紫外法和皮粉法测定塔拉单宁含量的对比研究

分别采用紫外法和皮粉法对5种不同含量的塔拉单宁进行对比研究,并利用SPSS软件对单宁含量测定结果进行显著性检验,结果表明：高纯度塔拉单宁（93%）分别用紫外法和皮粉法测定单宁含量时实验结果并未显著差异（P>0.05）,而4种纯度为60%左右塔拉单宁的实验结果均具有显著性差异（P < 0.05）,皮粉法测得的单宁含量均比用紫外法测得的结果高,差值约为1.5%~2.0%,并由此计算出紫外法测定塔拉单宁含量计算公式中的矫正常数p为1.03。紫外-可见吸收光谱与HPLC分析结果表明：塔拉单宁与五倍子单宁的最大吸收峰均为276 nm,同质量浓度下塔拉单宁的吸收峰强度高于五倍子单宁,塔拉单宁成分出峰时间主要在20~40 min,五倍子单宁主要在30~45 min。     

Studies on synthesis,characterization, and metal adsorption of mimosa and valonia tannin resins

A few thermosetting wood adhesive tannin resin system from formaldehyde reaction with both condensed and hydrolysable tannin has been developed. Polymerization of formaldehyde with mimosa tannin and valonia tannin was carried out at optimal conditions obtained from literature to establish the adhesive resin formulation. Formed reaction products were characterized by FTIR spectroscopy. The possible adsorption mechanisms for the adsorption of various metal ions onto tannin‐formaldehyde resins were proposed. Also, thermal analysis were studied and discussed by differential scanning calorimetry and thermogravimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 786–797, 2006     

Simple 13C-NMR methods for quantitative determinations of polyflavonoid tannin characteristics

A simple ¹³C-NMR method for the quantitative determination of polyflavonoid tannin characteristics was developed. The system is effective for use on concentrated (25–50%) solutions of natural and modified tannins. It allows the determination of the average degree of polymerization (DP _n) of the polyflavonoid, resorcinol vs. phloroglucinol proportion of the A-ring and catechol vs. pyrogallol proportion of the B-ring. The results obtained are consistent with existing data determined by other techniques. The method was also tried with tannin extract that was modified to form thermosetting adhesive intermediates, and with tannin modified by sulfonation, a common commercial modification for these materials. The results were again consistent with what was expected. The method affords the possibility to follow by a simple technique the variations in DP _n and MM?_n (number-average molecular weight) induced by chemical modifications of polyflavonoid tannin extracts and thus to correlate them with relevant structural modifications affecting these parameters. The method is not capable of distinguishing the relative proportions of the four important flavonoid units present in commercial polymeric tannin extract. It can only distinguish the relative proportions of (i) (procyanidins + prodelphinidins) vs. (profisetinidins + prorobinetinidins) and (ii) (prorobinetinidins + prodelphinidins) vs. (profisetinidins + procyanidins). © 1995 John Wiley & Sons, Inc.     

Tara tannin as active ingredient in electrospun fibrous delivery system

This study evaluated the releasing performance of tara tannin, a cocktail of plant polyphenols, incorporated in submicron fiber, produced by the electrospinning process. Polylactic acid was used as a polymer matrix that carried two loading levels of tara tannin, 14.3 and 22.3% dry weight in the final product. The fiber diameter of composite fibers was in the range 500–700 nm. The release of tara tannin was controlled by material attachment as there was no evidence of chemical bonding between materials. This was further confirmed by FTIR and DSC. From the five combinations of acid that were presented in tara tannin, galloylquinic acid, with the smallest molecular weight composition, was released in the largest proportion (%molar) and exhibited antioxidant activity. This was confirmed by 2,2‐diphenyl‐1‐picrylhydrazyl assay and HPLC‐MS analyses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43646.     

Oligomers distribution at the gel point of tannin–formaldehyde thermosetting adhesives for wood panels

Tannin–formaldehyde (TF) thermosetting wood adhesives for panel products for the building industry were examined to determine which oligomers were formed during the reaction between tannin and formaldehyde. The reaction products were examined by Matrix Assisted Laser Desorption/Ionization Time of Flight mass spectrometry. The analysis revealed that at the gel point, the adhesive was composed of unreacted flavonoid monomers and some oligomers, and due to reaction with formaldehyde, of methylolated tannin monomers and oligomers as well as flavonoids linked by methylene bridges. The slow gelling conditions used to prepare the TF hydrogel caused the unusual occurrence that not only the flavonoid units A-rings but also pyrogallol-type B-rings of the flavonoid units started to react with formaldehyde at the low pHs between 6 and 7 used for tannin adhesives and contributed to the network formed. This reaction was observed for the first time in this study.     

塔拉单宁水解废液回收奎尼酸的工艺试验

从塔拉单宁水解制备没食子酸的废液着手 ,用真空蒸发法分离去除盐酸 ,用不同的溶剂萃取法分离去除没食子酸 ,用活性炭吸附法和强碱阴离子交换法分离去除色素和糖类物质。从而提出了从塔拉单宁水解废液中回收目标产品奎尼酸的方法 ,产品得率约为理论值的 78%     

Industrial scale evaluation of cationic tannin as a binder for hardboard

Hardboards (HBs) (wet-process high-density fibreboards) were made in an industrial trial using a binder system consisting of cationic mimosa tannin and laccase or just cationic tannin without any thermosetting adhesive. The boards displayed superior mechanical strength compared to reference boards made with phenol–formaldehyde, easily exceeding the European standards for general-purpose HBs. The thickness swell of most of the boards was slightly greater than the standards would allow, so some optimisation is required in this area. The improved board properties appear to be mainly associated with ionic interactions involving quaternary amino groups in cationic tannin and negatively charged wood fibres rather than to cross-linking of fibres via laccase-assisted formation and coupling of radicals in tannin and fibre lignin.     

Combination of lignin polyol–tannin adhesives and polyethylenimine for the preparation of green water‐resistant adhesives

In this study, a green adhesive from renewable lignin and tannin was developed with polyethylenimine (PEI) with a method to improve the water resistance of the lignin/tannin adhesive. Lignin polyols were prepared through the liquefaction of oil‐palm empty fruit bunches. The characteristics of the adhesive samples were compared with those of a commercial phenol–formaldehyde resin. Three plywood specimens bonded with the new adhesive showed a very high tensile strength (63.04 MPa) and were very water resistant. The effect of the solid content of the adhesives on the tensile strength and gel time and various weight ratios of PEI on the tensile strength and water resistance of the plywood specimens were evaluated. Thermal stability tests revealed that the lignin polyol–tannin/PEI adhesives had a high heat resistance (360 °C). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43437.     

Thermosetting Adhesive Based on Tannin and Poly(N-Hydroxymethyl Acrylamide)

A thermosetting adhesive consisting of tannin and poly(N-hydroxymethylacrylamide) was studied. This adhesive is an environmentally friendly one using only water as the solvent and is partly based on a natural product. It showed good bonding strength and water resistance for a wood product although those properties were lower than the level of phenol-formaldehyde resin.     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.     

Matrix‐assisted laser desorption/ionization time‐of‐flight structure determination of complex thermoset networks: Polyflavonoid tannin–furanic rigid foams

Polyflavonoid tannin–formaldehyde–furfuryl alcohol rigid foams yield hardened, rigid, tridimensional networks in which there are covalently linked structures derived from the reaction of their main components. Thus, polyflavonoid tannin structures, tannin–formaldehyde structures, furanic structures derived by the self‐condensation of furfuryl alcohol, and mixed tannin–furane and tannin–furane–formaldehyde structures are all present in the continuous foam networks. Some complex, tridimensional structures involving tannin's flavonoid units, furan nuclei, and formaldehyde‐derived methylene bridges appear to be formed too. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry has been used to determine the different segments contributing to forming the complex thermosetting networks of the hardened foams. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Differential scanning calorimetry of hydrolysed mangrove tannin

Mangrove‐bark‐tannin adhesives are potential substitutes for phenol–formaldehyde (PF) wood‐bonding adhesives which are derived from petroleum, a finite natural resource. However, mangrove‐bark‐tannin adhesive exhibits poor adhesive properties, including brittleness, poor wet strength, and poor wood penetration. These shortcomings are due to its high reactivity and structural features. To reduce these shortcomings, the structure of the adhesive was modified by subjecting tannin to (a) caustic hydrolysis and (b) consecutive acetic anhydride and caustic hydrolysis. The effectiveness of these hydrolyses was determined by using differential scanning calorimetry (DSC) to monitor the reaction and cure characteristics of hydrolysed and unhydrolysed tannin with formaldehyde. These hydrolyses resulted in lowering both the activation energy and collision frequency of the cure reaction. Consequently, the initial reactivity of tannin towards paraformaldehyde, which was usually very high, was reduced. The resulting longer reaction time enhanced the extent of reaction, as was evident in the increase in heat of reaction of the hydrolysed tannin. © 2000 Society of Chemical Industry     

Mechanical characterization of industrial particleboard panels glued with cornstarch–mimosa tannin–urea formaldehyde resins

The aim of this work was to validate the utility and performance of optimal laboratory cornstarch–mimosa tannin-based resins in the industrial particleboard production. In this way, the cornstarch and mimosa tannin was introduced in the classic adhesive formulation in order to supply a part of urea-formaldehyde (UF). Our results show that industrial particleboard panels (8.2?m?×?1.85?m?×?19?mm) bonded with optimal cornstarch–mimosa tannin–UF (10:4:86; mass ratio) resins exhibited comparable mechanical properties to those of boards bonded with commercial UF resins and largely satisfied the exigencies of European norms EN 312. The formaldehyde emission levels obtained from panels bonded with cornstarch–mimosa tannin–UF were lower to those obtained from panels bonded with control UF. Finally, the addition of cornstarch and mimosa tannin improves markedly the water resistance of UF resins.     

The chemistry and development of tannin/urea–formaldehyde condensates for exterior wood adhesives

Novolak-like materials were prepared by condensation of urea–formaldehyde resins with resorcinol and/or resorcinolic A-rings of polyflavonoids such as condensed tannins. The copolymers formed were used as thermosetting and cold-setting exterior-grade wood adhesives. Condensation of tannins with small amounts of urea–formaldehyde resins can prevent the water deterioration normally experienced by the latter resins. Conversely, urea–formaldehyde resins improve crosslinking and strength of wood tannin–formaldehyde networks.     

CHT and TTT curing diagrams of polyflavonoid tannin resins

TTT and CHT curing diagrams for tannin-based adhesives were built by thermomechanical analysis (TMA) by following the in situ hardening directly in a wood joint, and the curve trends observed were similar to those previously observed for synthetic polycondensation resins on lignocellulosic substrates. Of the parameters that most influence the relative position of vitrification and gel curves on the diagrams (i.e., where the influence has been quantified), chief among them is the reactivity of the tannin with formaldehyde and any factor influencing it: thus, the inherent higher reactivity of the A-ring of the tannin (such as in procyanidins versus prorobinetinidins) and the pH of the tannin solution. The percentage formaldehyde hardener has some influence in CHT diagrams, especially for the slower-reacting tannins, but practically no influence in TTT diagrams within the 4–10% formaldehyde range used. As in the case of synthetic polycondensation adhesive resins, regression equations relating the internal bond strength of a wood particleboard, prepared under controlled conditions, with the inverse of the minimum deflection, obtained by constant heating rate TMA of a wood joint during resin cure, have been obtained for the two types of tannins of lower reactivity (profisetinidins/prorobinetinidins) but not for the faster-reacting procyanidin and prodelphinidin tannins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3220–3230, 2001     

Low Formaldehyde Emitting Biobased Wood Adhesives Manufactured from Mixtures of Tannin and Glyoxylated Lignin

Abstract

Kraft (LN-T-CO₂-2) and wheat straw (CIMV) glyoxalated lignin mixed with mimosa tannin and hexamine as a hardener were used as wood adhesive resins in particleboard fabrication. The adhesive systems proportion used were 40/60 and 50/50 w/w for lignin and tannin, respectively. The gel time test was determined by knowing the polymerization time between the different mixes under the controlled conditions. The results showed a slower polymerization with the kraft lignin/mimosa tannin blending than with the wheat straw lignin/mimosa tannin one. Thermomechanical analyses (TMA) tests were carried out as an indication of the final strength of the adhesive systems revealed by the elasticity modulus (MOE). The MOE results have demonstrated the best mechanical resistance values in 40/60 lignin/mimosa tannin proportion with respectively 3.422 and 3.347 (MPa), for CIMV and LN-T-CO₂-2, and 2.122 (MPa) for 50/50 proportion. Particleboards were prepared and the internal bond (IB) tests were carried out according to the European Standard EN 312. The IB tests confirmed the TMA results. The higher mechanical results of the IB were .43 and 0.53 (MPa), for CIMV and LN-T-CO₂-2 lignin in a 40/60 lignin/mimosa tannin proportion. They were classified as interior panel P2 in according with the standard request EN-312. Free-formaldehyde was determined through the flask method EN 717-3. Particleboards prepared with these natural adhesive resins registered emissions at least 87 and 75% lower than the commercial UF and MUF dhesive resins. The panels were classified as E0.     

Effects of natural-resource-based scavengers on the adhesion properties and formaldehyde emission of engineered flooring

In this study we investigated the effects of using four additives, wheat flour (WF), tannin, rice husk (RH) and charcoal, to melamine-formaldehyde (MF) resin for decorative veneer and base plywood in engineered flooring in order to reduce the formaldehyde emission levels and improve the adhesion properties. We determined the effects of variations in hot-press time, temperature and pressure on the bonding strength and formaldehyde emission. Blends of various MF resin/additive compositions were prepared. To determine and compare the effects of the additives, seven MF resin blends were prepared with the four different additives: four with a wt ratio of 8:2 (MF/WF, MF/tannin, MF/RH and MF/charcoal), and three in the wt ratio of 8:1:1 (MF/WF/tannin, MF/WF/RH and MF/WF/charcoal). The desiccator and perforator methods were used to determine the level of formaldehyde emission. The formaldehyde emission level decreased with all additives, except for RH. At a charcoal addition of only 20%, the formaldehyde emission level was reduced to nearly 0.1 mg/l. Curing of the high WF and tannin content in this adhesive system was well processed, as indicated by the increased lap-shear strength. In the case of WF, the lap shear strength was much lower due to the already high temperature of 130°C. The adhesive layer was broken when exposed to high temperature for extended time. In addition, both WF and tannin showed good mechanical properties. With increasing WF or tannin content, the initial adhesion strength increased. The MF resin samples with 20% added tannin or WF showed both good lap shear and initial adhesion strengths compared to the pure MF resin.     

Rheology of polyflavonoid tannin–formaldehyde reactions before and after gelling. II. Hardener influence and comparison of different tannins

Good correspondence of the gel‐time values obtained by two different methods, G′ = G″ and 1/η₀→0, was observed for different types of natural and modified tannin extracts. The pH presents the predominant effect on both the activation energies and the gel times observed, while the proportion of a paraformaldehyde hardener has a much lesser effect on these parameters. The rate constants of the different phases of the reaction of polycondensation with formaldehyde, both before and after the gel point, were obtained for the six commercial tannin extracts tested. The viscoelastic properties of the different tannins/formaldehyde gels were measured. The gel stiffness S, relaxation coefficient n, and relaxation time λ were determined and their dependence on the proportion of the formaldehyde hardener, on the temperature, and on the type of tannin was determined. The gel stiffness S appears to be influenced considerably by the proportion of the formaldehyde hardener. Its value decreased as the percentage of the hardener increased: This was due to early network immobilization and the resulting lower level of crosslinking resulting from it. The influence on S of the temperature is not very pronounced. The relaxation coefficient n appears to depend mainly on the reactivity of the tannin used: The faster the reactivity, the higher was the value of n. This appears to be valid exclusively in tannin extracts where the colloidal state is still present, while it is not valid in extracts where the colloidal state was eliminated by, for example, solvent extraction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 864–871, 2002     

Renewable polyol‐based polycarbamates and polycarbamate–formaldehyde thermosetting resins

Several polycarbamates and polycarbamate–formaldehyde (CF) resins were synthesized, and their properties were investigated aiming at developing of useful thermosetting polymer materials from simple polyols including those derived from renewable resources. Polycarbamates synthesized from polyols using two‐step laboratory routes showed good storage stabilities making them suitable as large volume industrial chemicals. Furthermore, syntheses and ¹³C‐NMR studies of CF resins showed the formation of oligomeric resins having hydroxymethyl and methylene groups with thermosetting curing properties that are similar to those of current urea–formaldehyde (UF) resins. Dynamic mechanical analysis studies showed somewhat slower curing rates for CF resins compared to UF resins. Bonding of particleboard and internal bond and free formaldehyde content measurements indicated high‐bond strength values and very low‐formaldehyde emission potentials for CF resins. The higher functionalities of CF resins appear to be the basis of good performances. Further investigations on scalable synthesis methods for polycarbamates and on the expansion of CF resins' bonding capabilities would need to be investigated in the future. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Eco-Friendly Adhesives Based on Tannin and N,N-Bis(2-Hydroxy-Ethyl) Fatty Amides (HEFAs) from Non-Traditional Oils for Wood Bonding

Abstract

Wood adhesives were formulated using tannin and N,N-bis(2-hydroxyethyl) fatty amides (HEFAs). The natural tannin-based adhesives can be used to replace formaldehyde-based adhesive systems and thereby reduce formaldehyde and volatile organic compound (VOC) emissions from adhesives used for plywoods. Performance properties of the adhesively bonded wood joints viz., tensile strength, impact strength and chemical resistance were measured. N,N-bis(2-hydroxyethyl) fatty amides (HEFAs) from non-traditional oils were mixed with a pure tannin-based adhesive as a crosslinker, and this increased the tensile strength, impact strength and chemical resistance of wood joints. The results revealed that a high performance and eco-friendly adhesive system for wood can be successfully formulated using tannin and HEFA.