 wt%.The novel GO-modified polyurethane adhesive exhibited good insulation property.The development of GO/PU thermal conductive adhesive will provide a facile method for effectively solving the “trade-off” problem between low filling and high thermal conductivity.

Bio-Renewable Sources for Synthesis of Eco-Friendly Polyurethane Adhesives—Review

Bio-renewable sources used during manufacturing of polyurethane (PU) adhesives have been used extensively from last few decades and replaced petrochemical based PU adhesive due to their lower environmental impact, easy availability, low cost and biodegradability. Bio-renewable sources, such as vegetable oils (like palm oil, castor oil, jatropha oil, soybean oil), lactic acid, potato starch and other bio-renewable sources, constitute a rich source for the synthesis of polyols which are being considered for the production of “eco-friendly” PU adhesives. Various bio-renewable sources for synthesis of bio-based PU adhesives and their potential applications are discussed in this review. This paper will focus on the progress of research in bio-based materials for adhesive application.

Synthesis of Water-dispersed Polyurethane Adhesive and Its Application in Pigment Printing

Water-dispersed polyurethane (PU) adhesive is a novel and highly efficient adhesive with broad application potential. In this study, the key parameters affecting the synthesis and application of this adhesive were examined, and optimal conditions were identified. The water-dispersed PU adhesive was successfully synthesized, and applied in the fastness test of pigment printing on cotton fabric. The data demonstrated that all the fastnesses of PU adhesive were better than that of the conventional PA one.

Bio-Inspired Gelatin-Based Adhesive Modified with Waterborne Polyurethane on Click Chemistry

As a non-toxic,highly reactive biomass material,gelatin is wildly used as the component of biomass-based adhesive.However,like most aqueous adhesives,gelatin-based adhesives suffer from long solidifying time or high solidifying temperature due to the low volatility of water,which highly limits the application potential of gelatinbased adhesives.Inspired by the fast adhesion of marine organisms through the formation of chemical crosslinks,herein,a kind of low temperature curable eco-friendly gelatin-based adhesive with good adhesive properties and fast curing at low temperature is developed by introducing clicking chemical Diels-Alder(DA)reaction between blocked waterborne polyurethane(MWPU)and gelatin.The furfuryl glycidyl ether(FGE)and 4-Maleimidophenol(4-HPM)for the DA reaction are grafted on gelatin,and the end-capping of MWPU,respectively.With the addition of MWPU and FGE,the cross-linking degree of gelatin increased,and the adhesion properties of the adhesive were improved.The shear strength and T-peel strength of the modified adhesive reached 0.95 MPa and 1.42 N/mm,respectively,after the curing time of 8 min at 40℃,which can meet the application requirements as adhesive for bio-medical use.

Effect of Microscale Contact State of Polyurethane Surface on Adhesion and Friction

The effect of microscale contact of rough surfaces on the adhesion and friction under negative normal forces was experimentally investigated. The adhesive force of single point contact - sapphire ball to flat polyurethane did not vary with the normal force. With rough surface contact, which was assumed to be a great number of point contacts, the adhesive force increased logarithmically with the normal force. Under negative normal force adhesive state, the tangential force （more than hundred mN） were much larger than the negative normal force （several mN） and increased with the linear decrease of negative normal force. The results reveal why the gecko＇s toe must slide slightly on the target surface when it makes contact on a surface and suggest how a biomimetic gecko foot might be designed.

Current Strategies of Surface Modifications to Polyurethane Biomaterials for Vascular Grafts

As the number of patients suffering from cardiovascular diseases and peripheral vascular diseases rises,the constraints of autologous transplantation remain unavoidable.As a result,artificial vascular grafts must be developed.Adhesion of proteins,platelets and bacteria on implants can result in stenosis,thrombus formation,and postoperative infection,which can be fatal for an implantation.Polyurethane,as a commonly used biomaterial,has been modified in various ways to deal with the adhesions of proteins,platelets,and bacteria and to stimulate endothelium adhesion.In this review,we briefly summarize the mechanisms behind adhesions,overview the current strategies of surface modifications of polyurethane biomaterials used in vascular grafts,and highlight the challenges that need to be addressed in future studies,aiming to gain a more profound understanding of how to develop artificial polyurethane vascular grafts with an enhanced implantation success rate and reduced side effect.

Bioactive citrate-based polyurethane tissue adhesive for fast sealing and promoted wound healing

As a superior alternative to sutures,tissue adhesives have been developed significantly in recent years.However,existing tissue adhesives struggle to form fast and stable adhesion between tissue interfaces,bond weakly in wet environments and lack bioactivity.In this study,a degradable and bioactive citrate-based polyurethane adhesive is constructed to achieve rapid and strong tissue adhesion.The hydrophobic layer was created with polycaprolactone to overcome the bonding failure between tissue and adhesion layer in wet environments,which can effectively improve the wet bonding strength.This citrate-based polyurethane adhesive provides rapid,non-invasive,liquid-tight and seamless closure of skin incisions,overcoming the limitations of sutures and commercial tissue adhesives.In addition,it exhibits biocompatibility,biodegradability and hemostatic properties.The degradation product citrate could promote the process of angiogenesis and accelerate wound healing.This study provides a novel approach to the development of a fast-adhering wet tissue adhesive and provides a valuable contribution to the development of polyurethane-based tissue adhesives.

Adhesion Improvement of Zirconium Coating on Polyurethane Modified by Plasmas

In order to improve the adhesion of the middle frequency magnetic sputtered zirconium coating on a polyurethane film,an anode layer source was used to pretreat the polyurethane film with nitrogen and oxygen ions.SEMs and AFM roughness profiles of treated samples and the contrast groups were obtained.Besides,XPS survey spectrums and high resolution spectrums were also investigated.The adhesion test revealed that ion bombardment could improve the adhesion to the polyurethane coating substrate.A better etching result of oxygen ions versus nitrogen predicts a higher bonding strength of zirconium coating on polyurethane and,indeed,the highest bonding strengths are for oxygen ion bombardment upto 13.3 MPa.As demonstrated in X-ray photoelectron spectroscopy,the oxygen ion also helps to introduce more active groups,and,therefore,it achieves a high value of adhesion strength.

Plant Oil-Based Waterborne Polyurethanes: A Brief Review

The increasing pressure from consumers and policy makers to reduce the use of synthetic polymers,whose production contributes to the depletion of non-renewable resources and are usually non-biodegradable,has prompted the efforts to find suitable bio-based sources for the production of polymers.Vegetable oils have been a frequently spotted in this search because they are versatile,highly available and a low cost liquid biosource,which can be used in the synthesis of a wide plethora of different polymers and reactive monomers.Following the same idea of reducing the environmental stress,the traditional polyurethanes that are soluble in organic solvents have been targeted for replacement,particularly in applications such as adhesives and coatings,in which the solvent is released to the atmosphere increasing the air pollution.Instead,waterborne polyurethanes(WBPU),which are polyurethane dispersions(PUD)prepared in aqueous media,release benign water to the atmosphere during use as supported or self-standing films for different applications.In this brief review,the contributions to the development of WBPUs based on vegetable oils are discussed,focusing mainly on the contributions of the last decade.The synthesis of ionic and nonionic PUDs,their characterization and the properties of the resulting dried materials,as well as derived composite materials are considered.

A Study on Adhesive Properties of Materials Based on Biomimetic Results of Gecko′s Feet

Many animals have a magic ability to move or hold on ceilings and walls because of the design of their adhesive pads. The experiments were carried out to study the effects of material properties (elastic modulus EM and chemical components CC) and contact geometry (surface roughness, connecting stiffness) on their adhesive properties. The adhesion of the lowest EM samples is the highest (15 kPa) and the surface roughness has strong effects on adhesion and the adhesion decreases to 1.5 kPa for the highest EM samples. The adhesive forces are heavily influenced by CC of polyurethane. Surface roughness heavily influences the adhesion and when the roughness is higher than R a 0.3 μm, the obtained adhesion of the samples is the same. The adhesion does not change with the normal forces when a sphere is used to contact with flat PU samples. But when the two matually contact surfaces are flat, the adhesion of a material increases with the normal load at first and then turns to slightly raise. The adhesion of them is the same for the contact angles from 1 to 3 degree when the samples are softly connected. But when they are adhesive hardly to each other the adhesion decreases with increase of the contact angle.

GRAFTING OF SULFOBETAINE ONTO A POLYURETHANE SURFACE TO IMPROVE BLOOD COMPATIBILITY

On the molecular level, it is believed that polymers containing zwitterionic structures should be compatible withblood. In this work polyurethane films were grafted with sulfobetaine by a three-step procedure. In the first step, the films'surfaces were treated with hexamethylene diisocyanate (HDI) in toluene at 50℃ in the presence of di-n-butyl tin dilaurate(DBTDL) as a catalyst. The extent of the reaction was monitored by ATR-IR spectra; a maximum number of free NCOgroups was obtained after a reaction time of 90 min. In the second step, the hydroxyl groups of N,N-dimethylethylethanolamine (DMEA) were allowed to react in toluene with NCO groups bound on the surface. In the thirdstep, sulfobetaines were formed on the surface through the ring-opening reaction between tertiary amine of DMEA and 1,3-propanesultone (PS). The surfaces of the films were characterized by ATR-IR and XPS showing that the grafted surfaceswere composed of sulfobetaine. The results of the contact angle measurement show that the surface was strongly hydrophilic.The platelet adhesion test demonstrated that the films grafted with sulfobetaine have excellent blood compatibility.

SYNTHETIC STUDIES ON BLOOD COMPATIBLE BIOMATERIALS 13:A NOVEL SEGMENTED POLYURETHANE CONTAINING PHOSPHORYLCHOLINE STRUCTURE:SYNTHESIS,CHARACTERIZATION AND BLOOD COMPATIBILITY EVALUATION

A new phosphorylcholine, (6-hydroxy) hexyl-2-(trimethylammonio) ethyl phosphate (HTEP), was synthesized andcharasterized. Segmented polyurethane (SPU) containing phosphorylcholine structure was synthesized based ondiphenylmethane diisocyanate (MDI), soft segment polytetramethylene glycol (PTMG) and HTEP, with 1,4-butanediol (BD)as a chain extender. The existence of phosphorylcholine structure on the surface of SPU was revealed by attenuated totalreflectance Fourier transform infrard spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and water contactangle measurements. The blood compatibilities of the polymers were evaluated by hemolytic testing and a platelet-richplasma (PRP) adhesion experiment, which was viewed by scanning electron microscopy (SEM) with polyurethane as areference. The novel segmented polyurethane containing phosphorylcholine structure showed improved blood compatibility.

Silane Terminated Prepolymers: An Alternative to Silicones and Polyurethanes

Silane terminated prepolymers for adhesives, sealants and coatings are of great industrial importance. They are very important because of their low toxicity over polyurethanes, silicones, and solvent-based products. Hence, many pieces of literature which deal with the synthesis, properties and applications of this Silane terminated polymers hybrid system exist. Silylated polyether (MS polymers) and Silylated Polyurethane Polymers (SPUR) are the bases for numerous sealants, adhesives and coatings used worldwide. A hybrid system mixed with organic-polyurethane proportion and inorganic-alkoxysilane proportion combines the benefits of conventional polyurethane and silicone-based products. This article reviews the chemistry of MS polymers and SPUR and their advantages and disadvantages in silyl terminated prepolymer-based adhesives, sealants and coatings as well as provides information on different end applications.