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WO1994009062A1 - Procede de reduction des emissions de formaldehyde d'un materiau en mousse a base de resine phenol-formaldehyde - Google Patents

Procede de reduction des emissions de formaldehyde d'un materiau en mousse a base de resine phenol-formaldehyde Download PDF

Info

Publication number
WO1994009062A1
WO1994009062A1 PCT/SE1993/000799 SE9300799W WO9409062A1 WO 1994009062 A1 WO1994009062 A1 WO 1994009062A1 SE 9300799 W SE9300799 W SE 9300799W WO 9409062 A1 WO9409062 A1 WO 9409062A1
Authority
WO
WIPO (PCT)
Prior art keywords
formaldehyde
foam material
solution
emission
ammonium salt
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/SE1993/000799
Other languages
English (en)
Inventor
Jan Olof Andersson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Casco Adhesives AB
Original Assignee
Casco Nobel AB
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 Casco Nobel AB filed Critical Casco Nobel AB
Priority to AU52886/93A priority Critical patent/AU5288693A/en
Publication of WO1994009062A1 publication Critical patent/WO1994009062A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/26—Condensation polymers of aldehydes or ketones with phenols only from mixtures of aldehydes and ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • This invention relates to a method for reducing the emission of formaldehyde from a foam material based on phenol- formaldehyde resin. More specifically, the invention concerns a method in which the foam material is treated with a solution of urea and thermally decomposable ammonium salt.
  • the treated foam material is especially suitable for floral decorations. It is known in the art to use foam materials of phenol- formaldehyde resins for heat and sound insulation. The foams are inexpensive to make, dimensionally stable as well as highly flame-resistant. Being of hydrophilic nature, phenolic resin foams absorb moisture, which has come out useful to florists. Thus, blocks of phenolic resin are used in the preparation of various floral decorations and arrangements. The blocks are able to absorb enough water for the flowers placed therein.
  • One object of the invention is, therefore, to provide a method for reducing the emission of formaldehyde from phenolic resin foam to extremely low levels. Another object of the invention is to provide a method that does not reduce the hydrophilicity of the foam. A further object of the invention is to provide a method that is both simple and effective. As appears from the appended claims, these objects are achieved by a method for reducing the emission of formaldehyde from foam material based on phenol-formaldehyde resin, in which the foam material is treated with a solution of urea and thermally decomposable ammonium salt which ammonium salt gives off ammonia in substantial amounts in a temperature range of 15-90°C.
  • the treatment with the solution of urea and ammonium salt gives a more than 95% reduction of the emission of formaldehyde, as compared with the initial content. Contents below 0.01 ppm (measured according to the 1 m 3 chamber method) are easily obtained. The method is easily implemented and has no adverse effects on the other properties of the foam. Compared e.g. with treatment with pure ammonia gas, the method according to the invention has the advantages of being highly efficient, improving the working environment and involving harmless chemicals.
  • phenolic resin foam is prepared from commercial resols with acid catalysts, but may also be produced from novolaks.
  • a typical initial solution used when preparing phenolic resin foam consists of liquid phenolic resin, expanding agent, catalyst, surfactant and modifier.
  • the formulations can be varied to enhance and alter such prop ⁇ erties as foam structure, combustibility and hydrophilicity.
  • foams are usually made in blocks which are cut to final size after intermediate storage.
  • the solution with which the foam material is treated contains 0.1-30% by weight of urea and 0.1-25% by weight of ammonium salt, the balance being water.
  • the solution may contain 0.1-20% by weight of aqueous ammonia with a concentration of 25% by weight of ammonia.
  • the solution contains 1-15% by weight of urea, 1-20% by weight of ammonium salt and 1-10% by weight of aqueous ammonia.
  • the ammonium salts used should be thermally decomposable and give off ammonia gas in a temperature range of 15-90°C.
  • Use is preferably made of ammonium carbonate, ammonium hydrogen carbonate, or mixtures thereof.
  • the ammonium carbonate can optionally be prepared by mixing ammonium hydrogen carbonate or an aqueous solution thereof and aqueous ammonia.
  • the inventive method is used for treating highly hydrophilic phenolic resin foams of low density.
  • These foams have a density of about 10-100 kg/m 3 , preferably 15-25 kg/m 3 .
  • "Highly hydrophilic foams” means foams which are able to bind as much as 900 1 of water or more per m 3 .
  • Such a foam, intended for floristic use, is manufactured by the company Oasis. It is also essential that the pH of the foams is acid, thereby to prevent unwanted growth in the foam.
  • the foam is treated in the form of sheets, rods or the like having their final thickness.
  • the solution can be applied with the aid of known technique, but is preferably sprayed onto the blocks or sheets.
  • the amount of solution to be applied depends on the concentration of the solution and the initial content of formaldehyde in the foam. Although this amount is easily established by a person skilled in the art, it may be mentioned, for guiding purposes, that 1- 5 1 of a saturated solution may conveniently be applied per m 3 .
  • the sheets are suitably stored to prevent or minimise evaporation. Thus, they may be stored in e.g. sealed packages for at least 24 hours so that as much as possible of the formaldehyde will have reacted.
  • each sheet was conveyed on a roller conveyor at about 60 m/min below an array of spray nozzles providing an evenly distributed curtain of the solution.
  • each sheet was treated on one side, to be immediately treated on the other side.
  • each sheet was at once put in a bag of polyethylene.
  • the bags were stacked, and a heavy sheet was put on top.
  • the sheets were removed, and their smell and appearance were evaluated and samples were taken for measuring the emission according to the REM method.
  • samples were taken for a more accurate measurement of the emission according to the 1 m 3 chamber method. After the chamber measurement had been completed, the pH and the water absorption were determined.
  • Three different solutions were prepared as follows.
  • Chamber method A sheet (80x500x1000 mm) was placed in a non- corrosive sheet-metal chamber with a volume of 1 m 3 . Then, 1 m 3 of clean air (23°C, 50% R.H.) was drawn through the chamber per hour. When a state of equilibrium had been attained (after 3-5 days) , the formaldehyde content of the drawn-out air was determined, and the results were indicated in mg HCHO/m 3 . pH: A block (80x80x110 mm) was saturated with distilled water. Then, the pH of water pressed out of the block was estab- lished.
  • Water absorption The absorption of water was measured by weighing the block before and after water had been absorbed in view of establishing the pH. The water absorption was indi ⁇ cated in g water per g dry foam.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

Procédé de réduction des émissions de formaldéhyde d'un matériau en mousse à base de résine phénol-formaldéhyde, consistant à traiter ledit matériau en mousse à l'aide d'une solution d'urée et d''un sel s'ammonium thermodécomposable, lequel dégage du gaz ammoniac en quantités substantielles dans une plage de températures comprise entre 15 et 90 °C. La solution contient 0,1 à 30 % en poids d'urée ainsi que 0,1 à 25 % en poids de sel d'ammonium, le solde étant de l'eau. Le sel d'ammonium se compose de carbonate d'ammonium, de carbone d'hydrogène d'ammonium ou de mélanges de ceux-ci.
PCT/SE1993/000799 1992-10-08 1993-10-04 Procede de reduction des emissions de formaldehyde d'un materiau en mousse a base de resine phenol-formaldehyde Ceased WO1994009062A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU52886/93A AU5288693A (en) 1992-10-08 1993-10-04 A method for reducing the emission of formaldehyde from a foam material based on phenol-formaldehyde resin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9202958A SE9202958L (sv) 1992-10-08 1992-10-08 Förfarande för att minska emissionen av formaldehyd från fenol-formaldehydhartsbaserat skummaterial
SE9202958-6 1992-10-08

Publications (1)

Publication Number Publication Date
WO1994009062A1 true WO1994009062A1 (fr) 1994-04-28

Family

ID=20387428

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1993/000799 Ceased WO1994009062A1 (fr) 1992-10-08 1993-10-04 Procede de reduction des emissions de formaldehyde d'un materiau en mousse a base de resine phenol-formaldehyde

Country Status (4)

Country Link
AU (1) AU5288693A (fr)
EE (1) EE9400214A (fr)
SE (1) SE9202958L (fr)
WO (1) WO1994009062A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100383251B1 (ko) * 2000-12-02 2003-05-12 한솔제지주식회사 포름알데히드 수지로부터 잔류 포름알데히드의 제거방법
WO2017081061A1 (fr) * 2015-11-13 2017-05-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de recyclage de matières contenant de la résine phénolique, en particulier de matières synthétiques composites fibreuses à base de résine phénolique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2917064A1 (de) * 1979-04-27 1980-11-13 Basf Ag Verfahren zur verminderung der formaldehydentwicklung von aminoplast-schaumstoffen
US4267277A (en) * 1980-01-07 1981-05-12 Rapco Foam, Inc. Method of producing urea-formaldehyde resin and foam having reduced formaldehyde emission
US4273883A (en) * 1980-04-08 1981-06-16 Korf Heinz L Urea-formaldehyde polymers having reduced formaldehyde emission and cellular urea formaldehyde foam which is resistant to acid-induced hydrolysis
US4490486A (en) * 1982-09-13 1984-12-25 Lough Merlin E Formaldehyde immobilization method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2917064A1 (de) * 1979-04-27 1980-11-13 Basf Ag Verfahren zur verminderung der formaldehydentwicklung von aminoplast-schaumstoffen
US4267277A (en) * 1980-01-07 1981-05-12 Rapco Foam, Inc. Method of producing urea-formaldehyde resin and foam having reduced formaldehyde emission
US4273883A (en) * 1980-04-08 1981-06-16 Korf Heinz L Urea-formaldehyde polymers having reduced formaldehyde emission and cellular urea formaldehyde foam which is resistant to acid-induced hydrolysis
US4490486A (en) * 1982-09-13 1984-12-25 Lough Merlin E Formaldehyde immobilization method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100383251B1 (ko) * 2000-12-02 2003-05-12 한솔제지주식회사 포름알데히드 수지로부터 잔류 포름알데히드의 제거방법
WO2017081061A1 (fr) * 2015-11-13 2017-05-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de recyclage de matières contenant de la résine phénolique, en particulier de matières synthétiques composites fibreuses à base de résine phénolique
US10633507B2 (en) 2015-11-13 2020-04-28 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method of recycling phenol resin-containing materials, especially phenol resin-based fiber composite materials

Also Published As

Publication number Publication date
AU5288693A (en) 1994-05-09
SE9202958D0 (sv) 1992-10-08
EE9400214A (et) 1996-02-15
SE9202958L (sv) 1994-04-09

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