WO2016202767A1 - Composite à base de polyuréthane pour la neutralisation d'un drainage minier acide (amd) - Google Patents

Composite à base de polyuréthane pour la neutralisation d'un drainage minier acide (amd) Download PDF

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Publication number
WO2016202767A1
WO2016202767A1 PCT/EP2016/063564 EP2016063564W WO2016202767A1 WO 2016202767 A1 WO2016202767 A1 WO 2016202767A1 EP 2016063564 W EP2016063564 W EP 2016063564W WO 2016202767 A1 WO2016202767 A1 WO 2016202767A1
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component
diisocyanate
process according
polyurethane
polyurethane composite
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PCT/EP2016/063564
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English (en)
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Wei Leng
Daniel Freidank
Su-Ting LIU
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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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/0058—≥50 and <150kg/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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to a polyurethane composite for neutralization of an acid mine drainage, to a process for preparing said polyurethane composite, to a process for neutralization of an acid mine drainage with said polyurethane composite, and also to the use of said polyurethane composite for neutralization of an acid mine drainage.
  • An object of the present invention is to provide a polyurethane composite for neutralization of an acid mine drainage in a controlled manner.
  • a further object of the present invention is to provide a process for preparing said polyurethane composite.
  • a further object of the present invention is to provide a process for neutralization of an acid mine drainage with said polyurethane composite.
  • a further object of the present invention is to provide the use of said polyurethane composite for neutralization of an acid mine drainage.
  • a polyurethane composite comprising a polyurethane matrix and a neutralization agent dispersed in the polyurethane matrix in a loading amount of 1 to 60 wt-%, preferably 3 to 50 wt-%, more preferably 5 to 40 wt-%, based on the whole polyurethane composite.
  • the present invention also relates to a process for preparing said
  • the present invention also relates to a process for neutralization of an acid mine drainage with said polyurethane composite. In another aspect, the present invention also relates to the use of said polyurethane composite for neutralization of an acid mine drainage.
  • Said polyurethane composite comprises a polyurethane matrix and a neutralization agent dispersed in the polyurethane matrix.
  • polyurethane to be used in the present invention are those that can be loaded with the neutralization agent, including but not limited to flexible polyurethane foam, rigid polyurethane foam or even compact polyurethane.
  • Examples of the neutralization agent to be used in the present invention is usually a base or a salt of strong base and weak acid, which can react with acid and is selected from the group consisting of alkali metal hydroxide such as sodium hydroxide, alkaline earth metal hydroxide such as calcium hydroxide, alkali metal carbonate such as sodium carbonate, alkaline earth metal carbonate such as calcium carbonate and calcium hydrogen carbonate. Alkaline earth metal carbonate is preferred. Calcium carbonate is more preferred.
  • the neutralization agent is used in a loading amount of 1 to 60 wt-%, preferably 3 to 50 wt-%, more preferably 5 to 40 wt-%, based on the whole polyurethane composite.
  • a neutralization agent is mechanically dispersed in one of components for a polyurethane which include component A which is a mixture of polyhydroxy compounds and additives preferably selected from the group consisting of blowing agents, cell openers, catalysts, surfactants, chain extenders, crosslinkers and the mixtures thereof, and component B which is an isocyanate, and then component A is mechanically mixed and reacted with component B.
  • polyetherols and/or polyesterols especially those having from 2 to 8 hydrogen atoms which are reactive toward isocyanate, in particular di- and/or trifunctional polyetherols and/or polyesterols.
  • the polyetherols used are obtained by known methods, for example by polymerization of alkylene oxides with addition of at least one starter molecule which comprises from 2 to 8, preferably from 2 to 6, reactive hydrogen atoms in bound form in the presence of alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal alkoxides such as sodium methoxide, sodium or potassium ethoxide or potassium isopropoxide, or Lewis acids such as antimony pentachloride, boron trifluoride etherate or bleaching earth, and also double metal cyanide compounds, known as DMC catalysts.
  • alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal alkoxides
  • Lewis acids such as antimony pentachloride, boron trifluoride etherate or bleaching earth
  • DMC catalysts double metal cyanide compounds
  • alkylene oxides preference is given to using one or more compounds having from 2 to 4 carbon atoms in the alkylene radical, e.g. tetrahydrofuran, 1 ,2- or 1 ,3-propylene oxide, 1 ,2- or 2,3-butylene oxide, in each case alone or in the form of mixtures, and preferably ethylene oxide and/or 1 ,2- or 1 ,3-propylene oxide.
  • alkylene radical e.g. tetrahydrofuran, 1 ,2- or 1 ,3-propylene oxide, 1 ,2- or 2,3-butylene oxide
  • Possible starter molecules are, for example, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, hexitol derivatives such as sorbitol, or diamine or polyamine, such as toluenediamine, ethylenediamine,
  • diethylenetriamine 4,4'-methylenedianiline, 1 ,3-propanediamine, 1 ,6-hexanediamine, and also other dihydric or polyhydric alcohols or difunctional or polyfunctional amines, and the mixtures thereof.
  • polyesterols used are usually prepared by condensation of polyfunctional alcohols having from 2 to 12 carbon atoms, e.g. ethylene glycol, diethylene glycol, butanediol,
  • Suitable polyesterols are the phthalic anhydride derived polyester polyols obtained from esterification of phthalic anhydride with an aliphatic polyhydric alcohol.
  • the phthalic anhydride derived polyester polyol is the reaction product of phthalic anhydride and diethylene glycol.
  • the polyhydroxy compounds used are preferably selected from the group consisting of trifunctional polyether polyol containing primary hydroxyl groups, a higher functional polyether polyol based on sucrose, phthalic anhydride-diethylene glycol copolymer, polyether polyol containing multiple hydroxyl groups and a primary amino group (-NH 2 ) as the starting point, for example, Lupranol 2090 available from BASF, Lupranol 3423 available from BASF, Stepanpol PS 3152 available from Stepan Jinling, Lupranol VP 9346 EX Korea available from BASF, and the mixtures thereof.
  • the polyhydroxy compounds are normally used in an amount of 60 to 99 wt-%, preferably 75 to 98 wt-%, more preferably 80 to 96 wt-%, based on the total weight of the component A.
  • blowing agents it is possible to use physical (inert) or reactive (chemical) blowing agents.
  • Physical blowing agents are well known to those in the art and include a variety of saturated and unsaturated hydrocarbons having relatively low molecular weights and boiling points. Examples are butane, isobutane, pentane, isopentane, hexane, and heptane. Generally the boiling point is chosen such that the heat of the polyurethane-forming reaction will promote volatilization.
  • the most commonly used physical blowing agents are currently the halocarbons, particularly the chlorofluorocarbons.
  • Examples are methyl chloride, methylene chloride, tnchlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, chlorodifluoromethane, the chlorinated and fluorinated ethanes, and the like. Brominated hydrocarbons may also be useful. Blowing agents are listed in the Polyurethane Handbook on page 101.
  • Chemical blowing agents are generally low molecular weight species which react with isocyanates to generate carbon dioxide. Water can be used as chemical blowing agent.
  • water can also be used in combination with physical blowing agents mentioned above.
  • the content of water is preferably greater than 40 wt-%, particularly preferably greater than 60 wt-% and very particularly preferably greater than 80 wt-%, based on the total weight of the blowing agent.
  • the blowing agent used is water, especially distilled water.
  • the blowing agents are normally used in an amount of 0.1 to 10 wt-%, preferably 0.8 to 5 wt-%, more preferably 1 .2 to 3 wt-%, based on the total weight of the component A.
  • the cell openers it is possible to use all compounds which can minimize the extent of formation of closed cells in preparing the polyurethane foams.
  • the cell openers are polyether polyols, especially trifunctional polyether polyols, for example Lupranol 2048 available from BASF.
  • the cell openers are normally used in an amount of 0 to 10 wt-%, preferably 1 to 6 wt-%, more preferably 1 .5 to 2.5 wt-%, based on the total weight of the component A.
  • catalysts it is possible to use all compounds which accelerate the isocyanate-polyol reaction. Such compounds are known and are described, for example, in “Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3 rd edition 1993, chapter 3.4.1 . These include amine-based catalysts and catalysts based on organic metal compounds.
  • organic tin compounds such as tin(ll) salts of organic carboxylic acids, e.g. tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexanoate and tin(ll) laurate, and the dialkyltin(IV) salts of organic carboxylic acids, e.g.
  • dibutyltin diacetate dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate
  • bismuth carboxylates such as bismuth(lll) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate or alkali metal salts of carboxylic acids, e.g.
  • potassium acetate or potassium formate and/or highly basic amines, for example tertiary amines such as triethylamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, 1 ,2-dimethylimidazole, dimethylcyclohexylamine,
  • tertiary amines such as triethylamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, 1 ,2-dimethylimidazole, dimethylcyclohexylamine
  • the catalysts used are selected from the group consisting of Dabco 33lv available from Air Product, Dabco 8154 available from Air Product, Dabco BL1 1 available from Air Product, Polycat 8 available from Air Product and the mixtures thereof.
  • the catalysts are normally used in an amount of 0.1 to 10 wt-%, preferably 0.3 to 8 wt-%, more preferably 0.5 to 5 wt-%, based on the total weight of the component A.
  • Suitable surfactants include any surfactant known in the art, such as a silicone surfactant which may include, but is not limited to, bulk and surface silicone surfactants and combinations thereof, and a non-silicone surfactant which may be used with the bulk and surface silicone surfactants or alone.
  • the surfactant may include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and combinations thereof.
  • the surfactant typically includes, but is not limited to, polyoxyalkylene polyol surfactants, alkylphenol ethoxylate surfactants, and combinations thereof.
  • the surfactant is selected from the group of silicone surfactants, salts of sulfonic acids, alkali metal and/or ammonium salts of oleic acid, stearic acid, dodecylbenzene- or dinaphthylmethane-disulfonic acid, and ricinoleic acid, foam stabilizers such as
  • siloxaneoxyalkylene copolymers and other organopolysiloxanes oxyethylated alkyl-phenols, oxyethylated fatty alcohols, paraffin oils, castor oil, castor oil esters, and ricinoleic acid esters, and cell regulators, such as paraffins, fatty alcohols, dimethylpolysiloxanes, and combinations thereof.
  • the surfactant is a silicone. More specifically, the silicone is typically a
  • the surfactant may be selected according to the reactivity of the polyhydroxy compounds used.
  • the surfactants used are selected from the group consisting of Tegostab 8734 If2 available from Evonik, Dabco DC 193 available from Air Product, and the mixtures thereof.
  • the surfactants are normally used in an amount of 0.1 to 10 wt-%, preferably 0.5 to 5 wt-%, more preferably 0.7 to 3 wt-%, based on the total weight of the component A.
  • Chain extenders and/or crosslinkers used are, in particular, bifunctional or trifunctional or higher-functional compounds, in particular diols, triols or both, in each case preferably having molecular weights of less than 350 g/mol, more preferably from 60 to 300 g/mol and in particular from 60 to 250 g/mol.
  • the bifunctional compounds are generally referred to as chain extenders and trifunctional or higher-functional compounds are generally referred to as crosslinkers.
  • Possibilities are, for example, aliphatic, cycloaliphatic and/or aromatic diols having from 2 to 14, preferably from 2 to 10, carbon atoms, e.g.
  • chain extenders used are selected from the group consisting of dipropylene and tripropylene glycols, and the mixtures thereof, especially dipropylene glycol.
  • the chain extenders are normally used in an amount of 0 to 20 wt-%, preferably 5 to 15 wt-%, more preferably 8 to 1 1 wt-%, based on the total weight of the component A.
  • the crosslinker used is glycerine.
  • the crosslinkers are normally used in an amount of 0 to 15 wt-%, preferably 1 to 8 wt-%, preferably 2 to 3.5 wt-%, based on the total weight of the component A.
  • the component B it is possible to use commonly known aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, examples being tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, 2-ethylbutylene 1 ,4- diisocyanate, pentamethylene 1 ,5-diisocyanate, butylene 1 ,4-diisocyanate, 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1 ,4- and/or 1
  • aliphatic diisocyanates in particular HDI
  • aromatic diisocyanates such as 2,2'-, 2,4'- and/or 4, 4'-MDI and mixtures of the aforementioned isomers, PMDI, mixtures of 2,2'-, 2,4'- and/or 4,4'-diphenylmethane diisocyanate and PMDI (crude MDI), more preferably 4,4'-MDI, PMDI.
  • prepolymers and mixtures of the above-described isocyanates and prepolymers can be used as isocyanate component.
  • prepolymers are prepared from the above- described isocyanates and the polyethers, polyesters or both.
  • the isocyanates used are selected from the group consisting of Lupranat ME available from BASF, Lupranat Ml available from BASF, Lupranat M 20 s available from BASF, and the mixtures thereof.
  • the isocyanates are normally used in an amount of 10 to 80 wt-%, preferably 25 to 70 wt-%, more preferably 30 to 65 wt-%, based on the sum of the component A and the component B.
  • a process for preparing said polyurethane composite in which the neutralization agent is mechanically dispersed in component A and then component A is mechanically mixed and reacted with component B.
  • component A and component B can be reacted in such amounts that the equivalence ratio of NCO groups of component B to the sum of the reactive hydrogen atoms of component A is 0.5-2:1 , preferably 0.85-1.25:1 , more preferably 0.95-1.15:1 (index by mole (-NCO: -OH)).
  • the neutralization agent is released out of polyurethane matrix, and reacts with acid.
  • the pH value changes from acidic to neutral and ends in basic.
  • the time span varies from several minutes to weeks, depending on the loading amount of neutralization agent (the more the shorter).
  • the neutralization agent shows controlled release by contacting with the acid mine drainage.
  • the release time can be controlled by varying the loading amount.
  • said polyurethane composite can also be used for neutralization of a solution containing mineral acid, particularly an aqueous solution containing sulfuric acid or hydrochloric acid. Therefore, the neutralization of a solution containing mineral acid can be used to simulate the neutralization of acid mine drainage.
  • Component A and 29.2 g of CaCC"3 were introduced into a 500 ml PE cup at room temperature and mixed at 1200 rpm for 5 min to form a mixture of Component A and CaCC"3.
  • Component B is a compound having Component B:
  • Component B was introduced in a 1 L PE bottle and heated to 47°C. The bottle was then put on two Rollers Bottle Mill for mixing until the temperature of mixture is decreased to room temperature.
  • Component B 122.92 g of Component B is added into 280 g of the mixture of Component A and CaCC"3 in a 500 ml PE cup and mixed at 1500 rpm for 5 seconds, and then the mixture is poured into a 25 * 25 * 25 (cm * cm * cm) PMMA mold. The foam is demoulded after 30min and the foam is cut into 6x6x6 cm pieces.
  • the change of pH is recorded with time, and results are illustrated in Figure 2.
  • Component A is a compound having Component A:
  • Component A and 76.25 g of CaCC"3 were introduced a 500 ml PE cup at room temperature and mixed at 1200 rpm for 5 min to form a mixture of component A and CaCC"3.
  • Component B is a compound having Component B:
  • the advantage of using rigid foam as matrix lies in that less material is required for neutralization, compared to flexible foam matrix.
  • neutralization agent shows controlled release by contacting with acid mine drainage, and release time can be controlled by varying the loading amount and the sample amount.
  • the polyurethane composite for neutralization according to the present invention is beneficial to environmental protection without directly throwing a base or a salt used as neutralization agent into acid mine drainage.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un composite à base de polyuréthane pour la neutralisation contrôlée d'un drainage minier acide, son procédé de préparation, un procédé de neutralisation d'un drainage minier acide à l'aide dudit composite à base de polyuréthane, ainsi que l'utilisation dudit composite à base de polyuréthane pour la neutralisation d'un drainage minier acide.
PCT/EP2016/063564 2015-06-19 2016-06-14 Composite à base de polyuréthane pour la neutralisation d'un drainage minier acide (amd) WO2016202767A1 (fr)

Applications Claiming Priority (2)

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CN2015081966 2015-06-19
CNPCT/CN2015/081966 2015-06-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485588A (zh) * 2018-04-11 2018-09-04 安平县三联过滤器材有限公司 一种双组份聚氨酯胶黏剂及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911379A (en) * 1955-07-11 1959-11-03 Pittsburgh Plate Glass Co Use of alkaline materials in the preparation of polyurethane foams
US3772219A (en) * 1972-01-19 1973-11-13 I Schwarz Flexible polyurethane foam composition
US4931481A (en) * 1986-09-27 1990-06-05 Bayer Aktiengesellschaft Process for the production of foams based on aromatic isocyanates using MG(OH)2 and the foams produced thereby
WO1996028251A1 (fr) * 1995-03-10 1996-09-19 Montech Pty. Ltd. Sorbant polymere pour procede de recuperation d'ions
GB2334960A (en) * 1996-10-24 1999-09-08 Sanyo Chemical Ind Ltd Composition capable of forming moldings of rigid polyurethane foam,moldings therof,and models made out of the moldings
US20120160752A1 (en) * 2010-12-24 2012-06-28 Korea Institute Of Geoscience And Mineral Resources(Kigam) Oxidation pond including baffles for treating acid mine drainage

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911379A (en) * 1955-07-11 1959-11-03 Pittsburgh Plate Glass Co Use of alkaline materials in the preparation of polyurethane foams
US3772219A (en) * 1972-01-19 1973-11-13 I Schwarz Flexible polyurethane foam composition
US4931481A (en) * 1986-09-27 1990-06-05 Bayer Aktiengesellschaft Process for the production of foams based on aromatic isocyanates using MG(OH)2 and the foams produced thereby
WO1996028251A1 (fr) * 1995-03-10 1996-09-19 Montech Pty. Ltd. Sorbant polymere pour procede de recuperation d'ions
GB2334960A (en) * 1996-10-24 1999-09-08 Sanyo Chemical Ind Ltd Composition capable of forming moldings of rigid polyurethane foam,moldings therof,and models made out of the moldings
US20120160752A1 (en) * 2010-12-24 2012-06-28 Korea Institute Of Geoscience And Mineral Resources(Kigam) Oxidation pond including baffles for treating acid mine drainage

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* Cited by examiner, † Cited by third party
Title
"Kunststoffhandbuch, Volume 7, Polyurethane", vol. 7, 1993, CARL HANSER VERLAG

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485588A (zh) * 2018-04-11 2018-09-04 安平县三联过滤器材有限公司 一种双组份聚氨酯胶黏剂及其制备方法和应用

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