WO1998006770A1 - Agent d'extinction thermique miscible avec l'eau - Google Patents

Agent d'extinction thermique miscible avec l'eau Download PDF

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Publication number
WO1998006770A1
WO1998006770A1 PCT/US1997/013797 US9713797W WO9806770A1 WO 1998006770 A1 WO1998006770 A1 WO 1998006770A1 US 9713797 W US9713797 W US 9713797W WO 9806770 A1 WO9806770 A1 WO 9806770A1
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WIPO (PCT)
Prior art keywords
composition
isocyanate
polyahl
polyoxyalkylene
monoahl
Prior art date
Application number
PCT/US1997/013797
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English (en)
Inventor
Camiel F. Bartelink
Ronald Van Voorst
Henri J.M. Gruenbauer
Martin Moeller
David Critchley
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The Dow Chemical Company
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Publication date
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Priority to AU40533/97A priority Critical patent/AU4053397A/en
Publication of WO1998006770A1 publication Critical patent/WO1998006770A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/60—Aqueous agents
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • This invention relates to aqueous compositions that comprise a water soluble urethane polymer, and the use of such compositions as a thermal quenching agent.
  • a thermal quenching agent is a substance that is able to remove heat from a body, such as for example a forged metal body composed of steel.
  • the primary purpose of the thermal quenching agent is to assist in the rapid cooling of the metal body and to minimize the possibility of high thermal or transformational stresses that can occur from too rapid a cooling of the metal body.
  • the rate of cooling should be such to permit essentially complete transformation to its Martensite structure with minimal induction of stress.
  • Water is the most commonly used quenching agent followed by the use of mineral oils. While having the advantage of ready availability and being non-toxic, water is a rapid quenching agent the use of which can frequently cause cracking and stress in metal. Oils, while not notably inducing crack or stress problems, have associated disadvantages such as a very slow quenching rate, fire hazards, smoke emissions, cleaning and disposal problems.
  • thermal cooling, or quenching rate intermediate to that provided by water and oil is highly desirable.
  • quenching agents based on water soluble polymers including notably cellulose-based derivatives, polyvinyl alcohol (PVA) and especially polyoxyalkylene glycols.
  • PVA polyvinyl alcohol
  • Polyoxyalkylene glycols have enjoyed good popularity as a thermal quenching agent because they can be synthesized to exhibit good water solubility; are hydrolytically stable; and are essentially unaffected by water quality or its hardness.
  • Polyoxyalkylene glycols, notably those having an oxyethylene content also exhibit a property referred to as "inverse solubility" rendering them particularly effective as a thermal quenching agent.
  • an aqueous-based polyoxyalkylene glycol composition As the temperature of an aqueous-based polyoxyalkylene glycol composition is increased, the solubility of the glycol decreases and at a given temperature it falls out of solution resulting in the composition having a turbid or cloudy appearance.
  • the temperature at which the glycol becomes insoluble is frequently referred to as the "cloud point" temperature.
  • the high temperature insolubility of polyoxyalkylene glycols can be used to advantage to reduce the rate of cooling when such aqueous compositions are employed as quenching agents thereby reducing the possibility of cracking or stress buildup in the metal. It is thought that when the polyoxyalkylene glycols comes out of solution it provides a coating on the hot metal which retards the rate of heat loss from the metal thus minimizing crack and stress formation.
  • the polyoxyalkylene glycol is taken back into solution leaving a cooled, and clean, metal.
  • aqueous polyoxyalkylene glycol solutions offer advantages over water as quenching agent, the rate of quenching and cooling can still be such that undesirable crack or stress formation can occur. It would be advantageous to have available an alternative thermal quenching agent which is able to combine the advantages provided by polyoxyalkylene glycol based quenching agents with the advantages of an oil quenching agent.
  • this invention relates to an aqueous-based composition
  • an aqueous-based composition comprising, based on the total weight of the composition, from 1 to 50 weight percent of a water soluble urethane polymer which is a liquid at room temperature and has a number average molecular weight of from 600 to 80000 wherein said polymer is the reaction product of a monoahl with an isocyanate-terminated intermediate obtained by coupling a polyisocyanate with a polyahl, and wherein said polymer is substantially free of any isocyanate functionality or any isocyanate-reactive functionality.
  • this invention relates to a water soluble urethane polymer having an average number molecular weight of from 600 to 80000 and being substantially free of any isocyanate functionality or any isocyanate-reactive functionality characterized in that said polymer is the reaction product of a monoahl with an isocyanate-terminated intermediate obtained by coupling a polyisocyanate with a polyahl, wherein: a) the polyisocyanate is an aromatic diisocyanate including 2,4-toluene diisocyanate or 2,4 ⁇ -methylene diphenylisocyanate; b) the polyahl is a polyoxyalkylene polyol containing from 2 to 8 hydroxyl groups per molecule and wherein the polyoxyalkylene backbone comprises oxyethylene and oxypropylene moieties in a parts by weight ratio of from 90 to10 to 10 to 90; and c) the monoahl is a polyoxyalkylene mono-alcohol wherein the polyoxyal
  • this invention relates to a process for reducing the temperature of a hot body, especially a metal body, by immersing said body in a quenching medium comprising a water soluble urethane polymer and wherein the quenching medium is an aqueous composition as mentioned above.
  • the aqueous-based composition of the present invention based on total weight of the composition, comprises from 1 to 50, preferably from 1 to 30, and more preferably from 5 to 20 weight percent of a water soluble urethane polymer being a liquid at room temperature and having a number average molecular weight of from 600 to 80000.
  • the urethane polymer to be described in more detail later, is the reaction product of a monoahl with an isocyanate-terminated intermediate obtained by coupling a polyisocyanate with a polyahl, and wherein said polymer is substantially free of any isocyanate functionality or any isocyanate-reactive functionality.
  • the aqueous-based composition of this invention has particular value as a quenching agent and when used in this context is characterized in that it exhibits a cooling rate observed at 300°C when cooling from 450°C to 150°C, of advantageously not more than 70°C per second, preferably not more than 50°C per second, and more preferably not more than 40 ⁇ C per second. Cooling rates exceeding this value are not desirable as cracking or stress of the hot body being cooled may occur.
  • the aqueous compositions of this invention also exhibit a cloud point in the manner as described above for the polyoxyalkylene glycols; in this respect the composition exhibits a cloud point of advantageously more than about 25°C, preferably greater than 35°C, and more preferably greater than 50°C, and yet more preferably greater than 70°C.
  • higher cloud points are more desirable as this permits the hot body once cooled to be sooner removed from the quenching composition with a reduced possibility of the urethane polymer being present on its surface.
  • the water soluble urethane polymer, hereinafter referred to as "adduct”, present in the aqueous composition of this invention is substantially free of any isocyanate functionality or any isocyanate-reactive group including hydroxyl, thiol, carboxylic acid, thiocarboxylic acid, or primary amine functionality, is a liquid at room temperature and comprises a plurality of urethane linkages.
  • the adduct is represented by the structural formula (I).
  • A is a residue from a polyisocyanate
  • B is a residue from a polyahl
  • M is a residue from a monoahl; and f is the number of isocyanate reactive groups formally present on the polyahl.
  • the adduct When the adduct is based on a difunctional polyahl, it will have a linear structure; when based on a triol, it will have a branched or three limb structure, and so forth.
  • polyisocyanate entity (A) incorporated into the adduct For each polyisocyanate entity (A) incorporated into the adduct, at least two urethane linkages are introduced.
  • the adduct will, in most cases, be a composition comprising predominantly an adduct of structure (I), with minor amounts of adducts corresponding to Structures (II) and (III).
  • Adduct II corresponds to a polyisocyanate (A) fully reacted with a monoahl (M);
  • Adduct III corresponds to a structure containing two or more polyahl (B) entities per adduct molecule. It is to be appreciated that adduct III may acquire a highly complexed, branched structure when the functionality of B is greater than 2, wherein each branch nominally will be terminated with a monoahl derived entity.
  • Adduct II and III comprising two or more B moieties is depicted as a linear adduct originating through the polyahl containing two isocyanate reactive groups per molecule.
  • An adduct corresponding to structure (II) can result when polyisocyanate reacts uniquely with monoahl; an adduct corresponding to Structure (III) can result when multiple molecules of polyisocyanate are able to react with multiple molecules of polyahl prior to reaction with monoahl.
  • the liquid urethane-containing adduct has a theoretical number average molecular weight of from 600 to 80000, preferably from 1000 to 60000, and more preferably from 2000 to 30000.
  • the adduct is constituted of substances corresponding to Structures (I), (II) and (III) these are present, based on total mole amount of said substances, in an amount of from: for (I), at least 65, preferably at least 75, more preferably at least 80, and up to 100 mole percent; for (II), less than about 35, preferably less than 25, more preferably less than 15, and most preferably 0 mole percent; and for (III), less than about 12, preferably less than about 10, more preferably less than about 7, yet more preferably less than about 5, and most preferably 0 mole percent.
  • the adduct composition comprises substances (I), (II), and (III) in the mole percent ranges of from 65 to 90; from 30 to 5; from about 6 to 1 respectively, wherein the total is to 100 percent.
  • the end product has a low content of adducts represented by structures (II) and (III).
  • structure (III) type substances can be minimized, then the resulting adduct is more likely to have a liquid characteristic at room temperature and especially when the polyahl used in the preparation of the adduct formally contained three or more isocyanate reactive groups per molecule.
  • the adduct composition is related to the manufacturing process, and particularly to the method of preparation of the intermediate product, from polyahl and polyisocyanate, prior to reaction with monoahl.
  • the adduct is best prepared by a solvent-free two-step process which comprises (1 ) reacting a polyisocyanate, in the absence of a urethane-promoting catalyst, with a polyahl containing isocyanate-reactive groups to provide an isocyanate-terminated intermediate; (2) reacting the isocyanate-terminated intermediate with a monoahl to provide the end product.
  • the intermediate has an isocyanate content of from 0.5 to 5, preferably from 1 to 4 weight percent and is a composition which comprises structures (IV), (V), and (VI) represented by the structural formulae:
  • A is the residue from a polyisocyanate
  • B is the residue from a polyahl
  • f is the number of isocyanate reactive groups formally present on the polyahl.
  • the polyisocyanate used in the process to prepare the adduct has at least two isocyanate moieties per molecules and which can be distinguished by a difference in reactivity, with respect to the isocyanate-reactive group of the polyahl.
  • the reactivity difference helps to optimize the preparation of an intermediate having a narrow molecular weight distribution and reduces the potential for formation of substances corresponding to structures (III) and (VI).
  • Suitable polyisocyanates can be aliphatic or preferably aromatic polyisocyanates and especially aromatic diisocyanates.
  • a further advantage to using aromatic diisocyanates, where the relative reaction rate of the individual isocyanate groups are different, is that it permits the amounts of free, non-reacted, polyisocyanate (V) that may be present in the isocyanate-terminated intermediate to be limited to the subsequent advantage of material requirements for the second process step, and further to the value of the adduct in end applications.
  • suitable aromatic polyisocyanates include toluene diisocyanate, methylene diphenylisocyanate and polymethylene polyphenylisocyanates.
  • 2,4 ' -methylene diphenylisocyanate and especially 2,4-toluene diisocyanate, or mixtures comprising such diisocyanate.
  • the polyahl used in the process comprises two or more isocyanate-reactive functional groups per molecule where such functional groups include -OH, -SH, -COOH, or -NHR, with R being hydrogen or an alkyl moiety.
  • Polyahls bearing -OH functionality are preferred.
  • the polyahl may contain up to about 8 such functional groups per molecule.
  • the polyahl contains from 2 to 8, more preferably from 3 to 8, and most preferably from 3 to 6 functional groups per molecule.
  • the polyahl used in the process of this invention has a molecular weight of from 200 to 20000; preferably from about 500, more preferably from about 1000, and yet more preferably from about 2000; and preferably up to about 15000, and more preferably up to about 10000.
  • the polyahl is a polyester or particularly a polyoxyalkylene polyol where the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof, including especially oxypropylene-oxyethylene and oxyethylene-oxybutylene mixtures.
  • polyols that have an oxyethylene content of at least 20, preferably at least 40, more preferably at least 60 weight percent, based on total weight of the polyol.
  • the polyahl is a poly(oxyethylene-oxypropylene) polyol with a functionality of from 3 to 6, a molecular weight of from 2000 to 10000, and containing the oxyethylene-oxypropylene moieties in a parts by weight ratio of from 90 to 10 to 10 to 90, preferably from 70 to 30 to 30 to 70.
  • the oxyethylene content may be randomly distributed through the polyoxyalkylene chain of the polyol, present as discrete oxyethylene blocks, or a combination of random distribution and blocks.
  • polyalkylene carbonate-based polyols and polyphosphate-based polyols.
  • the nature of the polyol selected depends on the desire whether or not to impart some water solubility to the adduct, which can be advantageous for certain applications and disadvantageous for other applications.
  • Suitable polyoxyalkylene polyols are exemplified by various commercially available polyols as used in polyurethane, lubricant, surfactancy applications and include polyoxypropylene glycols designated as VORANOLTM P-2000 and P-4000 with molecular weights of 2000 and 4000, respectively; polyoxypropylene-oxyethylene glycols such as DOWFAXTM DM-30 having a molecular weight of 600 and an oxyethylene content of about 65 weight percent, and SYNALOXTM 25D-700 having a molecular weight of 5500 and an oxyethylene content of 65 weight percent, all available from The Dow Chemical Company; polyoxyethylene triols available under the trademark TERRALOXTM and designated as product WG-100A and WG-116 having a molecular weight of 700 and 980, respectively; polyoxypropylene-oxyethylene triols designated as VORANOLTM CP 1000 and CP 3055 having a molecular weight of 1000 and 3000, respectively; and VORANOL
  • the monoahl used to prepare the urethane polymer required for the aqueous composition of this invention is an organic substance containing one isocyanate-reactive functional group per molecule such as -OH, -SH, -COOH, or -NHR wherein R is hydrogen or alkyl.
  • a monoahl having as the isocyanate-reactive functionality a hydroxyl group hereinafter referred to as a monol.
  • the monoahl optionally contains alternative functionalities which, under the conditions of the present invention, are not considered as being isocyanate reactive. Exemplary of such alternative functionalities can be alkene, alkyne, halogen, nitro, ester and siloxane.
  • the monol used in the process is chosen based on the intended end application of the products resulting from the process. When it is desired to influence, for example, the water miscibility of the adduct product an appropriate hydrophilic or hydrophobic monol is used. Any hydrophilic/hydrophobic characteristics introduced by way of the polyahl will also contribute to the overall characteristics of the adduct including its cloud point behavior in an aqueous environment.
  • Preferred monols for use in this invention are polyoxyalkylene monols with a molecular weight of from 150 to 6000, preferably from about 250, more preferably from about 500, yet more preferably from about 1000; and preferably up to about 5000, more preferably up to about 4000.
  • the oxyalkylene entity of the monol comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more, especially the combination of oxyethylene with oxypropylene, or oxyethylene with oxybutylene.
  • the monoahl used to obtain the adduct is a poly(oxyethylene-oxypropylene) monol with a molecular weight of from 1000 to 5000, and containing the oxyethylene-oxypropylene moieties in a parts by weight ratio of from 90 to 10 to 10 to 90, preferably from 70 to 30 to 30 to 70.
  • the water soluble urethane polymer present in the aqueous composition of this invention is obtained from toluene diisocyanate comprising, substantially, the 2,4-isomer; a poly(oxyethylene-oxypropylene) polyol with a functionality of from 3 to 6, a molecular weight of from 2000 to 10000, and containing the oxyethylene-oxypropylene moieties in a parts by weight ratio of from 90 to10 to 10 to 90; and a poly(oxyethylene-oxypropylene) monol with a molecular weight of from 1000 to 5000, and containing the oxyethylene-oxypropylene moieties in a parts by weight ratio of from 90 to 10 to 10 to 90.
  • the method of preparing the urethane-containing adduct is a two step process comprising a first and a second step and, optionally, an intermediate step between the first and second step.
  • the first step relates to the preparation of an isocyanate-terminated intermediate by reacting the polyisocyanate with the polyahl at a reaction temperature that does not exceed 100°C, in essentially anhydrous conditions.
  • essentially anhydrous conditions it is meant less than 1500, preferably less than 750, more preferably less than 350 ppm of water.
  • the reaction temperature advantageously is from 20°C, more preferably from 35°C; and preferably up to 80°C, more preferably up to 70°C. Operating in such a temperature range provides for an optimum reaction rate without loss of the difference in the relative reactivity difference of the individual isocyanate groups of the polyisocyanate.
  • the polyahl is added at a controlled rate to the polyisocyanate such that the reaction temperature does not exceed 100°C, and the total amount of polyahl added is a stoichiometric equivalent or less with respect to the polyisocyanate.
  • the total amount of polyahl advantageously does not exceed 0.99, preferably does not exceed 0.95 of an equivalent; and advantageously is at least 0.4, preferably at least 0.6, and more preferably from 0.85 of an equivalent per equivalent of isocyanate.
  • the polyahl is a polyol and is present in a total amount corresponding to from 0.85 to 0.95 of an equivalent.
  • the first process step is conducted in essentially anhydrous conditions and in the absence of a processing aid, as defined hereinabove.
  • a processing aid as defined hereinabove.
  • the resulting isocyanate-terminated intermediate has a higher free, unreacted, isocyanate content, corresponding to structure (V), before proceeding with the second step of the process, it can be advantageous to reduce such isocyanate content by, for example, distillation or extraction techniques using suitable solvents including pentane or hexane. Free, unreacted diisocyanate can participate in the second process step providing capped products, the presence of which in the final product may be detrimental to performance in certain end applications.
  • the isocyanate-terminated intermediate is reacted with a controlled amount of a monoahl to provide the adduct product.
  • the controlled amount is such to essentially convert all isocyanate functionality without leading to the accumulation of any isocyanate-reactive functionality in the end adduct product.
  • the amount required to achieve this result is determined by adding in increments the monoahl and directly monitoring the reaction mixture for presence of free reactive functionality, in this case isocyanate functionality. The incremental addition continuing until the presence of isocyanate functionality is reduced to a minimum or zero, without accumulation of any other isocyanate reactive functionality.
  • infrared spectrometry which permits the ready observation of the presence of isocyanate functionality by observing absorption at wavelengths of, for example, from 2200 to 2300 cm" ' - . Observation at other wavelengths in, for example, near-IR frequencies is also possible.
  • Use of a fourier transfer infrared spectrometer provides a convenient means of rapid observation for isocyanate functionality directly in the reaction vessel thus avoiding the need to take isolated samples. Traditional monitoring methods involving isolation and subsequent reactive chemical analysis, for example by titration itself subject to operator error, of material is avoided.
  • the process temperature is chosen for convenience of reaction time and can be greater than 100°C without detriment to the performance of the adduct in end applications.
  • reaction of the isocyanate-terminated intermediate with the monoahl can, if desired, be accelerated by use of a suitable urethane-promoting catalyst.
  • catalysts includes tertiary amine compounds and organotin compounds as used when preparing for example polyurethane foam by reaction of a polyisocyanate with a polyol.
  • Water soluble urethane polymers Polymer 1 to 6, were prepared by first reacting a poly(oxyethylene-oxypropylene) polyol with less than a stoichiometric amount of 2,4-toluene diisocyanate and subsequently reacting this intermediate product with a poly(oxyethylene-oxypropylene) monol present in an amount to convert essentially all isocyanate functionality to urethane. Details of the polyol and monol reactants and resulting urethane polymer are given in Table 1. Table 1
  • Aqueous compositions 1 to 6 containing 5 weight percent of respectively Polymers 1 to 6 were prepared and the quenching performance observed.
  • the static quenching ability of the compositions was observed using as equipment a QUENCHMASTER available from Drayton Probe System Ltd., Stoke-on-Trent, Staffordshire, GB and operated according to recommended procedures.
  • the cloud point of the polymers as a 1 weight percent aqueous solution was also observed according to test procedure ASTM D2024-65 (re-approved 1992) the observations are reported in Table 2.
  • aqueous compositions of this invention exhibit a moderated rate of cooling observed at 300°C, relative to the comparative compositions, while still retaining an overall attractive cooling time. From the present studies it appears that an optimum cooling rate is obtained when the poly(oxyethylene-oxypropylene) polyol contains the oxyethylene and oxypropylene moieties in a parts by weight ratio of about 60:40. It is also apparent that use of a monol having an elevated oxyethylene to oxypropylene parts by weight ratio provides for a higher cloud point temperature.
  • a liquid urethane polymer, Polymer 7 is prepared according to the above procedure by first reacting a polyether polyol (functionality 3; molecular weight 2900; 57 to 43 EO/PO) with a less than stoichiometric amount of an 80 to 20 mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate to provide an intermediate product which is subsequently reacted with a poly(oxyethylene-oxypropylene)monol of 2100 molecular weight and having an EO/PO ratio of 75 to 25.
  • Polymer 7 when as a 1 weight percent aqueous solution exhibits a cloud point temperature of 50°C.
  • An aqueous composition containing 5 weight percent of Polymer 7 exhibits a static cooling rate at 300 ⁇ C of 34.6°C per second, and a time of 18.9 seconds to cool the probe from 450°C to 150°C.
  • An aqueous composition containing 10 weight percent of Polymer 7 exhibits a static cooling rate at 300°C of 46.0°C per second, and a time of 9.7 seconds to cool the probe from 450°C to 150°C.
  • a shorter cooling time with increased concentration of the urethane polymer normally an increased cooling time is expected. The surprising observation has been confirmed by repeat studies.
  • a liquid urethane polymer, Polymer 8 was prepared according to the above procedure by firstly reacting a polyether polyol (functionality 6; molecular weight 5125; 50:50 EO/PO) with a less than stoichiometric amount of 2,4-toluene diisocyanate to provide an intermediate product which was subsequently reacted with a poly(oxyethylene-oxypropylene)monol of 1150 molecular weight and having an EO/PO ratio of 75 to 25.
  • Polymer 8 as a 1 weight percent solution exhibits a cloud point temperature of 27°C.
  • An aqueous composition containing 5 weight percent of Polymer 8 exhibits a static cooling rate at 300 ⁇ C of 68.0°C per second, and a time of 6.4 seconds to cool the probe from 450°C to 150°C.
  • An aqueous composition containing 10 weight percent of Polymer 8 exhibits a static cooling rate at 300°C of 63.9°C persecond, and a time of 7.6 seconds to cool the probe from 450°C to 150°C.

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Abstract

L'invention concerne une composition à base aqueuse qui comprend, par rapport au poids total de la composition, 1 à 50 % en poids d'un polymère uréthanne hydrosoluble qui est liquide à la température ambiante et qui présente un poids moléculaire moyen en nombre de 600 à 80 000, ledit polymère étant le produit réactionnel d'un monoahl avec un intermédiaire à extrémité isocyanate obtenu par copulation d'un polyisocyanate et d'un polyahl. Ledit polymère est sensiblement exempt de toute fonctionnalité isocyanate ou de toute fonctionnalité réactive à l'isocyanate. Les compositions selon l'invention sont avantageuses en tant qu'agent d'extinction thermique, permettent d'assurer des vitesses de refroidissement et des temps de refroidissement tels que le risque de formation de fissures et de tensions est réduit par rapport aux agents d'extinctions classiques tels que l'eau ou les polyoxyalkylèneglycols.
PCT/US1997/013797 1996-08-09 1997-08-08 Agent d'extinction thermique miscible avec l'eau WO1998006770A1 (fr)

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AU40533/97A AU4053397A (en) 1996-08-09 1997-08-08 A water miscible thermal quenching agent

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US68942996A 1996-08-09 1996-08-09
US08/689,429 1996-08-09

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WO1998006770A1 true WO1998006770A1 (fr) 1998-02-19

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WO2000005287A2 (fr) * 1998-07-23 2000-02-03 Huntsman Ici Chemicals, Llc Compositions d'isocyanates emulsifiables
WO2013130140A1 (fr) * 2011-12-01 2013-09-06 University Of Utah Research Foundation Dispositifs photoniques sur des substrats plans et courbés et leurs procédés de fabrication
JP2015040286A (ja) * 2013-08-23 2015-03-02 Dic株式会社 ウレタン樹脂組成物、皮革様シート及び積層体
US9445486B2 (en) 2009-08-21 2016-09-13 Titeflex Corporation Energy dissipative tubes

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WO1996034904A1 (fr) * 1995-05-01 1996-11-07 The Dow Chemical Company Produit d'addition contenant de l'urethane liquide

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005287A2 (fr) * 1998-07-23 2000-02-03 Huntsman Ici Chemicals, Llc Compositions d'isocyanates emulsifiables
WO2000005287A3 (fr) * 1998-07-23 2002-05-23 Huntsman Ici Chem Llc Compositions d'isocyanates emulsifiables
US6407196B1 (en) 1998-07-23 2002-06-18 Huntsman International Llc Emulsifiable isocyanate compositions
US9445486B2 (en) 2009-08-21 2016-09-13 Titeflex Corporation Energy dissipative tubes
US10293440B2 (en) 2009-08-21 2019-05-21 Titeflex Corporation Methods of forming energy-dissipative tubes
WO2013130140A1 (fr) * 2011-12-01 2013-09-06 University Of Utah Research Foundation Dispositifs photoniques sur des substrats plans et courbés et leurs procédés de fabrication
US9403186B2 (en) 2011-12-01 2016-08-02 University Of Utah Research Foundation Photonic devices on planar and curved substrates and methods for fabrication thereof
JP2015040286A (ja) * 2013-08-23 2015-03-02 Dic株式会社 ウレタン樹脂組成物、皮革様シート及び積層体

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