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WO1996033231A1 - Procede de preparation d'un melange de polyisocyanate et de phosphate stable en stockage - Google Patents

Procede de preparation d'un melange de polyisocyanate et de phosphate stable en stockage Download PDF

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Publication number
WO1996033231A1
WO1996033231A1 PCT/US1996/004120 US9604120W WO9633231A1 WO 1996033231 A1 WO1996033231 A1 WO 1996033231A1 US 9604120 W US9604120 W US 9604120W WO 9633231 A1 WO9633231 A1 WO 9633231A1
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WO
WIPO (PCT)
Prior art keywords
polyisocyanate
mixture
group
dissolved gases
acid phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1996/004120
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English (en)
Inventor
Steven B. Lowenkron
Donald M. Ference
Daniel P. Martone
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to BR9608163A priority Critical patent/BR9608163A/pt
Priority to AU54319/96A priority patent/AU5431996A/en
Priority to EP96911430A priority patent/EP0821706A1/fr
Priority to JP8531745A priority patent/JPH11503786A/ja
Priority to MX9707969A priority patent/MX9707969A/es
Publication of WO1996033231A1 publication Critical patent/WO1996033231A1/fr
Priority to NO974785A priority patent/NO974785D0/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
    • 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
    • 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
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/3885—Phosphate 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur

Definitions

  • This invention relates to the field of polyisocyanates and, more particularly, to the field of storage-stable polyisocyanate/phosphate mixtures.
  • mixtures of polyisocyanates and phosphates are useful for various purposes.
  • such can be used as binder resins having releasing properties for wood composite materials.
  • These polyisocyanate compositions are particularly useful as binders in the preparation of particle boards and similar materials. See, for example, U.S. Patents 3,428,592; 3,440,189; 3,557,263; 3,636,199; 3,870,665; 3,919,017; and 3,930,1 10. While some of these mixtures can be made relatively storage-stable in that they do not deposit solids or separate into two liquid phases during relatively short-term storage (see, for example, U.S Patent 4,258,169, Re.
  • the present invention solves the problem of pressurization of containers. It is an improvement in a process for producing a storage-stable mixture of a polyisocyanate and an acid phosphate, wherein dissolved gases are present, comprising subjecting the mixture to a negative pressure for a time sufficient to remove at least a portion of the dissolved gases therefrom. Preferably the amount of dissolved gases is reduced by at least 10 percent by weight. It has been found that this evacuation, which is preferably carried out at a vacuum pressure of less than 50 mm Hg (2 inches Hg), for a time sufficient to remove at least 90 percent of the dissolved gases in the mixture, more preferably at least 99 percent, results in a mixture which, thereafter, shows markedly decreased gas production.
  • the invention therefore reduces or eliminates problems associated with pressurization of smaller containers used to ship or store the mixture.
  • the polyisocyanate/phosphorus-containing compound mixtures which are treated in the present invention can be prepared from a variety of materials and via a variety of routes.
  • the starting material includes one or more phosphorus-containing compounds formed in situ, which function as a release agent when the material is used in formulations which contact certain types of metal surfaces. It is prepared starting with a polyisocyanate and an acid phosphate. This is preferably a mixture of an organic polyisocyanate and from 1 to 20 parts, per 100 parts by weight of the polyisocyanate, of an acid phosphate selected from the group consisting of acid phosphates having the formula:
  • each R is independently selected from the group consisting of alkyl having at least 3 carbon atoms, alkenyl having at least 3 carbon atoms, aryl, aryl substituted by at least one alkyl group, alkyl substituted by at least one acyloxy group, wherein the acyl group is the residue of an aliphatic monocarboxylic acid having at least 2 carbon atoms, and
  • Ri is selected from the group consisting of alkyl, aryl, and aryl substituted by at least one alkyl
  • one of A and B represents hydrogen and the other is selected from the group consisting of hydrogen, methyl, chloromethyl and 2,2,2-trichloroethyl
  • X is chalcogen selected from the group consisting of oxygen and sulfur
  • m is a number having an average value of 1 to 25.
  • alkyl having at least 3 carbon atoms means a saturated monovalent aliphatic radical, straight chain or branched chain, which has the stated minimum number of carbon atoms in the molecule.
  • Illustrative of such groups are propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl, as well as those having many more carbon atoms such astriacontyl, pentatriacontyl, including isomeric forms thereof.
  • alkyl when used without the above carbon atom limitation is also inclusive of methyl and ethyl.
  • alkenyl having at least 3 carbon atoms means a monovalent straight or branched chain aliphatic radical containing at least one double bond, and having the stated minimum number of carbon atoms in the molecule.
  • Illustrative of such groups are allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, pentacosenyl. triacontenyl, pentatria-contenyl, including isomeric forms thereof.
  • aryl means the monovalent radical obtained by removing one nuclear hydrogen atom from an aromatic hydrocarbon.
  • aryl phenyl, naphthyl, biphenyl, triphenyl.
  • aryl substituted by at least one alkyl means an aryl radical, as above defined, carrying at least one alkyl (as above defined) substituent.
  • alkyl as above defined
  • aliphatic monocarboxylic acid having at least 2 carbon atoms is inclusive of any alkanoic or alkenoic acid having the stated minimum number of carbon atoms.
  • Illustrative of such acids are acetic, propionic, butyric, hexanoic, octanoic, lauric, stearic, oleic, undecylenic, dodecylenic, isocrotonic, palmitic.
  • Each of the groups R and Ri in the formulae (I) and (II) set forth above can optionally be substituted by one or more inert substituents, i.e., substituents which do not contain active hydrogen atoms and which are therefore unreactive in the presence of the ° polyisocyanate.
  • inert substituents are alkoxy, dialkylmercapto, alkenyloxy, dialkenylmercapto, chloro, bromo, iodo, fluoro, cyano.
  • the acid phosphates of the formulae (I) and (II) are, for the most part, well-known in the art, and can be prepared by methods well-known in the art.
  • the acid phosphates (I) and (II) are obtained by reaction of the corresponding alcohol or thiol R-XH, 5 wherein R and X are as hereinbefore defined, with phosphorus pentoxide or phosphorus oxysulfide using the procedures described by Kosolapof, Organophosphorus Compounds, John Wiley and Sons, Inc (New York, 1950), pp. 220-221.
  • This reaction gives rise to a mixture of the mono- and di-acid phosphates, which mixture can be separated, if desired, for example by fractional crystallization of the barium and like salts as described in the above cited reference.
  • the individual acid phosphates in the mixture of the mono- and di-acid phosphates obtained in accordance with the above reaction can be employed as starting materials in the process of the invention.
  • acid phosphates having the formula (I) and (II) above, to a product containing the corresponding pyrophosphates and their sulfur-containing analogues, 5 such as thiophosphates and pyrophosphothiolates, by heating the acid phosphates in the presence of an organic polyisocyanate, with or without any other reactant such as phosphorus oxychloride, phosgene and the like. If the conditions of heating are carefully controlled as described herein, the resulting product is a homogeneous liquid which can be stored for prolonged periods without any tendency to undergo phase separation.
  • the reaction would be expected to result in the formation of the desired pyrophosphate in association with some polyphosphate (if a mono-ester is present).
  • the reaction also would be expected to give rise to the intermediate formation of the amine (IV) corresponding to the starting isocyanate.
  • the amine (I ) would be expected to react immediately with additional isocyanate to form a urea. If a polyisocyanate were used a poly urea would be expected to form, and such should normally be insoluble in the reaction product and separate as a solid either immediately or on standing.
  • reaction temperature is not the only important factor. It is found that the time for which heating is carried out is important and, in general, the higher the reaction temperature, the shorter the period for which the heating can be carried out without consequences which are fatal to the improvement of phase stability in the reaction product. Illustratively, even when the reaction temperature is as low as 60°C, it is found that there is a limited time beyond which further heating causes transformation of the pyrophosphates into what are believed to be higher polyphosphates. When the proportion of the latter in the reaction product reaches a sufficiently high level it is found that on subsequent cooling of the reaction product, the polyphosphates separate generally as a liquid layer immiscible with the polyisocyanate. Further, the higher the reaction temperature, the shorter the period for which the reaction of acid phosphate and polyisocyanate can be allowed to continue without the onset of the above described transformation of the pyrophosphates.
  • the time and the temperature for which the process described hereinabove can be carried out can vary according to the particular acid phosphate and polyisocyanate, as well as the concentration of the acid phosphate, which are employed.
  • the appropriate time in any given instance can be determined readily by a process of trial and error.
  • the reaction times which can be employed vary from several hours at 60°C down to a minute or less at the higher end of the temperature range (190 ⁇ Q. As set forth above, the higher the temperature employed, the shorter the reaction time which can be employed without deleterious results.
  • the manner in which the acid phosphate and the organic polyisocyanate are brought together can also, in certain cases, affect the ability to produce a phase-stable composition in accordance with the invention. It is possible in many instances to bring the two reactants together, in any conventional manner, at ambient temperature, and then to heat the resulting mixture at a temperature within the range set forth for a time which has been determined to give the desired result at the particular reaction temperature chosen. However, it is preferred to preheat the polyisocyanate to the selected reaction temperature and then to add the acid phosphate to the preheated polyisocyanate. When operating a batch type procedure, the addition can be carried out in a single charge or can be carried out slowly over a period of time.
  • the process of the invention can also be carried out in a continuous manner in which the mixture of polyisocyanate (preferably preheated) and acid phosphate is passed through a heating zone maintained at a temperature within the range set forth above.
  • the rate of flow of mixture through the heating zone is adjusted so that the residence time in the mixing zone corresponds to the selected reaction time.
  • a wide variety of conventional equipment can be employed for this purpose.
  • a particularly useful apparatus is that of the type in which the mixture to be heated is spread in the form of a thin film over the walls of the heating vessel.
  • Atypical example of such apparatus is that set forth in U.S. Pat. No. 2,927,634.
  • the polyisocyanate (preferably preheated) and the acid phosphate are charged continuously, in the appropriate proportions, to a stirred reactor in which the reactants are maintained at the desired temperature.
  • the reaction mixture is withdrawn from the reactor at the same rate as the fresh reactants are added and the rate of addition and withdrawal are such that the residence time of the mixture in the reactor corresponds to the
  • the reaction be carried out in the absence of oxygen and moisture, i.e., in the presence of an inert gas such as nitrogen in accordance with the usual practice of handling polyisocyanates.
  • an inert gas such as nitrogen in accordance with the usual practice of handling polyisocyanates.
  • an inert gas such as nitrogen in accordance with the usual practice of handling polyisocyanates.
  • nitrogen such as nitrogen
  • the final mixture is saturated with dissolved gases which include primarily carbon dioxide as evolved, and this is the case whether the reaction is carried out under a nitrogen blanket or under air.
  • the mixture will contain primarily nitrogen, since the nitrogen forces out the carbon dioxide being evolved by the reaction between the polyisocyanate and the acid phosphate. Minor proportions of other gases may also be present in some embodiments.
  • the proportions in which the polyisocyanate and the acid phosphates (I) and or (II) are employed in the process of the invention can vary over a wide range but advantageously the acid phosphate is employed in an amount corresponding from 1 to 20 parts by weight per 100 parts by weight of polyisocyanate.
  • the amount of acid phosphate employed is such that the polyisocyanate compositions produced in accordance with the invention contain from 0.1 , preferably from 3, to 15, preferably to 10, most preferably to 8, percent by weight of the acid phosphate.
  • the polyisocyanate employed in the process of the invention can be any organic polyisocyanate which contains at least two isocyanate groups per molecule.
  • organic polyisocyanates are diphenylmethane diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, ⁇ , ⁇ '-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and the mixtures of these latter two isomers which are available commercially, including triphenylmethane triisocyanates, 4,4-diisocyanatodiphenyl ether, and polymethylene polyphenyl polyisocyanates.
  • polyisocyanates are mixtures containing from 25 to 90 percent by weight of methylenebis(phenyl isocyanate) the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality higher than 2.0.
  • Such polyisocyanates and methods for their preparation are well-known in the art; see, for example, U.S. Patent Nos. 2,683,730; 2,950,263; 3,12,008 and 3,097,191.
  • polyisocyanates are also available in various modified forms.
  • One such form comprises a polymethylene polyphenyl polyisocyanate which has been subjected to heat treatment, generally at temperatures from 150°C to 300 ⁇ C until the viscosity (at 25°C) has been increased to a value within the range of 800 to 1500 centipoise (cps).
  • Another modified polymethylene polyphenyl polyisocyanate is one which has been treated with minor amounts of an epoxide to reduce the acidity thereof in accordance with U.S. Patent No. 3,793,362.
  • polymethylene polyphenyl polyisocyanates can also be employed in the form of prepolymers and quasi-prepolymers, i.e., the products obtained by reacting the polyisocyanate with a minor amount of a polyol, as well as in the form of polyisocyanates which have been partially blocked by reaction with a monohydric alcohol using procedures well-known in the art.
  • Carbodiimide- modified methane diphenyl diisocyanates can also be used.
  • polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the process of the invention.
  • Particularly preferred polymethylene polyphenyl polyisocyanates are those which contain from 35 to 65 percent by weight of methylenebis(phenyl isocyanate).
  • Also preferred are those polyisocyanates having viscosities of less than 500 centipoise (cps), more preferably less than 300 cps, and most preferably less than 200 cps.
  • acid phosphates of formulae (I) and (II) can be employed in the process of the invention, those acid phosphates wherein R represents alkyl or alkenyl and X represents O, and more particularly, those acid phosphates wherein R represents alkyl or alkenyl having from 8 to 18 carbon atoms and X represents O, exhibit advantages because of ready availability and low cost.
  • the increased stability as to carbon dioxide generation is effected particularly by the second step of the present invention, which involves subjecting the mixture to a negative pressure sufficient to remove at least a portion of the dissolved gases therefrom.
  • the negative pressure is a vacuum sufficient to remove at least 10 percent of the dissolved gases, more preferably at least 95 percent, and most preferably at least 99 percent.
  • the negative pressurization evacuated be to less than 50 mm Hg (2 inches Hg), and more preferably to less than 10 mm Hg (0.4 inch Hg).
  • the effective time of the evacuation varies, depending on the negative pressure employed as well as the concentration of the acid phosphate in the polyisocyanate.
  • the negative pressurization is held for at least 15 minutes, and more preferably at least 30 minutes, and most preferably from 1 to 3 hours. In a preferred embodiment this most preferred period of evacuation is applied while maintaining a pressure reading of less than 10 mm Hg (0.4 inch Hg).
  • Equipment useful for the negative pressurization includes vacuum pumps, jets, aspirators or other conventional equipment.
  • liquid, storage-stable polyisocyanate compositions prepared in accordance with the process of this invention are particularly useful as binder resins for use in the preparation of particle boards in accordance with methods well-known in the art, as described in the "Background” section references cited hereinabove.
  • the compositions useful in the process of this invention possess the advantage of preventing adherence of the particle board to metal surfaces such as caul plates and press plate platens used in the preparation of such a board.
  • the polyisocyanate compositions of the invention have a viscosity in the range of from 100 to 3000 centipoise (cps) to facilitate ease of handling in the equipment currently employed in the manufacture of particle board. Viscosities in the above range can be attained readily when employing polymethylene polyphenyl polyisocyanates having an initial viscosity of the order of 25 cps to 1000 cps and subjecting these polyisocyanates to the process of the invention. This represents an additional reason for employing such polyisocyanates in a preferred embodiment of the invention.
  • the polyisocyanate composition can be applied to the particle board chips, prior to heating and pressing of the latter, in the form of an aqueous emulsion or dispersion.
  • an emulsifying or dispersing agent it is desirable to employ an emulsifying or dispersing agent.
  • the agent can be incorporated into the polyisocyanate compositions of the invention so as to enable the particle board manufacturer to prepare the required emulsion or dispersion without the need to employ additional agents.
  • the agent can be any of those known in the art including anionic and nonionic emulsifying and dispersing agents.
  • agents include, for example, polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene; alkoxylated alkylphenols such as nonylphenoxypoly-(ethyleneoxy)ethanols; alkoxylated aliphatic alcohols such as ethoxylated and propoxylated aliphatic alcohols containing from 4 to 18 carbon atoms; glycerides of saturated and unsaturated fatty acids such as stearic, oleic, and ricinoleic acids; polyoxyalkylene esters of fatty acids such as stearic, lauric, oleic and like acids; fatty acid amides such as the dialkanolamides of fatty acids such as stearic, lauric, oleic and similar acids; and
  • a non-active hydrogen containing solvent or diluent can be employed.
  • such non-active hydrogen containing materials include esterified polyols and monols.
  • a reaction was carried out using as the acid phosphate a mixture of mono- and di- lauryl acid phosphate (TRYFAC* 5573, commercially available from Henkel Industries) and, as the polyisocyanate, a polymethylene polyphenyl polyisocyanate containing approximately 46.5 percent by weight of methylenebis(phenyl isocyanate) and having an isocyanate equivalent of 134.5 and a viscosity of 25°C of 173 cps (PAPI* 27, commercially available from The Dow
  • the polyisocyanate starting amount was 900 pounds, and was charged to a stainless steel reaction vessel equipped with an agitator and nitrogen sparge. It was heated to 80°C with stirring and 32.6 pounds of TRYFAC* 5573 were added over a 5-10 minute interval to control foaming resulting from carbon dioxide evolution. Upon completion of the TRYFAC* addition, the reaction was stirred at 80°C for two hours. Foaming of the reaction mixture was observed to continue. At the end of the reaction the nitrogen flow was shut off, full vacuum was applied (0-50 mm Hg, 0-2 inches Hg) while the temperature was maintained at 80°C, and the product was then cooled to ambient temperature. The vacuum was then discontinued and the product was drummed off. It was stored in an oven at 43-49°C and pressurization recorded as shown in Table 1. The NCO content of the final product was 30.1 percent by weight.
  • a reaction was carried out to illustrate the difference in the rate of drum pressurization between the Example 1 sample and a sample prepared using a similar preparation method but without the step of being subjected to a negative pressure

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Medical Uses (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention décrit un procédé de préparation d'une composition liquide, stable en stockage, contenant un polyisocyanate organique ainsi qu'un phosphate acide. Le procédé consiste à (1) chauffer un mélange de polyisocyanate et de phosphate acide à une température comprise entre 60 et 190 °C, et pour une durée appropriée, de sorte qu'aucune séparation de phase ne se produise lorsque le mélange réactionnel est refroidi jusqu'à la température ambiante, le mélange contenant des gaz dissous; et (2) soumettre le mélange à une pression négative assez grande pour y éliminer au moins une partie des gaz dissous. La pression négative réduit de façon appréciable le taux de l'évolution subséquente du dioxyde de carbone et permet donc d'obtenir une stabilité en stockage plus durable que si aucune étape de mise sous pression négative n'avait été effectuée. La mise sous pression négative réduit les problèmes associés à la mise sous pression des récipients.
PCT/US1996/004120 1995-04-17 1996-03-26 Procede de preparation d'un melange de polyisocyanate et de phosphate stable en stockage Ceased WO1996033231A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR9608163A BR9608163A (pt) 1995-04-17 1996-03-26 Processo para preparar uma composição de poliisocianato líquida e mistura de poliisocianato orgânico
AU54319/96A AU5431996A (en) 1995-04-17 1996-03-26 Process for preparing a storage-stable mixture of polyisocyanate and phosphate
EP96911430A EP0821706A1 (fr) 1995-04-17 1996-03-26 Procede de preparation d'un melange de polyisocyanate et de phosphate stable en stockage
JP8531745A JPH11503786A (ja) 1995-04-17 1996-03-26 ポリイソシアネートとホスフェートの貯蔵安定な混合物の製造方法
MX9707969A MX9707969A (es) 1995-04-17 1996-03-26 Proceso para preparar una mezcla estable al almacenamiento de poli-isocianato y fosfato.
NO974785A NO974785D0 (no) 1995-04-17 1997-10-16 Fremgangsmåte for fremstilling av en lagringsstabil blanding av polyisocyanat og fosfat

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42306095A 1995-04-17 1995-04-17
US08/423,060 1995-04-17

Publications (1)

Publication Number Publication Date
WO1996033231A1 true WO1996033231A1 (fr) 1996-10-24

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PCT/US1996/004120 Ceased WO1996033231A1 (fr) 1995-04-17 1996-03-26 Procede de preparation d'un melange de polyisocyanate et de phosphate stable en stockage

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EP (1) EP0821706A1 (fr)
JP (1) JPH11503786A (fr)
KR (1) KR19990007809A (fr)
CN (1) CN1181765A (fr)
AU (1) AU5431996A (fr)
BR (1) BR9608163A (fr)
CA (1) CA2218254A1 (fr)
CO (1) CO4410409A1 (fr)
MX (1) MX9707969A (fr)
NO (1) NO974785D0 (fr)
WO (1) WO1996033231A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024612A1 (fr) * 2000-09-20 2002-03-28 Basf Aktiengesellschaft Procede pour eliminer des metaux dissous de liquides organiques et nettoyant approprie
EP2825544B1 (fr) * 2012-03-15 2018-08-08 Basf Se Compositions d'isocyanate modifié et leurs procédés de préparation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006052987A1 (de) * 2006-11-10 2008-05-15 Bayer Materialscience Ag Kunststoffverbundelemente und ein Verfahren zu ihrer Herstellung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2382468A1 (fr) * 1977-03-01 1978-09-29 Asahi Chemical Ind Procede pour preparer un polyisocyanate organique
US4257995A (en) * 1979-05-03 1981-03-24 The Upjohn Company Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor
US4258169A (en) * 1980-03-26 1981-03-24 The Upjohn Company Polyisocyanate compositions containing in-situ formed pyrophosphate mold release agent and process of making
US4382108A (en) * 1981-12-21 1983-05-03 The Upjohn Company Novel compositions and process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2382468A1 (fr) * 1977-03-01 1978-09-29 Asahi Chemical Ind Procede pour preparer un polyisocyanate organique
US4257995A (en) * 1979-05-03 1981-03-24 The Upjohn Company Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor
US4258169A (en) * 1980-03-26 1981-03-24 The Upjohn Company Polyisocyanate compositions containing in-situ formed pyrophosphate mold release agent and process of making
US4382108A (en) * 1981-12-21 1983-05-03 The Upjohn Company Novel compositions and process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024612A1 (fr) * 2000-09-20 2002-03-28 Basf Aktiengesellschaft Procede pour eliminer des metaux dissous de liquides organiques et nettoyant approprie
EP2825544B1 (fr) * 2012-03-15 2018-08-08 Basf Se Compositions d'isocyanate modifié et leurs procédés de préparation

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NO974785L (no) 1997-10-16
NO974785D0 (no) 1997-10-16
EP0821706A1 (fr) 1998-02-04
CN1181765A (zh) 1998-05-13
CA2218254A1 (fr) 1996-10-24
KR19990007809A (ko) 1999-01-25
CO4410409A1 (es) 1997-01-09
AU5431996A (en) 1996-11-07
JPH11503786A (ja) 1999-03-30
BR9608163A (pt) 1999-02-09
MX9707969A (es) 1997-12-31

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