WO2004058843A1 - Composition resineuse a base de compose amino, aldehyde et tannique et son utilisation en tant qu'agent de collage de produits en bois composite - Google Patents

Composition resineuse a base de compose amino, aldehyde et tannique et son utilisation en tant qu'agent de collage de produits en bois composite Download PDF

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Publication number
WO2004058843A1
WO2004058843A1 PCT/AU2003/001712 AU0301712W WO2004058843A1 WO 2004058843 A1 WO2004058843 A1 WO 2004058843A1 AU 0301712 W AU0301712 W AU 0301712W WO 2004058843 A1 WO2004058843 A1 WO 2004058843A1
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WIPO (PCT)
Prior art keywords
resin composition
aldehyde
tannin
preparing
amino compound
Prior art date
Application number
PCT/AU2003/001712
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English (en)
Inventor
Leslie Gordon Wingham
Original Assignee
Borden Chemical Australia Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borden Chemical Australia Pty Ltd filed Critical Borden Chemical Australia Pty Ltd
Priority to AU2003291848A priority Critical patent/AU2003291848A1/en
Publication of WO2004058843A1 publication Critical patent/WO2004058843A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines

Definitions

  • This invention relates to resin compositions, methods of making them, and products made by using them. It has particular, although not exclusive application to resin compositions for use as binding agents to bind solid particles together so as to form useful products therefrom.
  • the invention has particular application to the manufacture of wood composite products, such as particle boards and medium density fibreboard (MDF), for use in the construction industry. The background to the invention will therefore be described with specific reference to this application to which it is particularly suited.
  • MDF medium density fibreboard
  • 'particle board' is made up from wood particulates (typically derived from saw milling and similar techniques for processing natural timbers), combined with a binding agent.
  • Useful binding agents for this purpose are natural and synthetic resins. Synthetic resins have particular advantages in this area, because they can be made to impart desirable properties to the resultant wood composite product (eg: improved water resistance over those possessed by natural timbers). Resins that are made containing condensed tannins are particularly attractive for use in the manufacture of particle board, because tannins are known in particular, for their ability to impart a degree of water resistance to resins formed from them.
  • condensed tannins as binding agents in the manufacture of wood composite materials requires the addition of a cross-linking agent just before their application to the substrate to be bound.
  • this cross-linking agent is paraformaldehyde powder, or a Urea formaldehyde concentrate.
  • a chemical reaction between the two elements commences, which results in the stability (and thus the shelf life) of the resultant resin being compromised.
  • stability is usually measured as the time taken for the resin system to become unstable, either physically and/or chemically.
  • Tannins are poly flavonoids of the general formula X depicted below:
  • the most common reactions of the A ring are examples of the electrophilic aromatic substitution, including where an electrophile displaces the hydrogen atom at C6 and/or C8.
  • the favoured site is C6.
  • Basic conditions increase the reactivity of the system.
  • the phenolic hydroxyl is a powerful electron donor, especially under basic conditions, increasing the electron density in the A Ring, thus making it a better nucleophile, as well as stabilising carbocation intermediates that result from nucleophilic attack.
  • Condensed tannins contain repeating units of the formula X depicted above, linked to one another by an inter- flavonoid bond.
  • the A Ring of the constituent flavonoid units retains only one highly reactive nucleophilic centre, the remainder of each unit accommodating the inter- flavonoid bond.
  • the flavonoid unit is repeated between 2 and 11 times, with an average degree of polymerisation of 4 to 5.
  • An exemplary tannin polymer of the kind described is represented in the formula Y depicted below.
  • Formaldehyde reacts with tannins to produce polymerisation through methylene bridge linkages at reactive sites on the flavonoid molecules, primarily on the A rings.
  • the reactivity for mimosa tannin is comparable to resorcinol.
  • formaldehyde to a tannin solution results in rapid polymerisation. Due to their size and shape, tannin molecules become immobile at low levels of concentration with formaldehyde, so that reactive sites are too far apart for further methylene bridge formation. The resulting cured resin is thus extremely water- and boil-resistant.
  • MUF resins are extensively used to impart water resistance to particle board and fibreboard.
  • melamine a petrochemical based material
  • Tannin is a natural product, more cost stable, cheaper than Melamine and can potentially be sourced locally.
  • tannins are therefore a suitable candidate for this purpose.
  • tannin and formaldehyde react readily with one another. This high reactivity makes it very difficult to maintain stability in the final resin solution. Free formaldehyde in the resin solution continues to react with the tannin, thereby increasing its viscosity and at the same time, shortening its shelf life.
  • reducing the level of available formaldehyde in the resin does alleviate this problem, but this reduces the reactivity of the components, and thus, the ability of the resin to cure during the formation of wood composite or like products, during manufacture.
  • the present invention aims to address one or more of the prior art problems mentioned above.
  • the invention generally provides a resin composition, the composition comprising a co-polymer of:
  • Tannins suitable for use in the invention may be obtained from wood and bark materials found throughout the world.
  • Preferred tannins for use in the invention are those known as condensed tannins. These tannins are obtained from the bark of the black wattle (mimosa) and other Acacia species, various species of pine, and from the wood of the quebracho tree.
  • a particularly preferred amino compound for use in the invention is urea.
  • Urea can be used in the form of a powder, prill, in granular form or as an aqueous solution.
  • Amino compounds suitable for this purpose also include the use of urea- formaldehyde monomeric products, such as monomethylol urea and dimethylol urea.
  • the stabiliser compound chosen must be such as to impart stability to the tannin-amino compound-aldehyde co-polymer. In this context, stability means that the co-polymer has a shelf life of:
  • the stabiliser compound may also be an amino-based heterocyclic compound.
  • Suitable compounds in this category include melamine (2 ( 4,6-triamino-1 ,3,5 triazine), melamine-formaldehyde monomeric products and melamine formaldehyde concentrate solutions.
  • Other suitable triazine materials include benzoguanamine, melam, melon, ammeline and other melamine derivatives.
  • Aldehydes suitable for use in the invention include formaldehyde, acetaldehyde and propionaldehyde.
  • Aldehydes also includes aldehyde generating agents, such as hexamine.
  • the aldehyde used in the invention is formaldehyde. This can be used in the invention in many forms, including:
  • the composition according to the invention is a tannin-urea-formaldehyde co-polymer.
  • the invention also provides a method of preparing a resin composition in which the resin composition comprises a tannin-amino compound-aldehyde copolymer, the method comprising the following steps:
  • step (a) is performed before step (b).
  • step (a) the aldehyde is reacted with the stabiliser compound under alkaline conditions.
  • a preferred pH range for this reaction is between 7.5 and 9.5.
  • the molar ratio of aldehyde to stabiliser compound is from 5:1 to 140:1.
  • a particularly preferred molar ratio is about 40:1.
  • the temperature of the reactants is from 50°C to 90°C.
  • the resulting solution derived from the aldehyde-stabiliser compound reaction is then reacted further with an amino compound under falling pH conditions.
  • this further reaction step is performed at pH values from 9.5 to 6.5.
  • the reaction is also carried out at temperatures between 80°C and atmospheric reflux.
  • an aqueous tannin solution containing between 30% and 60% tannin solids (by weight) is then added to the pre-existing reagents according to the preceding steps of the method.
  • the pH in the system is between 5.0 and 7.5. It is further preferred that the temperature of the reaction system is between 40°C and 75°C.
  • step (b) after the tannin solution is added to the reaction system, a further quantity of the amino compound is added to give a molar ratio of aldehyde to amino compound of from 1.45 to 1.9.
  • reaction system is then allowed to react until the desired condensation viscosity is achieved.
  • condensation viscosity is between 60 and 200 cps.
  • reaction is terminated by:
  • the sulphite comprises sodium sulphite. This can be used either in powder form, or as an aqueous solution.
  • the molar ratio of aldehyde to amino compound in the reaction system is adjusted with a quantity of amino-aldehyde concentrate. It is further preferred that the pH is finally adjusted to between 6.5 and 8.0.
  • the invention further comprises a resin composition produced in accordance with the method aspect of the invention.
  • the invention yet further provides a method of using a resin composition containing a tannin-amino-aldehyde co-polymer as a binding agent in the production of a material which comprises solids mixed with the resin.
  • the resin composition is a tannin-urea-formaldehyde of the kind previously described.
  • the products produced by the use of the resin composition are products which contain particulates made from wood (such as wood shavings, wood fibre or other wood particulates) in combination with the resin composition.
  • Particularly preferred wood composite products formed in accordance with the method aspect of the invention include:
  • the final temperature is maintained at 60°C and pH between 5.9 and 6.4.
  • the reacting mixture is then condensed to 140cps measured at 25°C or Gardner tube value F.
  • the reacting mixture Upon reaching this viscosity, the reacting mixture is cooled to below 30°C while charging 1g of (20%) sodium sulphite solution and 11.25 g of urea.
  • the pH of the product is then adjusted to between 7 and 7.5 with sodium hydroxide solution to achieve a final viscosity of between 70 and 90 cps and a solid content of 59.8%.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition résineuse comprenant un copolymère de: (a) un tannin; (b) un composé amino (tel que de l'urée, de l'urée monométhylole ou de l'urée diméthylole); (c) un aldéhyde (tel qu'un formaldéhyde, un paraformaldéhyde ou un acétaldéhyde); (d) un stabilisant (tel qu'un composé hétérocyclique à base d'amino, notamment la mélamine, des composés d'addition formaldéhyde-mélamine-monomère, du benzoguanamine, du mélame, du mélon, de l'amméline et d'autres dérivés de mélamine) en vue de fournir une stabilité au copolymère aldéhyde à composé amino-tannique, la stabilité étant manifeste comme durée de stockage d'au moins 21 jours à 12 °C ou au moins 8 jours à 25 °C.
PCT/AU2003/001712 2002-12-24 2003-12-22 Composition resineuse a base de compose amino, aldehyde et tannique et son utilisation en tant qu'agent de collage de produits en bois composite WO2004058843A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003291848A AU2003291848A1 (en) 2002-12-24 2003-12-22 A tannin, aldehyde, amino compound- based resin composition and its use as a binding agent for composite wood products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2002953568 2002-12-24
AU2002953568A AU2002953568A0 (en) 2002-12-24 2002-12-24 Novel chemical composition, method of making same, and products made therefrom

Publications (1)

Publication Number Publication Date
WO2004058843A1 true WO2004058843A1 (fr) 2004-07-15

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AR (1) AR043321A1 (fr)
AU (1) AU2002953568A0 (fr)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013163245A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites faits avec des compositions de liant comprenant des tanins et des composés aldéhydiques multifonctionnels
WO2013163242A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites constitués de compositions liantes catalysées à l'acide de lewis comprenant des acides tanniques et des aldéhydes multifonctions
WO2014037681A2 (fr) 2012-09-10 2014-03-13 Huttenes Albertus France Procédé d'obtention d'un corps pour fonderie à partir d'un mélange granulaire comprenant une résine polycondensée modifée et un capteur de formaldéhyde
WO2017023218A1 (fr) * 2015-04-21 2017-02-09 Kastamonu Entegre Agac Sanayi Anonim Sirketi Procédé de production de résines contenant un polyflavonoïde et des dérivés et leur application dans des produits de panneaux composites à base de bois
CN107987763A (zh) * 2017-11-30 2018-05-04 中南林业科技大学 一种低甲醛释放脲醛树脂胶黏剂及其制备方法
US20210237041A1 (en) * 2008-06-18 2021-08-05 Board Of Trustees Of The University Of Arkansas Doped-carbon composites, synthesizing methods and applications of the same

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JPS50146629A (fr) * 1974-05-17 1975-11-25
JPS54148697A (en) * 1978-05-13 1979-11-21 Hohnen Oil Method of manufacturing reinforced corrugated cardboard
JPS58179281A (ja) * 1982-04-14 1983-10-20 Sumitomo Bakelite Co Ltd 木材用粉末樹脂接着剤の製造方法
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US20030079833A1 (en) * 2001-10-18 2003-05-01 Akzo Nobel N.V.. Method of gluing wood based materials

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210237041A1 (en) * 2008-06-18 2021-08-05 Board Of Trustees Of The University Of Arkansas Doped-carbon composites, synthesizing methods and applications of the same
WO2013163245A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites faits avec des compositions de liant comprenant des tanins et des composés aldéhydiques multifonctionnels
WO2013163242A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites constitués de compositions liantes catalysées à l'acide de lewis comprenant des acides tanniques et des aldéhydes multifonctions
US20130287993A1 (en) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Composite products made with binder compositions that include tannins and multifunctional aldehydes
US8674019B2 (en) 2012-04-27 2014-03-18 Georgia-Pacific Chemicals Llc Composite products made with lewis acid catalyzed binder compositions that include tannins and multifunctional aldehydes
CN104334326A (zh) * 2012-04-27 2015-02-04 佐治亚-太平洋化工品有限公司 采用含单宁和多官能醛的路易斯酸催化的粘合剂组合物制造的复合产品
CN104349878A (zh) * 2012-04-27 2015-02-11 佐治亚-太平洋化工品有限公司 采用含单宁和多官能醛的粘合剂组合物制造的复合产品
WO2014037681A2 (fr) 2012-09-10 2014-03-13 Huttenes Albertus France Procédé d'obtention d'un corps pour fonderie à partir d'un mélange granulaire comprenant une résine polycondensée modifée et un capteur de formaldéhyde
CN104619437A (zh) * 2012-09-10 2015-05-13 胡坦斯·阿尔伯图斯法国公司 用于由包含改性缩聚树脂和甲醛清除剂的粒状混合物获得铸型体的方法
US10137494B2 (en) 2012-09-10 2018-11-27 Huttenes Albertus France Method for obtaining a foundry body from a granular mixture comprising a modified polycondensed resin and a formaldehyde scavenger
WO2017023218A1 (fr) * 2015-04-21 2017-02-09 Kastamonu Entegre Agac Sanayi Anonim Sirketi Procédé de production de résines contenant un polyflavonoïde et des dérivés et leur application dans des produits de panneaux composites à base de bois
CN107987763A (zh) * 2017-11-30 2018-05-04 中南林业科技大学 一种低甲醛释放脲醛树脂胶黏剂及其制备方法

Also Published As

Publication number Publication date
AU2002953568A0 (en) 2003-01-16
AR043321A1 (es) 2005-07-27

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