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EP0000933B1 - Hydrophobic polyurethane foams, process for their manufacture and their use to absorb oil and halogenated hydrophobic compounds, which may be halogenated, from water - Google Patents

Hydrophobic polyurethane foams, process for their manufacture and their use to absorb oil and halogenated hydrophobic compounds, which may be halogenated, from water Download PDF

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Publication number
EP0000933B1
EP0000933B1 EP78100702A EP78100702A EP0000933B1 EP 0000933 B1 EP0000933 B1 EP 0000933B1 EP 78100702 A EP78100702 A EP 78100702A EP 78100702 A EP78100702 A EP 78100702A EP 0000933 B1 EP0000933 B1 EP 0000933B1
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EP
European Patent Office
Prior art keywords
compounds
water
polyurethane foams
hydrophobic
polyhydroxy compounds
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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.)
Expired
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EP78100702A
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German (de)
French (fr)
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EP0000933A1 (en
Inventor
Wolfgang Dr. Jarre
Rolf Dr. Wurmb
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BASF SE
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BASF SE
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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/281—Monocarboxylic acid compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/905—Hydrophilic or hydrophobic cellular product

Definitions

  • the invention relates to polyurethane foams with densities of 5 to 26.5 g / liter which, owing to their hydrophobic character and their content of closed and open cells, are particularly suitable for the absorption of oil and, if appropriate, halogen-containing, hydrophobic compounds in water.
  • polyurethane foams from polyisocyanates, polyhydroxy compounds, optionally chain extenders, auxiliaries and additives is known from numerous patent and literature publications. For example, we would like to refer to the monographs by JH Saunders and KC Frisch, High Polymers, Volume XVI "Polyurethanes" Part I and II (Interscience Publishers, New York), and R. Vieweg and A. Höchtlen, Kunststoff-Hanbuch, Volume VII , Polyurethane, Carl Hanser Verlag, Kunststoff.
  • open-cell foams made of polyurethanes, urea-formaldehyde condensates, polystyrene, cellulose acetate and others for oil absorption from water surfaces.
  • open-cell foams made of polyurethanes, urea-formaldehyde condensates, polystyrene, cellulose acetate and others for oil absorption from water surfaces.
  • US Pat. No. 3,779,908 a dispersion of crude oil in water is allowed to flee through a flexible, open-cell foam for oil absorption.
  • Oleophilic semi-hard to hard foams are further distributed according to US Pat. No. 3,886,067 on oil-containing water surfaces and, after oil absorption on the foam, collected and removed again.
  • the object of the present invention was to develop polyurethane foams which do not have these disadvantages.
  • the polyurethane foams should be quickly produced on site from polyurethane systems that are space-saving in liquid form and therefore inexpensive to transport.
  • polyurethane foams are particularly suitable for absorbing oil and halogen-containing hydrophobic solvents from water if they are hydrophobic and at the same time have closed and open cells in certain proportions.
  • hydrophobic polyurethane foams according to the invention are made both by the prepolymer process and preferably by the one-shot process from organic polyisocyanates, polyhydroxy compounds, blowing agents, catalysts, optionally chain extenders, auxiliaries and additives with the additional use of lipophilic compounds, preferably based on fatty acids and / or Fatty acid derivatives, advantageously produced on site.
  • Linear and / or branched hydroxyl-containing polyethers having molecular weights of from about 300 to about 10,000, preferably from about 1,000 to about 6,000 and hydroxyl numbers from about 700 to about 20, preferably from 200 to 40, are expediently used as the polyhydroxy compounds.
  • the hydroxyl-containing polyethers are prepared by reacting one or more, optionally substituted, alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains at least two active hydrogen atoms bonded.
  • alkylene oxides are: tetrahydrofuran, 1,2- and 2,3-butylene oxide and preferably propylene oxide. Mixtures of propylene oxide and ethylene oxide with an ethylene oxide content, preferably less than 20% by weight, based on the total weight of the mixture, can also be used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • starter molecules are: water, aliphatic and aromatic dicarboxylic acids, such as adipic acid and terephthalic acid, and preferably dihydric and polyhydric alcohols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1-hexanediol , 6, glycerin, trimethylolpropane, 2,4,6-hexanetriol, pentaerythritol, sorbitol and sucrose.
  • dihydric and polyhydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1-hexanediol , 6, glycerin, trimethylolpropane, 2,4,6-hexanetriol, pentaerythritol, sorbitol and sucrose.
  • the polyhydroxy compounds used are preferably di- and tri-functional hydroxyl-containing polypropylene oxides with molecular weights of 2,000 to 6,000.
  • Suitable lipophilic compounds are, for example, optionally substituted, saturated and / or unsaturated aliphatic fatty acids with 10 to 25, preferably 12 to 20 carbon atoms in the molecule and their derivatives, preferably their esters with 2 to 20 carbon atoms in the alcohol radical and amides. Lipophilic fatty acid esters and amides which contain isocyanate-reactive groups and are thus incorporated into the polyurethane foam structure are particularly preferred.
  • Examples include: fatty acids such as capric, lauric, myristic, palmitic, stearic, arachinic, lignoceric, palmitic, oleic, ricinoleic, linoleic and linolenic acids; Fatty acid esters, such as castor oil, tall oil and adducts of the fatty acid and propylene and / or ethylene oxides and fatty acid amides, such as oleic acid mono- and diethanolamide, ricinoleic mono- and diethanolamide and their N, N-dialkylamides, such as ricinoleic acid dimethylaminopropylamide.
  • fatty acids such as capric, lauric, myristic, palmitic, stearic, arachinic, lignoceric, palmitic, oleic, ricinoleic, linoleic and linolenic acids
  • Fatty acid esters such as castor oil, tall oil and
  • polyhydroxy compounds and lipophilic compounds are used in molar proportions from 1: 3 to 1:20, preferably from 1: 6 to 1:15 and in particular from about 1:10 to produce the hydrophobic polyurethane foams according to the invention.
  • chain extenders in addition to the higher molecular weight polyhydroxy compounds.
  • the chain extenders have molecular weights less than 300, preferably from 80 to 200, and preferably have two active hydrogen atoms.
  • the polyurethane foams according to the invention are preferably produced without the use of chain extenders.
  • Water is used as the blowing agent, which reacts with isocyanate groups to form carbon dioxide. If the hydrophobic polyurethane foams according to the invention are produced by the prepolymer process, it has proven to be advantageous to foam the prepolymer having NCO end groups under water, that is to say in the presence of a large excess of water.
  • the quantitative ratio of water molecule to NCO group of the prepolymer can accordingly be as large as desired, but the value should not be less than about 5: 1. For example, molar ratios of water to NCO group in the prepolymer from 8: 1 to 1,000: 1 and larger have proven successful.
  • hydrophobic polyurethane foams according to the invention are produced by the one-shot process, it may be advantageous, depending on the type of polyhydroxy compounds and lipophilic compounds used, to mix the water used as blowing agent with a solubilizer.
  • Suitable solubilizers are all organic solvents with boiling points of 20 ° to 110 ° C., preferably 30 ° to 70 ° C., which are infinitely miscible with water and inert to isocyanate groups under the reaction conditions. Examples include acetone, methyl ethyl ketone, dioxane and tetrahydrofuran; acetone is preferably used.
  • the water is mixed with the solubilizer in such amounts that the weight ratio of water to solubilizer is 1: 1 to 10: 1, preferably 2: 1 to 4: 1.
  • the polyurethane foams according to the invention can be produced directly on site in the water. In these cases it has proven advantageous to accelerate the reaction between the polyhydroxy compounds, the water, optionally chain extenders and the lipophilic compounds, provided that these Zerewitinoff contain active groups bound in the molecule, and the highly reactive catalysts known to the organic polyisocanates, for example tertiary ones Amines, such as dimethylbenzylamine, N-methyl- or N-ethylmorpholine, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo (3,3,0) octane and preferably triethylene diamine and metal salts such as tin dioctoate , Lead octoate and tin diethylhexoate and preferably tin (II) salts and dibutyltin dilaurate, and preferably mixtures of tertiary amines and organic tin salts.
  • Amines such as dimethylbenzylamine,
  • the amount to be used is determined empirically depending on the reactivity of the chosen catalyst or the catalyst mixture determined by constitution. If the polyurethane foams according to the invention are produced on site by the one shot process, the catalysts and amounts must be selected such that the starting times at reaction temperatures from 0 ° to 35 ° C. are approximately 2 to 10 seconds, preferably 2 to 5 seconds.
  • the start time (creamtime) is the time of the trouble-free pourability of the foamable mixture, ie the time available from mixing to the start of a visible reac tion, in which mixing of the starting materials, discharge from the mixing element and spraying of the reaction mass must be carried out.
  • polyurethane block foams are produced from the starting components mentioned above using conventional catalysts for the production of block foam, which as such are spread out on the oil-containing water surface, can be collected and pressed out after the absorption of oil, or can be comminuted and used as a filling material for absorption columns can.
  • Auxiliaries and additives can also be incorporated into the reaction mixture. Examples include stabilizers, hydrolysis protection agents, pore regulators and surface-active substances.
  • surface-active substances are considered which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the foams.
  • examples include siloxane-oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or castor oil esters and Turkish red oil, which are used in amounts of 0.2 to 6 parts by weight per 100 parts by weight of polyisocyanate.
  • the polyurethane foams according to the invention can be produced by the prepolymer and preferably by the one-shot process.
  • a mixture of polyhydroxy compound, lipophilic compound, water and optionally chain extender with the organic polyisocyanate in the presence of auxiliaries and additives is usually used at temperatures from 0 ° to 35 °, preferably 15 ° to 25 ° ° C implemented in such amounts that the ratio of Zerewitinoff active hydrogen atoms of the polyhydroxy compounds, lipophilic compounds and optionally chain extenders to the NCO group of the polyisocyanate is 0.7 to 1.3: 1, preferably approximately 1: 1, and the ratio of all Zerewitinoff active hydrogen atoms bonded to polyhydroxy compound, lipophilic compound, optionally chain extender and water to the NCO group of the polyisocyanate is approximately 1.3 to 5: 1, preferably 1.5 to 3: 1.
  • the starting components can be fed in individually and mixed intensively in the mixing chamber.
  • hydrophobic polyurethane foams according to the invention on water and the separation of those containing 01 and / or halogen; Polyurethane foams impregnated with hydrophobic solvents from the water surface are made with the aid of known devices which are expediently installed on ships or in aircraft. ,
  • the prepolymers containing NCO groups are advantageously atomized under water
  • Suitable polymer solvents are preferably those which are readily miscible with the prepolymer containing NCO groups and the oil to be absorbed, for example methylene chloride, toluene, cyclohexane, hexane and others
  • the foamable prepolymer mixture is expanded with simultaneous foaming by the carbon dioxide formed during the reaction of the prepolymers containing NCO groups with water, and the expanding and already expanded material rises to the surface of the water d absorbs the overlying oil or solvent layer from below.
  • the polyurethanes impregnated with oil and optionally halogen-containing, hydrophobic solvents can then be separated from the water surface using known methods.
  • the prepolymers containing NCO groups the polyisocyanates and mixtures of polyhydroxy compounds and lipophilic compounds mentioned above are reacted in the presence of any auxiliaries and additives in amounts such that the ratio of NCO groups to total hydroxyl of the mixture is 50: 1 to 2: 1, preferably 15: 1 to 5: 1.
  • hydrophobic polyurethane foams according to the invention have a high absorption capacity for.
  • Oil for example crude, heating and diesel oil and for halogen if necessary containing hydrophobic compounds, for example solvents such as hexane, benzene, toluene, aniline, chloroform, carbon tetrachloride, dichloroethane and hexachiorcyclopentadiene.
  • the prepolymer solution containing NCO groups is then atomized under water.
  • the specific weight of the prepolymer containing NCO groups is 1.3546 g / cm 3 without solvent.
  • the density of the prepolymer solution can be varied from 0.922 to 1.333 g / cm 3 by mixing the prepolymer with organic solvents.
  • the tests show the very high oil absorption capacity of the foams according to the invention in comparison to conventional rigid and flexible foams.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Polyurethanes Or Polyureas (AREA)
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Description

Die Erfindung betrifft Polyurethanschaumstoffe mit Dichten von 5 bis 26,5 g/Liter, die aufgrund ihres hydrophoben Charakters und ihres Gehalts an geschlossenen und offenen Zellen vorzüglich zur Absorption von Öl und gegebenenfalls halogenhaltigen, hydrophoben Verbindungen in Gewässern geeignet sind.The invention relates to polyurethane foams with densities of 5 to 26.5 g / liter which, owing to their hydrophobic character and their content of closed and open cells, are particularly suitable for the absorption of oil and, if appropriate, halogen-containing, hydrophobic compounds in water.

Die Herstellung von Polyurethanschaumstoffen aus Polyisocyanaten, Polyhydroxyverbindungen, gegebenenfalls Kettenverlängerungsmitteln, Hilfs- und Zusatzstoffen ist aus zahlreichen Patent- und Literaturveröffentlichungen bekannt. Verweisen möchten wir beispielsweise auf die Monographien von J. H. Saunders und K. C. Frisch, High Polymers, Band XVI "Polyurethanes" Teil I und II (Verlag Interscience Publishers, New York), und R. Vieweg und A. Höchtlen, Kunststoff-Hanbuch, Band VII, Polyurethane, Carl Hanser Verlag, München.The production of polyurethane foams from polyisocyanates, polyhydroxy compounds, optionally chain extenders, auxiliaries and additives is known from numerous patent and literature publications. For example, we would like to refer to the monographs by JH Saunders and KC Frisch, High Polymers, Volume XVI "Polyurethanes" Part I and II (Interscience Publishers, New York), and R. Vieweg and A. Höchtlen, Kunststoff-Hanbuch, Volume VII , Polyurethane, Carl Hanser Verlag, Munich.

Es ist ferner vorgeschlagen worden, zur Ölabsorption von Wasseroberflächen offenzellige Schaumstoffe aus Polyurethanen, Harnstoff-Formaldehydkondensaten, Polystyrol, Celluloseacetat u.a. zu verwenden. Nach Angaben der US-PS 3 779 908 läßt man zur Ölabsorption eine Dispersion von Rohöl in Wasser durch einen flexiblen, offenzelligen Schaumstoff fleißen. Oleophile halbharte bis harte Schaumstoffe werden ferner gemäß US-PS 3 886 067 auf ölhaltigen Wasseroberflächen verteilt und nach erfolgter Ölabsorption an den Schaumstoff wieder gesammelt und entfernt.It has also been proposed to use open-cell foams made of polyurethanes, urea-formaldehyde condensates, polystyrene, cellulose acetate and others for oil absorption from water surfaces. to use. According to US Pat. No. 3,779,908, a dispersion of crude oil in water is allowed to flee through a flexible, open-cell foam for oil absorption. Oleophilic semi-hard to hard foams are further distributed according to US Pat. No. 3,886,067 on oil-containing water surfaces and, after oil absorption on the foam, collected and removed again.

Nachteilig an den beschriebenen Verfahren ist, daß sie auf offener See, insbesondere bei rauhem Seegang, nicht angewandt werden können, der Transport der voluminösen Schaumstoffpartikel an den Einsatzort kostspielig ist und die Ölaufnahme gering ist, da offenzellige Schaumstoffpartikel in Wasser rasch absinken und geschlossenzellige eine zu geringe Oberfläche aufweisen.The disadvantages of the described methods are that they cannot be used on the open sea, especially in rough seas, the transport of the voluminous foam particles to the place of use is expensive and the oil absorption is low, since open-cell foam particles sink rapidly in water and closed-celled ones too have a small surface area.

Aufgabe der vorliegenden Erfindung war es, Polyurethanschaumstoffe zu entwickeln, die diese Nachteile nicht aufweisen. Die Polyurethanschaumstoffe sollten am Einsatzort aus Polyurethansystemen, die in flüssiger Form raumsparend und daher preisgünstig transportabel sind, schnell hergestellt werden.The object of the present invention was to develop polyurethane foams which do not have these disadvantages. The polyurethane foams should be quickly produced on site from polyurethane systems that are space-saving in liquid form and therefore inexpensive to transport.

Überraschenderweise wurde gefunden, daß Polyurethanschaumstoffe zur Absorption von Öl und halogenhaltigen hydrophoben Lösungsmitteln aus Wasser besonders dann geeignet sind, wenn sie hydrophob sind und gleichzeitig geschlossene und offene Zellen in bestimmten Verhältnissen besitzen.Surprisingly, it has been found that polyurethane foams are particularly suitable for absorbing oil and halogen-containing hydrophobic solvents from water if they are hydrophobic and at the same time have closed and open cells in certain proportions.

Gegenstand der vorliegenden Erfindung sind somit hydrophobe Polyurethaneschaumstoffe zur Absorption von Öl und/oder gegebenenfalls halogenhaltigen, hydrophoben Verbindungen aus Wasser, hergestellt durch Umsetzung von organischen Polyisocyanaten mit Polyhydroxyverbindungen in Gegenwart von Wasser als Treibmittel und Katalysatoren sowie gegebenenfalls lipophilen Verbindungen, Kettenverlängerungsmitteln, Hilfsmitteln und Zusatzstoffen, die dadurch gekennzeichnet sind, daß die hydrophoben Polyurethanschaumstoffe

  • a) eine Dichte von 5 bis 26,5 g/Liter, vorzugsweise 6,8 bis 18 g/Liter besitzen,
  • b) die Zahl der geschlossenen Zellen 3 bis 3096, vorzugsweise 10 bis 20% und der offenen Zellen 97 bis 70%, vorzugsweise 90 bis 80%, bezogen auf die Gesamtzahl an Zellen, beträgt und
  • c) als Polyhydroxyverbindungen lineare und/oder verzweigte hydroxylgruppenhaltige Polyether mit Molekulargewichten von 300 bis 10000 verwendet werden, die durch Polymerisation von Tetrahydrofuran, 1,2- und 2,3-Butylenoxid, Propylenoxid oder Mischungen aus Propylenoxid und Ethylenoxid mit einem Ethylenoxidgehalt von kleiner als 20 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, erhalten werden.
The present invention thus relates to hydrophobic polyurethane foams for the absorption of oil and / or optionally halogen-containing, hydrophobic compounds from water, produced by reacting organic polyisocyanates with polyhydroxy compounds in the presence of water as blowing agents and catalysts and, if appropriate, lipophilic compounds, chain extenders, auxiliaries and additives, which are characterized in that the hydrophobic polyurethane foams
  • a) have a density of 5 to 26.5 g / liter, preferably 6.8 to 18 g / liter,
  • b) the number of closed cells is 3 to 3096, preferably 10 to 20% and the open cells is 97 to 70%, preferably 90 to 80%, based on the total number of cells, and
  • c) linear and / or branched hydroxyl-containing polyethers with molecular weights of 300 to 10,000 are used as polyhydroxy compounds, which are obtained by polymerizing tetrahydrofuran, 1,2- and 2,3-butylene oxide, propylene oxide or mixtures of propylene oxide and ethylene oxide with an ethylene oxide content of less than 20 wt .-%, based on the total weight of the mixture can be obtained.

Die erfindungsgemäßen hydrophoben Polyurethanschaumstoffe werden sowohl nach dem Präpolymerverfahren als auch vorzugsweise nach dem one shot-Verfahren aus organischen Polyisocyanaten, Polyhydroxyverbindungen, Treibmitteln, Katalysatoren, gegebenenfalls Kettenverlängerungsmitteln, Hilfs- und Zusatzmitteln unter zusätzlicher Mitverwendung von lipophilen Verbindungen, vorzugsweise auf Basis von Fettsäuren und/oder Fettsäurederivaten, vorteilhafterweise am Einsatzort, hergestellt.The hydrophobic polyurethane foams according to the invention are made both by the prepolymer process and preferably by the one-shot process from organic polyisocyanates, polyhydroxy compounds, blowing agents, catalysts, optionally chain extenders, auxiliaries and additives with the additional use of lipophilic compounds, preferably based on fatty acids and / or Fatty acid derivatives, advantageously produced on site.

Zu den zur Herstellung der hydrophoben Polyurethanschaumstoffe verwendbaren Aufbaukomponenten ist folgendes auszuführen:

  • Als organische Polyisocyanate kommen vorzugsweise aromatische Di- und Polyisocyanate in Frage. Im einzelnen seien z.B. genannt: 2,4- und 2,6-Toluylen-diisocyanat, 2,4'-, 4,4'- und 2,2'-Diphenylmethan-diisocyanat sowie deren Isomerengemische und Mischungen aus Toluylendiisocyanaten und Diphenylmethandiisocyanaten. Vorzugsweise verwendet werden jedoch technische Mischungen aus Diphenylmethan-diisocyanaten und Polyphenylpolymethylen-Polyisocyanaten (Roh-MDJ).
The following is to be stated about the structural components that can be used to produce the hydrophobic polyurethane foams:
  • Aromatic di- and polyisocyanates are preferred as organic polyisocyanates. The following may be mentioned in detail, for example: 2,4- and 2,6-tolylene diisocyanate, 2,4'-, 4,4'- and 2,2'-diphenylmethane diisocyanate as well as their isomer mixtures and mixtures of tolylene diisocyanates and diphenylmethane diisocyanates. However, technical mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (raw MDJ) are preferably used.

Als Polyhydroxyverbindungen werden zweckmäßigerweise lineare und/oder verzweigte hydroxylgruppenhaltige Polyäther mit Molekulargewichten von ungefähr 300 bis ungefähr 10 000, vorzugsweise von ungefähr 1 000 bis ungefähr 6 000 und Hydroxylzahlen von ungefähr 700 bis ungefähr 20, vorzugsweise von 200 bis 40 verwendet. Die hydroxylgruppenhaltigen Polyäther werden durch Umsetzung von einem oder mehreren, gegebenenfalls substituierten Alkylenoxiden mit 2 bis 4 Kohlenstoffatomen im Alkylenrest mit einem Startermolekül, das mindestens zwei aktive Wasserstoffatome gebunden enhält, hergestellt. Als Alkylenoxide seien beispielhaft genannt: Tetrahydrofuran, 1,2-und 2,3-Butylenoxid und vorzugsweise Propylenoxid. Verwendet werden können ferner Mischungen aus Propylenoxid und Äthylenoxid mit einem Äthyienoxidgehait vorzugsweise kleiner als 20 Gew.%, bezogen auf das Gesamtgewicht der Mischung. Die Alkylenoxide können einzeln, alternierend nacheinander oder als Mischungen verwendet werden.Linear and / or branched hydroxyl-containing polyethers having molecular weights of from about 300 to about 10,000, preferably from about 1,000 to about 6,000 and hydroxyl numbers from about 700 to about 20, preferably from 200 to 40, are expediently used as the polyhydroxy compounds. The hydroxyl-containing polyethers are prepared by reacting one or more, optionally substituted, alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains at least two active hydrogen atoms bonded. Examples of alkylene oxides are: tetrahydrofuran, 1,2- and 2,3-butylene oxide and preferably propylene oxide. Mixtures of propylene oxide and ethylene oxide with an ethylene oxide content, preferably less than 20% by weight, based on the total weight of the mixture, can also be used. The alkylene oxides can be used individually, alternately in succession or as mixtures.

Als Startermoleküle kommen beispielsweise in Betracht: Wasser, aliphatische und aromatische Dicarbonsäuren, wie Adipinsäure und Terephthalsäure und vorzugsweise zwei- und mehrwertige Alkohole, wie Äthylenglykol, Propandiol-1,2, Propandiol-1,3, Butandiol-1,4, Hexandiol-1,6, Glycerin, Trimethylolpropan, Hexantriol-2,4,6, Pentaerythrit, Sorbit und Saccharose.Examples of suitable starter molecules are: water, aliphatic and aromatic dicarboxylic acids, such as adipic acid and terephthalic acid, and preferably dihydric and polyhydric alcohols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1-hexanediol , 6, glycerin, trimethylolpropane, 2,4,6-hexanetriol, pentaerythritol, sorbitol and sucrose.

Als Polyhydroxyverbindungen werden vorzugsweise di- und tri-funktionelle hydroxylgruppenhaltige Polypropylenoxide mit Molekulargewichten von 2 000 bis 6 000 verwendet.The polyhydroxy compounds used are preferably di- and tri-functional hydroxyl-containing polypropylene oxides with molecular weights of 2,000 to 6,000.

Geeignete lipophile Verbindungen sind beispielsweise gegebenenfalls substituierte, gesättigte und/oder ungesättigte aliphatische Fettsäuren mit 10 bis 25, vorzugsweise 12 bis 20 Kohlenstoffatomen im Molekül sowie deren Derivate, vorzugsweise deren Ester mit 2 bis 20 Kohlenstoffatomen im Alkoholrest und Amide. Besonders bevorzugt sind solche lipophilen Fettsäureester und -amide, die mit Isocyanat reagierende Gruppen gebunden enthalten und so ins Polyurethanschaumstoffgerüst eingebaut werden. Im einzelnen seien beispielhaft genannt: Fettsäuren, wie Caprin-, Laurin-, Myristin-, Palmitin-, Stearin-, Arachin-, Lignocerin-, Palmitin-, Öl-, Ricinolein-, Linolsäure und Linolensäure; Fettsäureester, wie Ricinusöl, Tallöl und Addukte aus den genannten Fettsäure und Propylen- und/oder Äthylenoxide und Fettsäureamide, wie Ölsäuremono- und -diäthanolamid, Ricinolsäuremono- und - diäthanolamid sowie deren N,N-Dialkylamide, wie Ricinolsäure-dimethylaminopropylamid.Suitable lipophilic compounds are, for example, optionally substituted, saturated and / or unsaturated aliphatic fatty acids with 10 to 25, preferably 12 to 20 carbon atoms in the molecule and their derivatives, preferably their esters with 2 to 20 carbon atoms in the alcohol radical and amides. Lipophilic fatty acid esters and amides which contain isocyanate-reactive groups and are thus incorporated into the polyurethane foam structure are particularly preferred. Examples include: fatty acids such as capric, lauric, myristic, palmitic, stearic, arachinic, lignoceric, palmitic, oleic, ricinoleic, linoleic and linolenic acids; Fatty acid esters, such as castor oil, tall oil and adducts of the fatty acid and propylene and / or ethylene oxides and fatty acid amides, such as oleic acid mono- and diethanolamide, ricinoleic mono- and diethanolamide and their N, N-dialkylamides, such as ricinoleic acid dimethylaminopropylamide.

Zur Herstellung der erfindungsgemäßen hydrophoben Polyurethanschaumstoffe werden die obengenannten Polyhydroxyverbindungen und lipophilen Verbindungen in molaren Mengenverhältnissen von 1:3 bis 1:20, vorzugsweise von 1:6 bis 1:15 und insbesondere von ungefähr 1:10 verwendet.The above-mentioned polyhydroxy compounds and lipophilic compounds are used in molar proportions from 1: 3 to 1:20, preferably from 1: 6 to 1:15 and in particular from about 1:10 to produce the hydrophobic polyurethane foams according to the invention.

Gegebenenfalls kann es zweckmäßig sein, neben den höhermolekularen Polyhydroxyverbindungen zusätzlich Kettenverlängerungsmittel zu verwenden. Die Kettenverlängerungsmittel besitzen Molekulargewichte kleiner als 300, vorzugsweise von 80 bis 200, und weisen vorzugsweise zwei aktive Wasserstoffatome auf. In Betracht kommen beispielsweise aliphatische und/oder aromatische Diole mit 2 bis 14, vorzugsweise 4 bis 10 Kohlenstoffatomen, wie Äthylenglykol, Propandiol, Decandiol-1,10 und vorzugsweise Butandiol-1,4, Hexandiol-1,6 und Bis-(2-hydroxyäthyl)-hydrochinon. Die erfindungsgemäßen Polyurethanschaumstoffe werden jedoch vorzugsweise ohne Mitverwendung von Kettenverlängerungsmitteln hergestellt.It may be appropriate to use chain extenders in addition to the higher molecular weight polyhydroxy compounds. The chain extenders have molecular weights less than 300, preferably from 80 to 200, and preferably have two active hydrogen atoms. For example, aliphatic and / or aromatic diols with 2 to 14, preferably 4 to 10 carbon atoms, such as ethylene glycol, propanediol, 1,10-decanediol and preferably 1,4-butanediol, 1,6-hexanediol and bis- (2- hydroxyethyl) hydroquinone. However, the polyurethane foams according to the invention are preferably produced without the use of chain extenders.

Als Treibmittel wird Wasser verwendet, das mit Isocyanatgruppen unter Bildung von Kohlendioxid reagiert. Werden die erfindungsgemäßen hydrophoben Polyurethanschaumstoffe nach dem Präpolymerverfahren hergestellt, so hat es sich als vorteilhaft erwiesen, das NCO-Endgruppen aufweisende Präpolymere unter Wasser, das heißt in Gegenwart eines großen Wasserüberschusses zu verschäumen. Das Mengenverhältnis von Wassermolekül zu NCO-Gruppe des Präpolymeren kann demnach beliebig groß sein, wobei der Wert von ungefähr 5:1 jedoch zweckmäßigerweise nicht unterschritten werden sollte. Gut bewährt haben sich beispielsweise molare Mengenverhältnisse von Wasser zu NCO-Gruppe im Präpolymeren von 8:1 bis 1 000:1 und größer.Water is used as the blowing agent, which reacts with isocyanate groups to form carbon dioxide. If the hydrophobic polyurethane foams according to the invention are produced by the prepolymer process, it has proven to be advantageous to foam the prepolymer having NCO end groups under water, that is to say in the presence of a large excess of water. The quantitative ratio of water molecule to NCO group of the prepolymer can accordingly be as large as desired, but the value should not be less than about 5: 1. For example, molar ratios of water to NCO group in the prepolymer from 8: 1 to 1,000: 1 and larger have proven successful.

Werden die erfindungsgemäßen hydrophoben Polyurethanschaumstoffe jedoch nach dem one shot-Verfahren hergestellt, so kann es je nach Art der verwendeten Polyhydroxyverbindungen und lipophilen Verbindungen gegebenenfalls vorteilhaft sein, das als Treibmittel dienende Wasser mit einem Lösungsvermittler zu vermischen. Als Lösungsvermittler sind alle organischen Lösungsmittel mit Siedepunkten von 20° bis 110°C, vorzugsweise 30° bis 70°C geeignet, die unbegrenzt mit Wasser mischbar und unter den Reaktionsbedingungen gegenüber Isocyanatgruppen inert sind. Genannt seien beispielsweise Aceton, Methyläthylketon, Dioxan und Tetrahydrofuran, vorzugsweise verwendet wird Aceton. Das Wasser wird hierzu mit dem Lösungsvermittler in solchen Mengen gemischt, daß das Gewichtsverhältnis von Wasser zu Lösungsvermittler 1:1 bis 10:1, vorzugsweise 2:1 bis 4:1 beträgt.However, if the hydrophobic polyurethane foams according to the invention are produced by the one-shot process, it may be advantageous, depending on the type of polyhydroxy compounds and lipophilic compounds used, to mix the water used as blowing agent with a solubilizer. Suitable solubilizers are all organic solvents with boiling points of 20 ° to 110 ° C., preferably 30 ° to 70 ° C., which are infinitely miscible with water and inert to isocyanate groups under the reaction conditions. Examples include acetone, methyl ethyl ketone, dioxane and tetrahydrofuran; acetone is preferably used. For this purpose, the water is mixed with the solubilizer in such amounts that the weight ratio of water to solubilizer is 1: 1 to 10: 1, preferably 2: 1 to 4: 1.

Die erfindungsgemäßen Polyurethanschaumstoffe können direkt vor Ort in den Gewässern hergestellt werden. In diesen Fällen hat es sich als vorteilhaft erwiesen, der Reaktionsmischung zur Beschleunigung der Umsetzung zwischen den Polyhydroxyverbindungen, dem Wasser, gegebenenfalls Kettenverlängerungsmitteln und den lipophilen Verbindungen, sofern diese Zerewitinoff aktive Gruppen im Molekül gebunden enthalten, und den organischen Polyisocanaten bekannte hochreaktive Katalysatoren, beispielsweise tertiäre Amine, wie Dimethylbenzylamin, N-Methyl- bzw. N-Äthylmorpholin, Dimethylpiperazin, 1,2-Dimethylimidazol, 1-Aza-bicyclo-(3,3,0)-octan und vorzugsweise Triäthylen-diamin und Metallsalze, wie Zinn-dioctoat, Bleioctoat und Zinn-diäthylhexoat und vorzugsweise Zinn-IIsalze und Dibutylzinndilaurat sowie vorzugsweise Mischungen aus tertiären Aminen und organischen Zinnsalzen hinzuzufügen. Zur Erzielung von verschäumungstechnisch günstigen Reaktionszeiten wird in Abhängigkeit von der durch Konstitution bestimmten Reaktivität des gewählten Katalysators bzw. des Katalysatorgemisches die einzusetzende Menge empirisch ermittelt. Werden die erfindungsgemäßen Polyurethanschaumstoffe nach dem one shot-Verfahren vor Ort hergestellt, so müssen die Katalysatoren und -mengen so ausgewählt werden, daß die Startzeiten bei Reaktionstemperaturen von 0° bis 35°C ungefähr 2 bis 10 Sekunden, vorzugsweise 2 bis 5 Sekunden betragen. Als Startzeit (creamtime) ist hierbei die Zeit der störungsfreien Vergießbarkeit der schaumfähigen Mischung zu verstehen, d.h. der zur Verfügung stehende Zeitabschnitt vom Vermischen bis zum Beginn einer sichtbaren Reaktion, in welchem Vermischen der Ausgangstoffe, Austrag aus dem Mischorgan und Versprühen der Reaktionsmasse durchgeführt werden müssen.The polyurethane foams according to the invention can be produced directly on site in the water. In these cases it has proven advantageous to accelerate the reaction between the polyhydroxy compounds, the water, optionally chain extenders and the lipophilic compounds, provided that these Zerewitinoff contain active groups bound in the molecule, and the highly reactive catalysts known to the organic polyisocanates, for example tertiary ones Amines, such as dimethylbenzylamine, N-methyl- or N-ethylmorpholine, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo (3,3,0) octane and preferably triethylene diamine and metal salts such as tin dioctoate , Lead octoate and tin diethylhexoate and preferably tin (II) salts and dibutyltin dilaurate, and preferably mixtures of tertiary amines and organic tin salts. In order to achieve reaction times which are favorable in terms of foaming, the amount to be used is determined empirically depending on the reactivity of the chosen catalyst or the catalyst mixture determined by constitution. If the polyurethane foams according to the invention are produced on site by the one shot process, the catalysts and amounts must be selected such that the starting times at reaction temperatures from 0 ° to 35 ° C. are approximately 2 to 10 seconds, preferably 2 to 5 seconds. The start time (creamtime) is the time of the trouble-free pourability of the foamable mixture, ie the time available from mixing to the start of a visible reac tion, in which mixing of the starting materials, discharge from the mixing element and spraying of the reaction mass must be carried out.

Nach einer anderen Verfahrensvariante werden aus den obengenannten Ausgangskomponenten unter Verwendung von üblichen Katalysatoren zur Blockschaumherstellung Polyurethan-Blockschaumstoffe hergestellt, die als solche auf der ölhaltigen Wasseroberfläche ausgebreitet, nach der Absorption von Öl eingesammelt und ausgepreßt werden können oder die zerkleinert und als Füllmaterial für Absorptionssäulen Anwendung finden können.According to another process variant, polyurethane block foams are produced from the starting components mentioned above using conventional catalysts for the production of block foam, which as such are spread out on the oil-containing water surface, can be collected and pressed out after the absorption of oil, or can be comminuted and used as a filling material for absorption columns can.

Der Reaktionsmischung können auch noch Hilfsmittel und Zusatzstoffe einverleibt werden. Genannt seien beispielsweise Stablisatoren, Hydrolysenschutzmittel, Porenregler und oberflächenaktive Stoffe.Auxiliaries and additives can also be incorporated into the reaction mixture. Examples include stabilizers, hydrolysis protection agents, pore regulators and surface-active substances.

In Betracht kommen beispielsweise oberflächenaktive Substanzen, welche zur Unterstützung der Homogenisierung der Ausgangsstoffe dienen und gegebenenfalls auch geeignet sind, die Zellstruktur der Schaumstoffe zu regulieren. Genannt seien beispielhaft Siloxan-Oxyalkylen-Mischpolymerisate und andere Organopolysiloxane, oxäthylierte Alkylphenole, oxäthylierte Fettalkohole, Paraffinöle, Rizinusöl- bzw. Rizinolsäureester und Türkischrotöl, die in Mengen von 0,2 bis 6 Gewichtsteilen pro 100 Gewichtsteile Polyisocyanat angewandt werden.For example, surface-active substances are considered which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the foams. Examples include siloxane-oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or castor oil esters and Turkish red oil, which are used in amounts of 0.2 to 6 parts by weight per 100 parts by weight of polyisocyanate.

Nähere Angaben über die obenganannten üblichen Zusatz- und Hilfstoffe sind der Fachliteratur, beispielsweise der Monographie von Saunders und Frisch "High Polymers" Band XVI, "Polyurethanes", Teil 1 und 2, 1967 zu entnehmen.Further information on the above-mentioned customary additives and auxiliaries can be found in the specialist literature, for example the monograph by Saunders and Frisch "High Polymers" Volume XVI, "Polyurethanes", Parts 1 and 2, 1967.

Wie bereits dargelegt wurde, können die erfindungsgemäßen Polyurethanschaumstoffe nach dem Präpolymer- und vorzugsweise nach dem one shot-Verfahren hergestellt werden.As already explained, the polyurethane foams according to the invention can be produced by the prepolymer and preferably by the one-shot process.

Erfolgt die Polyurethanschaumstoffherstellung nach dem one shot-Verfahren, so wird üblicherweise eine Mischung aus Polyhydroxyverbindung, lipophiler Verbindung, Wasser und gegebenenfalls Kettenverlängerungsmittel mit dem organischen Polyisocyanat in Gegenwart von Hilfs-und Zusatzstoffen bei Temperaturen von 0° bis 35°, vorzugsweise 15° bis 25°C in solchen Mengen zur Umsetzung gebracht, daß das Verhältnis von Zerewitinoff aktiven Wasserstoffatomen der Polyhydroxyverbindungen, lipophilen Verbindungen und gegebenenfalls Kettenverlängerungsmitteln zu NCO-Gruppe des Polyisocyanats 0,7 bis 1,3:1, vorzugsweise ungefähr 1:1 beträgt und das Verhältnis sämtlicher Zerewitinoff aktiver Wasserstoffatome-gebunden an Polyhydroxyverbindung, lipophile Verbindung, gegebenenfalls Kettenverlängerungsmittel und Wasser zu NCO-Gruppe des Polyisocyanats ungefähr 1,3 bis 5:1, vorzugsweise von 1,5 bis 3:1 ist. Bei Verwendung einer Misch--kammer mit mehreren Zulaufdüsen können die Ausgangskomponenten einzeln zugeführt und in der Mischkammer intensiv vermischt werden. Als besonders zweckmäßig hat es sich jedoch erwiesen, nach dem Zweikomponenten-Verfahren zu arbeiten und die Mischung aus Polyhydroxyverbindung, lipophiler Verbindung, gegebenenfalls Kettenverlängerungsmittel und Wasser sowie Katalysatoren, Hilfsmitteln und Zusatzstoffen zu der Komponente A zu vereinigen und als Komponente B die organischen Polyisocyanate zu verwenden. Vorteilhaft ist hierbei nicht nur, daß die Komponenten A und B getrennt beschränkte Zeit gelagert und raumsparend transportiert werden können, sondern vorteilhaft ist insbesondere, daß die Komponenten zur Herstellung der Polyurethanschaumstoffe vor Ort nur intensiv gemischt werden müssen. Die Verteilung der erfindungsgemäßen hydrophoben Polyurethanschaumstoffe auf Gewässern sowie die Abtrennung der mit 01 und/oder halogenhaltigen; hydrophoben Lösungsmitteln getränkten Polyurethanschaumstoffe von der Wasseroberfläche erfolgt mit Hilfe bekannter Vorrichtungen, die zweckmäßigerweise auf Schiffen oder in Flugzeugen installiert sind. ,If the polyurethane foam is produced by the one shot process, a mixture of polyhydroxy compound, lipophilic compound, water and optionally chain extender with the organic polyisocyanate in the presence of auxiliaries and additives is usually used at temperatures from 0 ° to 35 °, preferably 15 ° to 25 ° ° C implemented in such amounts that the ratio of Zerewitinoff active hydrogen atoms of the polyhydroxy compounds, lipophilic compounds and optionally chain extenders to the NCO group of the polyisocyanate is 0.7 to 1.3: 1, preferably approximately 1: 1, and the ratio of all Zerewitinoff active hydrogen atoms bonded to polyhydroxy compound, lipophilic compound, optionally chain extender and water to the NCO group of the polyisocyanate is approximately 1.3 to 5: 1, preferably 1.5 to 3: 1. If a mixing chamber with several inlet nozzles is used, the starting components can be fed in individually and mixed intensively in the mixing chamber. However, it has proven to be particularly expedient to work according to the two-component process and to combine the mixture of polyhydroxy compound, lipophilic compound, optionally chain extender and water, as well as catalysts, auxiliaries and additives, into component A and to use the organic polyisocyanates as component B. . It is advantageous not only that components A and B can be stored separately for limited time and transported in a space-saving manner, but it is particularly advantageous that the components for producing the polyurethane foams only have to be mixed intensively on site. The distribution of the hydrophobic polyurethane foams according to the invention on water and the separation of those containing 01 and / or halogen; Polyurethane foams impregnated with hydrophobic solvents from the water surface are made with the aid of known devices which are expediently installed on ships or in aircraft. ,

Werden die Polyurethanschaumstoffe nach dem Präpolymerverfahren 1--rgestellt, so werden die NCO-Gruppen aufweisende Präpolymeren, vorzugsweise in Form von (ösungen in organischen Lösungsmitteln, vorteilhafterweise unter Wasser verdüst. Durch Variation des Lösungsmittels kann das Sink-, Steigoder Schwebeverhalten über die Dichte der Präpolymerlösung in gewissen Grenzen variiert werden. Als geeignete Lösungsmittel kommen vorzugsweise solche in Betracht, die mit dem NCO-Gruppen aufweisenden Präpolymeren und dem zu absorbierenden Öl gut mischbar sind. Genannt seien beispielsweise Methylenchlorid, Toluol, Cylclohexan, Hexan u.a. Durch Wahl des Katalysators kann der Zeitpunkt der Umsetzung zu Polyurethanen beeinflußt werden. Durch das bei der Reaktion der NCO-Gruppen haltigen Präpolymeren mit Wasser gebildete Kohlendioxid wird die schaumfähige Präpolymermischung unter gleichzeitigem Aufschäumen aufgetrieben. Das expandierende und bereits expandierte Material steigt an die Wasseröberfläche und absorbiert von unten die aufliegende Öl- bzw. Lösungsmittelschicht. Die mit Öl und gegebenenfalls halogenhaltigen, hydrophoben Lösungsmittel getränkten Polyurethane können danach mit bekannten Methoden von der Wasseroberfläche abgetrennt werden. Zur Herstellung der NCO-Gruppen haltigen Präpolymeren werden die bereits genannten Polyisocyanate und Mischungen aus Polyhydroxyverbindungen und lipophilen Verbindungen in Gegenwart von gegebenenfalls Hilfs- und Zusatzstoffen in solchen Mengen zur Umsetzung gebracht, daß das Verhältnis von NCO-Gruppen zu Gesamthydroxyl der Mischung 50:1 bis 2:1, vorzugsweise 15:1 bis 5:1 beträgt.If the polyurethane foams are prepared according to prepolymer process 1 - , the prepolymers containing NCO groups, preferably in the form of solutions in organic solvents, are advantageously atomized under water Suitable polymer solvents are preferably those which are readily miscible with the prepolymer containing NCO groups and the oil to be absorbed, for example methylene chloride, toluene, cyclohexane, hexane and others The foamable prepolymer mixture is expanded with simultaneous foaming by the carbon dioxide formed during the reaction of the prepolymers containing NCO groups with water, and the expanding and already expanded material rises to the surface of the water d absorbs the overlying oil or solvent layer from below. The polyurethanes impregnated with oil and optionally halogen-containing, hydrophobic solvents can then be separated from the water surface using known methods. To prepare the prepolymers containing NCO groups, the polyisocyanates and mixtures of polyhydroxy compounds and lipophilic compounds mentioned above are reacted in the presence of any auxiliaries and additives in amounts such that the ratio of NCO groups to total hydroxyl of the mixture is 50: 1 to 2: 1, preferably 15: 1 to 5: 1.

Die erfindungsgemäßen hydrophoben Polyurethanschaumstoffe besitzen aufgrund ihres chemischen Aufbaus, ihrer Dichte und des Verhältnisses von offenen zu geschlossenen Zellen ein hohes Absorptionsvermögen für. Öl, beispielsweise Roh-, Heiz- und Dieselöl sowie für gegebenenfalls halogenhaltige hydrophobe Verbindungen, beispielsweise Lösungsmittel wie Hexan, Benzol, Toluol, Anilin, Chloroform, Tetrachlorkohlenstoff, Dichloräthan und Hexachiorcyclopentadien.Because of their chemical structure, their density and the ratio of open to closed cells, the hydrophobic polyurethane foams according to the invention have a high absorption capacity for. Oil, for example crude, heating and diesel oil and for halogen if necessary containing hydrophobic compounds, for example solvents such as hexane, benzene, toluene, aniline, chloroform, carbon tetrachloride, dichloroethane and hexachiorcyclopentadiene.

Die in den Beispielen genannten Teile beziehen sich auf das Gewicht.The parts mentioned in the examples relate to the weight.

Beispiel 1example 1

Zur Herstellung des Polyurethanschaumstoffes wird eine Mischung aus

Figure imgb0001

  • bei Raumtemperatur mit
  • 200 Teilen einer Mischung aus Diphenylmethan-diisocyanaten und Polyphenyl-polymethylen-polyisocyanaten (Roh-MDJ)
  • zur Reaktion gebracht.
A mixture of is used to produce the polyurethane foam
Figure imgb0001
  • at room temperature with
  • 200 parts of a mixture of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (raw MDJ)
  • brought to reaction.

Vergleichsbeispiel AComparative Example A Eine Mischung ausA mix of

Figure imgb0002
werden bei Raumtemperatur mit

  • 118 Teilen Toluylendiisocyanat

umgesetzt.
Figure imgb0002
 are using at room temperature
  • 118 parts of tolylene diisocyanate

implemented.

Vergleichsbeispiel BComparative Example B

Man verfährt analog den Angaben von Vergleichsbeispiel A, verwendet jedoch anstelle von Rizinusöl 20 Teil TallölThe procedure is analogous to that of Comparative Example A, but 20 parts of tall oil are used instead of castor oil

Vergleichsbeispiel CComparative Example C

Man verfährt analog den Angaben von Vergleichsbeispiel B, verwendet jedoch anstelle von Toluylendiisocyanat 200 Teile Roh-MDJ.The procedure is analogous to that of Comparative Example B, but 200 parts of crude MDJ are used instead of tolylene diisocyanate.

Beispiel 2 bis 5Examples 2 to 5

Zur Herstellung von Polyurethanschaumstoffen werden Mischungen aus den in Tabelle 1 zusammengefaßten Komponenten bei Raumtemperatur (25°C) mit

  • 200 Teilen einer Mischung aus Diphenylmethan-diisocyanaten und Polyphenyl-polymethylen-polyisocyanaten (Roh-MDJ)

umgesetzt.For the production of polyurethane foams, mixtures of the components summarized in Table 1 are used at room temperature (25 ° C.)
  • 200 parts of a mixture of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (raw MDJ)

implemented.

Die erhaltenen Kenndaten und das Ölaufnahmevermögen der Schaumstoffe gemäß Beispiele 2 bis 5 und Vergleichsbeispiel A bis C sind in Tabelle 2 zusammengefaßt.

Figure imgb0003
Figure imgb0004
 The characteristic data obtained and the oil absorption capacity of the foams according to Examples 2 to 5 and Comparative Examples A to C are summarized in Table 2.
Figure imgb0003
Figure imgb0004

Beispiel 6Example 6

  • 25 Teil einer Mischung, bestehend aus
  • 21,7 Teilen eines trifunktionellen Polypropylenoxids mit einer OH-Zahl von 400 (Lupranol 3130 der BASF AG)
  • 21,7 Teilen eines Umsetzungsproduktes aus Ölsäure und Diäthanolamin (Luprintan HDF der BASF AG)
  • 1,3 Teilen eines silikonhaltigen Stabilisators (DC 190 der Dow Corning) und
  • 0,5-2 Teilen eines Aminkatalysators (Niax A1 der Union Carbide)

werden mit 25 bis 75 Teilen eines organischen Lösungsmittels verdünnt und anschließend mit 100 Teilen Roh-MDJ zu einem Isocyanatgruppen haltigen Präpolymeren umgesetzt.
  • 25 part of a mixture consisting of
  • 21.7 parts of a trifunctional polypropylene oxide with an OH number of 400 (Lupranol 3130 from BASF AG)
  • 21.7 parts of a reaction product from oleic acid and diethanolamine (Luprintan HDF from BASF AG)
  • 1.3 parts of a silicone-containing stabilizer (DC 190 from Dow Corning) and
  • 0.5-2 parts of an amine catalyst (Union Carbide Niax A1)

are diluted with 25 to 75 parts of an organic solvent and then reacted with 100 parts of crude MDJ to form a prepolymer containing isocyanate groups.

Die NCO-Gruppen haltige Präpolymerlösung wird anschließend unter Wasser verdüst.The prepolymer solution containing NCO groups is then atomized under water.

Die Art und Menge der organischen Lösungsmittel sowie die verwendeten Katalysatorkonzentrationen sind in Tabelle 3 zusammengefaßt.The type and amount of the organic solvents and the catalyst concentrations used are summarized in Table 3.

Das spezifische Gewicht des NCO-Gruppen haltigen Präpolymeren beträgt lösungsmittelfrei 1,3546 g/cm3.The specific weight of the prepolymer containing NCO groups is 1.3546 g / cm 3 without solvent.

Wie Tabelle 3 zeigt, kann durch Mischen des Präpolymeren mit organischen Lösungsmitteln die Dichte der Präpolymerlösung von 0,922 bis 1,333 g/cm3 variiert werden.

Figure imgb0005
As shown in Table 3, the density of the prepolymer solution can be varied from 0.922 to 1.333 g / cm 3 by mixing the prepolymer with organic solvents.
Figure imgb0005

Beispiel 7 bis 19 und Vergleichsbeispiele D und EExamples 7 to 19 and Comparative Examples D and E

Analog den Angaben von Beispiel 1 werden aus den in Tabelle 4 zusammengefaßten Ausgangskomponenten erfindungsgemäße Polyurethanschaumstoffe und gemäß Tabelle 5 zum Stand der Technik gehörende Vergleichsprodukte hergestellt.Analogous to the information in Example 1, polyurethane foams according to the invention and table 5 comparative products according to the prior art are produced from the starting components summarized in Table 4.

Als Katalysator zur Herstellung der erfindungsgemäßen Schaumstoffe wird eine Mischung aus

  • 4 Teilen Dimethyläthanolamin,
  • 3 Teilen Triäthylen-diamin (ODabco 33LV der Firma Houdry Process) und
  • 2 Teilen eines Aminkatalysators (@Niax A 1 der Union Carbide Corp.)

verwendet.
Figure imgb0006
Figure imgb0007
 A mixture of is used as a catalyst for producing the foams according to the invention
  • 4 parts of dimethylethanolamine,
  • 3 parts of triethylene diamine (ODabco 33LV from Houdry Process) and
  • 2 parts of an amine catalyst (@Niax A 1 from Union Carbide Corp.)

used.
Figure imgb0006
Figure imgb0007

Abkürzungen:Abbreviations:

Figure imgb0008
Figure imgb0008

Das Ölaufnahmevermögen der erfindungsgemäß hergestellten Schaumstoffe und Vergleichschaumstoffe wurde auf folgende Weise ermittelt:

  • Eine Wasseroberfläche von 1200 cm2 wurde mit 250 g der in Tabelle 6 genannten unpolaren Flüssigkeiten überschichtet. Auf die verunreinigte Oberfläche wurde eine 5 mm dicke Schaumstoffplatte 15 Minuten aufgelegt. Die Ölaufnahme wurde durch Auswiegen der Schaumplatte als das Vielfache des Schaumstoffgev thts nach folgender Gleichung bestimmt:
    Figure imgb0009
The oil absorption capacity of the foams and comparative foams produced according to the invention was determined in the following way:
  • A water surface of 1200 cm 2 was covered with 250 g of the non-polar liquids listed in Table 6. A 5 mm thick foam sheet was placed on the contaminated surface for 15 minutes. The oil absorption was determined by weighing the foam sheet as a multiple of the foam weight according to the following equation:
    Figure imgb0009

Die erhaltenen Ölaufnahmefaktoren sind in Tabelle 6 zusammengefaßt.

Figure imgb0010
The oil absorption factors obtained are summarized in Table 6.
Figure imgb0010

Die Versuche zeigen das sehr hohe Ölaufnahmevermögen der erfindungsgemäßen Schaumstoffe im Vergleich zu konventionellen Hart- und Weichschaumstoffen.The tests show the very high oil absorption capacity of the foams according to the invention in comparison to conventional rigid and flexible foams.

Säulentrennung: Eine Glas-Säule wurde mit Schaumstoffschnitzeln gefüllt und mit einer Mischung aus Wasser und unpolaren Flüssigkeiten bis zur Sättigung der Schaumstoffschnitzel beschickt. Die erhaltenen Ölaufnahmefaktoren sind in Tabelle 7 zusammengefaßt.

Figure imgb0011
Column separation: A glass column was filled with foam chips and charged with a mixture of water and non-polar liquids until the foam chips were saturated. The oil absorption factors obtained are summarized in Table 7.
Figure imgb0011

Claims (3)

1. Hydrophobic polyurethane foams for the absorption of oil and/or hydrophobic compounds, which may or may not contain halogen, from water, produced by reacting organic polyisocyanates with polyhydroxy compounds in the presence of water as blowing agent and catalysts, with or without lipophilic compounds, chain extenders, assistants and additives, which foams have (a) a density of from 5 to 26.5 g/liter, and in which (b) the number of closed cells is from 3 to 30%, and the number of open cells is from 97 to 70%, based on the total number of cells, and in which (c) the polyhydroxy compounds used are linear and/or branched hydroxyl-containing polyethers which have molecular weights of from 300 to 10,000 and are obtained by polymerizing tetrahydrofuran, 1,2- and 2,3-butylene oxide, propylene oxide or a mixture of propylene oxide and ethylene oxide in which the ethylene oxide content is less than 20% by weight, based on the total weight of the mixture.
2. Hydrophobic polyurethane foams as claimed in claim 1, in which (c) the polyhydroxy compounds used are di- or trifunctional hydroxyl-containing polypropylene oxides having molecular weights of from 2000 to 6000.
3. Hydrophobic polyurethane foams as claimed in claim 1, produced by the one-shot process in the presence of lipophilic compounds, which foams have (a) a density of from 6.8 to 18 g/liter, and in which (d) the lipophilic compounds used are substituted or unsubstituted, saturated and/or unsaturated aliphatic fatty acids of 10 to 25 carbon atoms, and their esters with alcohols of 2 to 20 carbon atoms, and their amides, with the proviso that (e) the molar ratio of polyhydroxy compounds to lipophilic compounds is from 1:3 to 1:20, and (f) the starting components are reacted in such amounts that (i) the ratio of all hydrogen atoms which are capable of undergoing a Zerewitinoff reaction and are bonded to the polyhydroxy compounds, water, lipophilic compounds and any chain extender, to the NCO groups of the polyisocyanates is from 1.3 to 5:1, and (ii) the ratio of hydrogen atoms which are capable of undergoing a Zerewitinoff reaction and are bonded to the polyhydroxy compounds, lipophilic compounds and any chain extender, to the NCO groups of the polyisocyanates is from 0.7 to 1.3:1.
EP78100702A 1977-08-25 1978-08-18 Hydrophobic polyurethane foams, process for their manufacture and their use to absorb oil and halogenated hydrophobic compounds, which may be halogenated, from water Expired EP0000933B1 (en)

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