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WO1997009360A1 - Melanges de liants aqueux a faible teneur en formaldehyde libre s'utilisant dans la production de materiaux derives du bois - Google Patents

Melanges de liants aqueux a faible teneur en formaldehyde libre s'utilisant dans la production de materiaux derives du bois Download PDF

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Publication number
WO1997009360A1
WO1997009360A1 PCT/EP1996/003796 EP9603796W WO9709360A1 WO 1997009360 A1 WO1997009360 A1 WO 1997009360A1 EP 9603796 W EP9603796 W EP 9603796W WO 9709360 A1 WO9709360 A1 WO 9709360A1
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WO
WIPO (PCT)
Prior art keywords
formaldehyde
urea
melamine
mol
component
Prior art date
Application number
PCT/EP1996/003796
Other languages
German (de)
English (en)
Inventor
Anton Meier
Christel Hittinger
Hermann Schatz
Gunter Lehmann
Tilmann Reiner
Manfred Niessner
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1997009360A1 publication Critical patent/WO1997009360A1/fr

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Classifications

    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C08G12/36—Ureas; Thioureas
    • C08G12/38—Ureas; Thioureas and melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present invention relates to aqueous binder mixtures which are suitable for the production of wood-based materials containing
  • the molar ratio of the amount of melamine used (component a1) to the total amount of urea (components (a2) and (B)) is 1: 3.5 to 1:13 and the molar ratio of formaldehyde (component a3) to those in the Components (a1), (a2) and (B) present -NH 2 groups is 0.2: 1 to 0.7: 1.
  • the invention relates to processes for their production, their use as binders for the production of wood-based materials, and wood-based materials which can be obtained using these binder mixtures.
  • Binders based on aqueous aminoplast resins made from urea and formaldehyde, which are suitable for gluing shredded wood, for example wood chips and wood fibers, to the corresponding wood materials, for example wood chipboard or wood fiber boards, are generally known ( see Ulimanns Encyklopadie der Technische Chemie, 4th edition, volume 7, pp. 413 to 422).
  • the binders are applied to the shredded wood in the manufacture of the wood-based materials, after which they are pressed together at elevated temperatures, the binder hardening.
  • the aminoplast resins should have good processing properties and should enable the economical production of wood-based materials with good usage properties.
  • Important processing properties are high reactivity and low viscosity with a high solids content at the same time, so that short working cycles, in particular short pressing times, are sufficient to process wood chips which have been wetted with the glue resins into high-quality chipboard.
  • Wood-based materials with good mechanical properties and, in particular, good water resistance can be obtained from those amino resins which, in addition to formaldehyde and urea, have also been produced using melamine or phenol, the melamine-containing aminoplast resins (MUF resins) compared to the phenol-containing resins have the advantage that the wood materials made from them do not darken (cf. loc. eit. p. 417)
  • MUF resins Mixtures of aqueous MUF resins and urea are known from DE-A 34 42 454.
  • the MUF resins are produced by condensing a mixture of formaldehyde, urea and melamine, into which the formaldehyde has been introduced partly or completely in the form of a concentrated aqueous solution with urea, under weakly basic conditions. It is recommended that up to about 50% of the urea, based on the total amount of urea, be added to these resins after the condensation. There is no information on the molar ratio of formaldehyde to amino groups in the urea and melamine used and on the molar ratio of melamine to urea.
  • Example 3 of this document describes a size resin which is prepared by adding 65% urea to an aqueous MUF resin, based on the total amount of urea contained in the finished size resin.
  • the molar ratio of urea to melamine is 3.08: 1 and the ratio of formaldehyde to amino groups is 0.67.
  • the glue resins obtained according to this teaching have a satisfactory level of application technology, as far as their processing properties and the use properties of the derived timber products are concerned. Your free form content However, aldehyde is still too high and does not meet today's requirements.
  • the glue resins should have the lowest possible free formaldehyde content, because such glue resins release formaldehyde only to a small extent when they are processed into wood-based materials and the formaldehyde emission of the wood-based materials produced with these glue resins is also reduced.
  • the melamine (component a1) and the urea (component a2) are suitably used in solid form.
  • the formaldehyde (component a3) is usually used in the form of a 30 to 50% strength by weight aqueous solution or in the form of paraformaldehyde.
  • Component (a4) are compounds which react with formaldehyde in a condensation or addition reaction which are different from phenol or a polycondensation-capable phenol derivative.
  • Phenol derivatives capable of polycondensation are generally aromatic alcohols which can react with formaldehyde in a condition or addition reaction, for example those described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A19, pp. 371 to 384 for the production of phenolic resins.
  • sulfites, disulfites and hydrogen sulfites can be used, which preferably contain alkali metals and the ammonium ion as cations.
  • urea derivatives e.g. Ethylene urea, ethylene diurea and dipropylene tris urea
  • guanamines e.g. Benzoguanamine
  • amides e.g. Epsilon-caprolactam
  • alcohols e.g. Ethylene glycol into consideration.
  • the starting materials (a1), (a2) and (a4) can also be used as a mixture with formaldehyde (component a3) or as formaldehyde adducts or formaldehyde condensates.
  • solutions are preferably adjusted so that they have a total formaldehyde content of 30 to 60% by weight, preferably 40 to 55% by weight and a total urea content of 15 to 40, preferably 20 to 30% by weight.
  • They generally contain, in addition to free formaldehyde and mono- and polymethylolurea compounds which contain only one unit derived from urea, preferably less than 10% by weight of urea-formaldehyde condensation products or addition products which contain more than one derived from urea Unit included.
  • component (A) is generally carried out in such a way that components (al) to (a4) in an aqueous solution, at 60 to 100, preferably from 75 to 95 ° C. and a pH of 7, 5 to 10, preferably 8.2 to 9.0 is allowed to react until the solution has a viscosity of 150 to 2000, preferably 150 to 1000 mPa s, after which the solution is allowed to cool until it becomes a Temperature of 10 to 80, preferably from 40 to 75 ° C.
  • the concentration of the starting materials (al to (a4) in the aqueous solution is generally 30 to 80, preferably 55 to 75, very particularly preferably from 60 to 70% by weight.
  • reaction product of components (a1) to (a4) is mixed with urea.
  • the urea (component B) is preferably added in pure solid form or in the form of a 40 to 80, preferably 60 to 70% by weight aqueous solution.
  • the manner of mixing is not critical and is conveniently carried out by stirring the urea (component B) into the reaction product.
  • the amount of component (B) is preferably 0.55 to 0.75 per mole of the total amount of urea used as components (a2) and (B).
  • the molar ratio of the amount of melamine used (component a1) to the total amount of urea used (components (a2) and (B)) is 1: 3.5 to 1:13 and preferably 1: 3.5 to 1: 6.
  • the molar ratio of the amount of formaldehyde used (component a3) to the —NH 2 groups present in components (a1), (a2) and (B) is 0.2: 1 to 0.7: 1 and preferably 0.4: 1 to 0.7: 1.
  • Reaction products of formaldehyde (component a3) with components (al), (a2) and (a4) are used as starting materials (for example methylolurea).
  • the amount of -NH groups also relates to the amount of -NH 2 groups that were originally present in components (a2) and (a4) before they were reacted with formaldehyde.
  • the binder mixtures obtainable by the process according to the invention are preferably adjusted to a pH of 7 to 10, preferably 8.5 to 9.5 and can be stored for more than 6 weeks at a storage temperature of approximately 20 ° C. without their physical and application properties noticeably changing.
  • the generally customary bases such as alkali or alkaline earth metal hydroxides, preferably in the form of their aqueous solutions, tertiary amines, for example tri- (C (- to C 6 -alkyl) amines such as tributylamine and triethylamine and tertiary Ci bis C ⁇ -alkanolamines, for example triethanolamine, methyldiethanolamine can be used.
  • tertiary amines for example tri- (C (- to C 6 -alkyl) amines
  • tributylamine and triethylamine and tertiary Ci bis C ⁇ -alkanolamines for example triethanolamine, methyldiethanolamine
  • the binder mixtures generally have a solids content (in accordance with DIN 12 605) of 50 to 75, preferably 60 to 70% by weight and a viscosity of 10 to 2000, preferably 10 to 1000, mPas.
  • polyhydric alcohols, sugars and water-soluble polymers built up from monomers such as acrylamide, ethylene oxide, N-vinylpyrrolidone, vinyl acetate or copolymerizable mixtures of these monomers can be added to the binder mixtures become.
  • monomers such as acrylamide, ethylene oxide, N-vinylpyrrolidone, vinyl acetate or copolymerizable mixtures of these monomers
  • they generally do not contain effective amounts of phenol or condensable phenol derivatives.
  • the binder mixtures are particularly suitable as binders for the production of composite materials made from comminuted plastic or textile fibers and, in particular, wood-based materials such as plywood, wooden beams made of plywood or plywood and, above all, wood fiber boards and chipboard (see Ullmanns Encyklopadie der Technischen Chemie, 4 Edition, 1976, Volume 12, pp. 709 to 727) made of shredded wood.
  • the wood-based materials are manufactured using the methods generally known in this field.
  • the gluing is advantageously carried out by pressing the comminuted wood provided with the binder mixtures at temperatures of 120 to 250 ° C.
  • the aminoplast resin hardens quickly and wood materials with good mechanical properties are obtained that are largely insensitive to the effects of moisture.
  • the binder mixtures contain only a very low content of free formaldehyde, as a result of which the formaldehyde emission of the binders when they are processed into wood-based materials and that of the finished wood-based materials can be significantly reduced.
  • a mixture of 1.64 kg of melamine, 4.34 kg of an aqueous solution of 50% by weight of formaldehyde and 25% by weight of urea and 2.37 kg of a 40% by weight aqueous formaldehyde solution was at a pH -Value from 8.5 to 9 (the pH was adjusted with sodium hydroxide solution) until the mixture had a viscosity of 650 mPa s and then cooled to 60 ° C. Then 1.64 kg of urea were added, the mixture was cooled to room temperature and the pH was adjusted to 9.5 with sodium hydroxide solution.
  • a mixture of 1.27 kg of melamine, 2.59 kg of an aqueous solution of 50% by weight of formaldehyde and 25% by weight of urea and 1.39 kg of a 40% by weight aqueous formaldehyde solution was at a pH -Value from 8.5 to 9 (the pH was adjusted with sodium hydroxide solution) until the mixture had a viscosity of 650 mPa s and then cooled to 60 ° C. Then 1.22 kg of urea were added, the mixture was cooled to room temperature and the pH was adjusted to 9.5 with sodium hydroxide solution.
  • the information given in the examples on the viscosities relates to measurements according to DIN 53 018.
  • the viscosity is then measured in a rotary viscometer at 20 ° C. and a shear rate of 500 s _1 .
  • the free formaldehyde content was determined according to de Jong, as described in Z. Anal. Chem. Volume 281 from 1976, pages 17 to 21 is described.
  • the free formaldehyde is reacted under weakly alkaline reaction conditions with an amount of sulfite which is greater than the amount of formaldehyde, an adduct of formaldehyde and sulfite being formed. Then the closed sulfite titrated at a weakly acidic pH, then the sulfite-formaldehyde adduct formed is hydrolyzed and the sulfite released is determined by titration with iodine.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne des mélanges de liants aqueux s'utilisant dans la production de matériaux dérivés du bois, qui contiennent A) une résine aminoplaste comprenant a1) de la mélamine, a2) entre 0,8 et 6 moles d'urée par mole de mélamine, a3) entre 2 et 20 moles de formaldéhyde par mole de mélamine et a4) entre 0 et 1 mole d'un autre composé pouvant réagir avec le formaldéhyde dans une réaction par addition ou dans une réaction par condensation, le composé différant du phénol ou d'un dérivé de phénol apte à la polycondensation, par mole de mélamine, et B) entre 0,55 et 0,75 mole d'urée par mole du volume total d'urée utilisé comme constituants (a2) et (B), sous réserve que le rapport molaire du volume de mélamine utilisé (constituant (a1)) au volume total d'urée (constituants (a2) et (B)), soit compris entre 1 : 3,5 et 1 : 13 et que le rapport molaire du formaldéhyde (constituant (a3)) aux groupes -NH2 présents dans les constituants (a1), (a2) et (B) soit compris entre 0,2 : 1 et 0,7 : 1.
PCT/EP1996/003796 1995-09-05 1996-08-29 Melanges de liants aqueux a faible teneur en formaldehyde libre s'utilisant dans la production de materiaux derives du bois WO1997009360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995132719 DE19532719A1 (de) 1995-09-05 1995-09-05 Wässrige Bindemittelmischungen mit geringem freiem Formalehydgehalt für die Herstellung von Holzwerkstoffen
DE19532719.5 1995-09-05

Publications (1)

Publication Number Publication Date
WO1997009360A1 true WO1997009360A1 (fr) 1997-03-13

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DE (1) DE19532719A1 (fr)
WO (1) WO1997009360A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002077051A1 (fr) * 2001-03-23 2002-10-03 Cytec Technology Corp. Resines melamine-uree-formaldehyde liquides stables
CN108102057A (zh) * 2017-12-26 2018-06-01 中国林业科学研究院林产化学工业研究所 一种室外级环保型中密度纤维板用胶黏剂的制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1681147A1 (fr) * 2005-01-13 2006-07-19 DSM IP Assets B.V. Panneau à fibres orientées
WO2006091072A1 (fr) * 2005-01-13 2006-08-31 Dsm Ip Assets B.V. Carte à toron orienté
DE102007038041A1 (de) * 2007-08-10 2009-02-12 Kronotec Ag Verfahren zur Vermeidung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen
DE102007055415C5 (de) * 2007-11-19 2018-11-29 SWISS KRONO Tec AG Verfahren zur Verminderung der Emission von gesättigten und ungesättigten Aldehyden aus Holzwerkstoffen
CN118460153B (zh) * 2024-04-30 2025-02-11 广州原野实业有限公司 一种长开放时间且耐湿性强的聚醋酸乙烯酯乳液木工胶黏剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0062389A1 (fr) * 1981-04-07 1982-10-13 METHANOL CHEMIE NEDERLAND V.o.F. Fabrication de panneaux de particules et liant
DE4011159A1 (de) * 1990-04-06 1991-10-10 Basf Ag Waessrige melamin-modifizierte aminoharze

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0062389A1 (fr) * 1981-04-07 1982-10-13 METHANOL CHEMIE NEDERLAND V.o.F. Fabrication de panneaux de particules et liant
DE4011159A1 (de) * 1990-04-06 1991-10-10 Basf Ag Waessrige melamin-modifizierte aminoharze

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002077051A1 (fr) * 2001-03-23 2002-10-03 Cytec Technology Corp. Resines melamine-uree-formaldehyde liquides stables
US6548625B2 (en) 2001-03-23 2003-04-15 Cytec Technology Corp. Stable liquid melamine urea formaldehyde resins, hardeners, adhesive compositions, and methods for making same
US6723825B2 (en) 2001-03-23 2004-04-20 Cytec Technology Corp. Stable liquid melamine urea formaldehyde resins, hardeners, adhesive compositions, and methods for making same
CN108102057A (zh) * 2017-12-26 2018-06-01 中国林业科学研究院林产化学工业研究所 一种室外级环保型中密度纤维板用胶黏剂的制备方法

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Publication number Publication date
DE19532719A1 (de) 1997-03-06

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