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    • 专利摘要:
    FOAM COMPOSITIONThe invention provides polyurethane and polyisocyanurate foams and methods for their preparation. More particularly, the invention relates to polyurethane and polyisocyanate foams: closed cell, and methods for their preparation. Foams are characterized by a thin, uniform cell structure and little or no foam collapse. The foams are produced with a polyol premix composition comprising a combination of a hydroaloolefin blowing agent, a polyol, a silicone surfactant, and a non-amine catalyst used individually or in combination with an amine catalyst.
    公开号:BR112012014267A2
    申请号:R112012014267-4
    申请日:2010-12-16
    公开日:2020-08-25
    发明作者:Michael Vanderpuy；David John Williams；Clifford P. Gittere
    申请人:Honeywell International Inc.；
    IPC主号:
    专利说明:

    - FOAM COMPOSITION i Field of the Invention The present invention is related to polyurethane and polyisocyanate foams and methods for their preparation.
    Fundamentals of the Invention Low density, rigid to semi-rigid polyurethane or polyisocyanate foams are useful in a wide variety of insulation applications, including roof systems, construction use panels, construction envelope insulation, spray applied foams, two-component foaming foam, insulation for refrigerators and freezers, and so-called integral skin for application such as steering wheels in vehicles and other parts of automotive and aerospace cabins, shoe soles, and amusement park supports. Fundamental to the large-scale commercial acceptance of rigid polyurethane foams - is its ability to provide a good balance of properties. For example, rigid polyurethane and polyisocyanate foams are known to provide exceptional thermal insulation and excellent flame resistant properties, and superior structural properties even at reasonably low densities. Integral skin type foams are known to produce a hard outer skin
    . durable and a padded core with cells.
    NNE “Rigid or semi-rigid foams = polyurethane and polyisocyanate are known in the art by reacting a polyisocyanate with one or more polyols in. presence of one or more blowing agents, one or more catalysts, one or more surfactants and, optionally, other ingredients. blowing agents include hydrocarbons, fluorocarbons, chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, halogenated hydrocarbons, ethers, esters, aldehydes, alcohols, ketones, organic acid or gas, most often CO, as generating materials.
    Heat is generated when the polyisocyanate reacts with the polyol, and volatilizes the blowing agent contained in the liquid mixture, thus forming bubbles in the system.
    In the case of gas-generating materials, gaseous species are generated by thermal decomposition or reaction with one or more of the ingredients used to produce the polyurethane or polyisocyanate foam.
    As the polymerization reaction progresses, the liquid mixture becomes a solid - 20 with cells, which traps the blowing agent in the foam cells.
    If a surfactant is not used in the foaming composition, the bubbles simply pass through the liquid mixture without forming a foam or forming a foam with large, irregular cells, which makes it useless.
    The foam industry has historically used
    'liquid fluorocarbon blowing agents due to TT' its ease of use and ability to produce foams with | superior mechanical and thermal insulation properties.
    Fluorocarbons not only act as blowing agents due to their volatility, but are also encapsulated or trapped in the closed cellular structure of the rigid foam and are the major contributors to the low thermal conductivity properties of rigid polyurethane foams.
    Fluorocarbon based blowing agents also produce a foam having a favorable k-factor.
    The k-factor is the transfer rate of thermal energy by conduction through a homogeneous material with dimensions of approximately 0.10 mº (1 ftº) by 2.5 cm (1 inch) thick, in 1 hour, where there is a difference of one degree Fahrenheit across the two surfaces of the material.
    Since the utility of closed cell polyurethane foams is based, in part, on their thermal insulation properties, it would be advantageous to identify the materials that produce lower k-factor foams. - 20 preferred blowing agents also have low global warming potential.
    Among these are hydroaloolefins including hydrofluorolefins of which trans-1,3,3,3-tetrafluorpropene (1234ze (E)) and 1,1,1,4,4,4 hexafluorbut-2-ene (1336mzzm (2)) are of particular interest and hydrochlorofluorolefins of which trans-1-chloro-3,3,3-trifluorpropene (1233zd (E)) is of particular
    " interest. Processes for the manufacture of trans-1,3,3,3- Tetrafluorpropene are disclosed in US patents US 7,230,146 and 7,189,884. Processes for m— manufacturing -of .. --trans-l-chloro-3,3,; 3-trifluorpropene --— - —are—— disclosed in US patents US 6,844,475 and
    6,403,847.
    It is convenient in many applications to supply components for polyurethane or polyisocyanate foams in pre-mixed formulations. More typically, the foam formulation is premixed in the form of two components. Polyisocyanate and optionally isocyanate-compatible raw materials, including but not limited to blowing agents and non-reactive surfactants, comprise the first component, commonly referred to as component “A”. A polyol or mixture of polyols, one or more surfactants, one or more catalysts, one or more blowing agents, and other optional components, including but not limited to flame retardants, dyes, compatibilizers, and solubilizers comprise the second ”20 component , commonly referred to as component “B” “. Therefore, polyurethane or polyisocyanate foams are readily prepared by mixing components A and B, either by manual mixing for small preparations and, preferably, by mechanical mixing techniques to form blocks, ingots, laminates, panels by localized spill. and other items, foams
    | 'applied by spraying, foaming and the like. CT optionally, other ingredients, such as retarders = | flame retardants, dyes, auxiliary blowing agents, and others and polyols can be added to the mixing head or reaction site. Most conveniently, however, they are all incorporated in a component B, A disadvantage of two component systems, especially those that use certain hydroaloolefins, including 1234ze (E), 1336 (2), and 1233zd (E), is the service life of component B. Normally, when a foam is produced by combining components A and B, a good foam is obtained. However, if the polyol premix composition is aged, prior to treatment with the polyisocyanate, the foams are of inferior quality and may even collapse during foaming.
    Summary of the Invention It has now been discovered that the source of the problem is the reaction of certain amine catalysts with certain hydroaloolefins including 1234ze, 1233zd, 1336mzzm, and / or '20 combinations of those mentioned. It was found that after .e. decomposition of the blowing agent, the molecular weight of polymeric silicone surfactants, if present, is adversely altered.
    Although it is possible to solve the problem by separating the blowing agent, surfactant and catalyst, for example, by adding the blowing agent, the catalyst
    . amine, or polyisocyanate surfactant: (component “A”) or by introducing the blowing agent, amine catalyst, or surfactant —A using a separate current from component “A” -or “B”, a preferred solution is one that does not require a change in the way in which the foams are made. It has now been discovered that non-amine catalysts, for example, inorganic metal catalysts, organo-metal catalysts and / or quaternary ammonium carboxylate catalysts, either individually or in combination with amine catalysts, can extend the shelf life of pre- polyol mixtures containing hydroaloolefins, such as, but not limited to 1234ze (E), 1233zd (E), and / or 1336mzzm (Z), such that good quality foams can be produced even if the polyol mixture has been aged for several weeks or months.
    Therefore, the invention relates to rigid to semi-rigid polyurethane & polyisocyanate foams and methods for their preparation, foams 7 20 which are characterized by a fine uniform cellular structure and little or no foam collapse. Foams are produced with an organic polyisocyanate and a polyol premix composition that comprises a combination of a blowing agent, which is preferably a hydroaloolefin, a polyol, a silicone surfactant, and a catalyst in which the catalyst comprises a or more
    a non-amine catalyst, preferably an inorganic or organometallic compound or a quaternary ammonium carboxylate catalyst, and may also include one or more - amine catalysts. - Detailed Description of the Invention The invention provides a polyol premix composition that comprises a combination of a blowing agent, one or more polyols, one or more silicone surfactants, and a catalyst in which the catalyst is a non-catalyst amine, such as an inorganic or organo-metallic compound or quaternary ammonium carboxylate material used alone or in combination with amine catalysts, wherein the blowing agent comprises one or more hydroaloolefins and, optionally, a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gas-generating material, water or combinations thereof.
    The invention also provides a method of preparing a polyurethane or polyisocyanate foam comprising reacting an organic polyisocyanate with the polyol premix composition.
    The blowing agent component comprises a hydroaloolefin, preferably comprising at least one or a combination of 1234ze (E), 1233zd (E), and / or
    7 1336mzzm (2) and, optionally, a hydrocarbon, Lo fluorocarbon, chlorocarbon,. fluorochlorocarbomide, halogenated hydrocarbon, ether, fluorinated ether, ester, "alcohol, aldehyde, ketone, organic acid, gas, water or gas generation material. or combinations thereof.
    The hydroaloolefin preferably comprises at least one haloalkene such as a filiuoralkene or chlorofluoralkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond.
    Preferred hydroaloolefins include, but are not limited to, trifluorpropenes and tetrafluorpropenes such as (1234), such as pentafluorpropenes (1225) and chlorotrifloropropenes such as (1233), chlorodifluorpropenes and chlorotrifluorpropenes and chlorotetrafluorpropene and hexafluorbutene (1336) and combinations thereof. Most preferred that the compounds of the present invention are the tetrafluorpropene, pentafluorpropene, and chlorotrifloropropene compounds in which the unsaturated terminal carbon has no more than one F or Cl substituent. Included. 20 1,3,3,3-tetrafluorpropene (1234ze); 1,1,3,3- .. tetrafluorpropene; 1,2,3,3,3-pentafluorpropene (1225ye), 1,1,1-trifluorpropene; 1,2,3,3, 3-pentafluorpropene, 1,1,1,3,3-pentafluorpropene (1225zc) and 1,1,2,3,3-pentafluorpropene (1225yc); (2) -1,1,1,2,3-pentafluorpropene (1225yez); l1-chloro-3,3,3-trifluorpropene (1233zd), 1,1,1,4,4,4-hexafluorbut-2-ene - (1336mMzzmM) or combinations
    of those mentioned, and any and all Lo stereoisomers for each of these. | TA Preferred Hydroaloolefins have a Global Warming Potential (PAG) of not more than 150, —more preferably not more than 100 and even more preferably not more than 75. As used here, “PAG” is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in “The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meterorological Association's Global Ozone Research and Monitoring Project”, which is incorporated by reference. Preferred hydroaloolefins also preferably have an Ozone Destruction Potential (PDO) of not more than 0.05, more preferably not more than 0.02 and even more preferably about zero. As used herein, “PDO” is as defined in “The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meterorological Association's Global Ozone Research and Monitoring Project”, which is hereby incorporated by reference.
    ”- 20 Preferred blowing coagent options include non-exclusively water, organic acids that produce CO2, and / or CO, hydrocarbons; ethers, halogenated ethers; esters, alcohols, aldehydes, ketones, pentafluorbutane; pentafluorpropane; hexafluorpropane; heptafluorpropane; trans-1,2-dichlorethylene; methylal, methyl formate, 1-chloro-1,2,2,2-tetrafluoroethane (124); 1,1-dichloro-1-
    - fluorethane (141b), 1,1,1,2-tetrafluoroethane (134a), 1,1,2,2- tetrafluoroethane (1390); TI-chloro-Ll, i-difluorethane (1426), 1,1,1,3,3-pentafluorbutane (365mfc) 1,1,1,2,3;, 3, 3 "- heptafluorpropane (227ea); trichlorofluoromethane - (11), dichlorodifluoromethane (12); dichlorofluoromethane (22); 1,1,1,3,3, 3-hexafluorpropane (236fa), 1,1,1,2,3,3-hexafluorpropane (236ea), 1, 1,1,2,3,3,3-heptafluorpropane (227ea), difluoromethane (32); 1,1-difluorethane (152a), 1,1,1,3,3-pentafluorpropane (245fa); butane; isobutane; normal pentane, isopentane, cyclopentane, or combinations thereof, In certain embodiments, the blowing coagents include one or a combination of water and / or normal pentane, isopentane, or cyclopentane, which may be provided with one or a combination of the hydroaloolefin blowing agents The blowing agent component is usually present in the polyol premix composition in an amount of from about 1% w to about 3% w, preferably from about 3% w to about 25% w, and more preferably from about 5% p to about - 20% 25%, for example of the polyol premix composition.
    . When both a hydroaloolefin and an optional blowing agent are present, the hydroaloolefin component is usually present in the blowing agent component in an amount of about 5% w to about 90% w, preferably from about 7% p to about 80% p, and more preferably from about 10% p
    . up to about 70 wt%, by weight of the blowing agent; and the optional “blowing agent” is usually present in the “ÉúÚU blowing agent” component in an amount of from about - 95% w to about 10% w, preferably from about 93% w to about 20 % w, and more preferably from about 90% w to about 30% w, by weight of the blowing agent component.
    The polyol component, which includes mixtures of polyols, can be any polyol which reacts in a known manner with an isocyanate in the preparation of a polyurethane and polyisocyanate foam.
    Useful polyols comprise one or more of a sucrose-containing polyol; phenol, a polyol containing phenol formaldehyde; a glucose-containing polyol; a sorbitol-containing polyol; a polyol containing methylglycoside; an aromatic polyester polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol; copolymers grafted from polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more - 20 of (b), where (a) is selected from glycerin, .. ethylene glycol, dietylene — glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soybean oil , lecithin, liquid resin, palm oil, and castor oil, and (b) is selected from ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide, and combinations thereof.
    The component
    Polyol 7 is usually present in the pre-TT composition "polyol blend in an amount of about 60% w to about 95% w, preferably from about 65% w to - about 95% w, and more preferably from about 70 wt% to about 90 wt% by weight of the polyol premix composition.
    The following polyol premix composition contains a silicone surfactant. The silicone surfactant is used to form a foam from the mixture, as well as to control the size of the foam bubbles so that a foam of a desired cell structure is obtained. Preferably, a foam with small bubbles or cells contained therein of uniform size is desired since it has the most desirable physical properties; such as compressive strength and thermal conductivity. In addition, it is essential to have a foam with stable cells that do not collapse before formation or during the rise of the foam. Silicone surfactants for use in the preparation of - 20 polyurethane or polyisocyanate foams are available under a number of commercial names known to those usually skilled in the art. Such materials have been found to be applicable over a wide variety of formulations that allow uniform cell formation and maximum gas trapping to achieve very low density foam structures. O
    A preferred silicone surfactant comprises a polysiloxane block polyoxyalphaduylem. Some representative —— silicone surfactants useful for the = - the present invention are from Momentive L-5130, L-5180, 1-5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193, DC-197, DC-5582, and DC-5598; and B-8404, B-8407, B-8409 and B-8462 from Evonik Industries AG of Essen, Germany. Others are disclosed in U.S. Patent Nos.
    2,834,748; 2,917,480; 2,846,458 and 4,147,847. The silicone surfactant component is generally present in the polyol premix composition in an amount of about 0.5% w to about 5.0% w, preferably from about 1.0% w to about 4.0 wt%, and more preferably from about 1.5 wt% to about 3.0 wt%, by weight of the polyol premix composition.
    The polyol premix composition may optionally contain a non-silicone surfactant, such as a non-ionic non-silicone surfactant. This may include oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffinic oils, castor oil esters, ricinoleic acid esters, red Turkey oil, peanut oil, paraffins, and fatty alcohols. A preferred non-ionic non-silicone surfactant is LK-443, which is commercially available from Air Products Corporation. When a nonionic non-silicone surfactant is used, it is normally present in the polyol premix composition in
    "an amount of about 0.25% w to about 3.0% w, - preferably from about 0.5% w to about = 2.5%, and more preferably from about from - 0.75% w - to about 2.0% w, by weight of the polyol premix composition.
    The following inventive polyol premix composition contains a catalyst or catalysts, at least one of which is a non-amine catalyst. In one embodiment, catalysts - “non-amine are inorganic- or organometallic compounds. Useful inorganic- or organometallic compounds include, but are not limited to, organic salts, Lewis acid halides, or the like, of any metal, including, but not limited to, transition metals, post-transition (weak) metals, rare earth metals (eg, lanthanides), metalloids, alkali metals, alkaline earth metals, or the like. Examples of such metals can include, but are not limited to, bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium,. 20 titanium, mercury, zinc, antimony, uranium, cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium, zirconium, or combinations thereof. Non-exclusive examples of such inorganic- or organometallic catalysts include, but are not limited to, bismuth nitrate, lead 2-ethyloxate, lead benzoate, lead naphthenate, ferric chloride, antimony trichloride, antimony glycolate,
    - tin salts of carboxylic acids, DN dialkyl salts of carboxylic acids, potassium acetate,
    potassium octoate, potassium 2-ethyloxate, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, alkali metal carboxylic acid salts, N- (2- hydroxy- Sodium S-nonylphenol) -methyl-N-methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, or combinations thereof.
    These catalysts are usually present in the polyol premix composition in an amount of about 0.25% w to about 3.0% w, preferably from about 0.3% w to about 2.5 wt%, and more preferably from about 0.35 wt% to about 2.0 wt%, by weight of the polyol premix composition.
    Although these are usual amounts, the amount of said catalyst can vary widely, and the appropriate amount can easily be determined by those ordinarily skilled in the art.
    In another embodiment of the invention, the non-amine catalyst is a quaternary ammonium carboxylate.
    Useful . Quaternary ammonium carboxylates include, but are not limited to: (2-hydroxypropyl) 2-ethylhexanoate - trimethylammonium (TMR sold by Air Products and Chemicals) and (2-hydroxypropyl) -trimethylammonium formate (TMR-2nd sold by Air Products and Chemicals). These quaternary ammonium carboxylate catalysts are
    'generally present in the NS polyol premix composition' an amount of about 0.25 wt to about 3.086 wt, preferably from about 0.3 wt% to about 2.5 wt%, and more preferably from about 0.35% to about 2.0 wt%, by weight of the polyol premix composition. Although these are usual amounts, the amount of said catalyst can vary widely, and the appropriate amount can easily be determined by those ordinarily skilled in the art.
    In another embodiment, the non-amine catalyst is used in combination with an amine catalyst. Such amine catalysts can include any compound that contains an amino group and that exhibits the catalytic activity provided herein. Such compounds may be linear or cyclic non-aromatic or aromatic in nature. Useful, non-limiting amines include, primary amines, secondary or tertiary amines. Useful tertiary amine catalysts not only include N, N, N ', No., N Ҽ-pentamethyldiethyltriamine, N, N-dicyclohexylmethylamine, N, N-7 20-ethyldiisopropylamine, N, N-dimethylcyclohexylamine; N, N- dimethylisopropylamine; N-methyl-N-isopropylbenzylamine; N-methyl-N-cyclopentylbenzylamine; N-isopropyl-N-sec-butyl-trifluorethylamine, N, N-diethyl- (a-phenylethyl) -amine, N, N, N-tri-n-propylamine, or combinations thereof. Useful secondary amine catalysts do not exclusively include dicyclohexylamine; t-butylisopropylamine, di-t-butylamine;
    7 cyclohexyl-t-butylamine, di-sec-butylamine, “Dicyclopentylanmine, di- (a-trifluormethylethyl) -amine, di- (ar phenylethyl) -amine, or combinations thereof. Useful primary amine catalysts do not exclusively include: triphenylmethylamine and 1,1-diethyl-n-propylamine. Other useful amines include morpholines, imidazoles, ether-containing compounds, and the like. These include: dimorpholinodiethyl ether N-ethylmorpholine N-methylmorpholine ether bis (dimethylaminoethyl imidizole n-methylimidazole 1,2-dimethylimidazole dimorpholinodimethylether N, N, N ', N', N ”, Nº-pentamethylethylenetriamine N, ', N,' No. ”, No.-pentaethyldiethylenetriamine N, N, N ', N', N”, No. ”“ - pentamethyldipropylenetriamine bis ether (diethylaminoethyl) 7 20 bis ether (dimethylaminopropyl).
    o In embodiments where an amine catalyst is provided, the catalyst can be supplied in any amount to achieve the function of the present invention, without affecting the foaming or storage stability of the composition, as characterized herein. For this purpose, the amine catalyst can be supplied in
    'quantities less than or greater than those of. non-amine catalyst. o: TS
    The preparation of polyurethane or polyisocyanate foams using the compositions described herein can follow any of the methods well known in the art that can be employed, see Saunders and Frisch, Volumes I and
    II Polyurethanes Chemistry and Technology, 1962, John Wiley and Sons, New York, NY or Gum, Reese, Ulrich, Reaction
    Polymers, 1992, Oxford University Press, New York, NY or
    Klempner and Sendijarevic, Polymeric Foams and Foam
    Technology, 2004, Hanser Gardner Publications, Cincinnati, OH.
    In general, polyurethane or polyisocyanate foams are prepared by combining an isocyanate, the polyol premix composition, and other materials, such as optional flame retardants, dyes, or other additives.
    These foams can be rigid, flexible or semi-rigid, and can have a closed cell structure,
    an open cell structure or a mixture of open and closed cells,
    - 20 It is convenient in many applications to supply components for polyurethane or polyisocyanate foams in pre-mixed formulations.
    More typically, the foam formulation is premixed into two components. isocyanate and, optionally, other isocyanate-compatible raw materials, including but not limited to blowing agents and certain agents
    'silicone surfactants, comprise the first component, Ns “normally referred to as component“ A ”, to the composition of the“ polyol blend, including surfactant, catalysts, blowing agents, and "other optional ingredients comprise the second component, normally referred to as the “B” component.
    In any given application, component “B” may not contain all of the components listed above, for example, some formulations omit the flame retardant if a flame retardant is not a desired property for the foam.
    Therefore, polyurethane or polyisocyanate foams are readily prepared by combining components A and B, either by manual mixing for small preparations and, preferably, by mechanical mixing techniques to form blocks, ingots, laminates, panels by localized spill and other items, foams applied by spraying, foaming and the like.
    Optionally, other ingredients, such as flame retardants, dyes, auxiliary blowing agents, and other polyols 7 20 can be added to the mixing head or reaction site.
    Most conveniently, however, they are all incorporated into a component B, as described above.
    A suitable foamable composition to form a polyurethane or polyisocyanate foam can be formed 25. by reacting an organic polyisocyanate and the polyol premix composition described above.
    Any polyisocyanate
    'organic can be used in the synthesis of - T polyurethane or polyisocyanate foam including aliphatic and aromatic de - polyisocyanates. Suitable polyisocyanates. aliphatic organics include.polyisocyanate .... cycloaliphatic, araliphatic, aromatic and heterocyclic isocyanates which are well known in the field of polyurethane chemistry. These are described in, for example, US patents 4,868,224; 3,401,190; 3,454,606;
    3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124,605; and 3, .201,372, Preferred as a class are aromatic polyisocyanates. Representative of organic polyisocyanates correspond to the formula: R (NCO) z where R is a polyvalent organic radical that is either aliphatic, aralkyl, aromatic or mixtures thereof, ez is an integer that corresponds to the valence of R and is at least two . Representatives of the organic polyisocyanates contemplated herein include, for example, 720 aromatic diisocyanates; such as, toluene 2, 4- ". diisocyanate, toluene 2,6-diisocyanate, mixtures of toluene 2,4- and 2,6-diisocyanate, toluene diisocyanate crude, methylene diphenyl diisocyanate, methylene diphenyl diisocyanate and the like; aromatic triisocyanates; such as 4.4 ', 4 "triisocyanate - triphenylmethane, toluene 2,4,6-triisocyanate; the
    'aromatic ttetraisocyanates such as 4,4'- dimethyldiphenylmethane-2,2', 5,5'-tetraisocyanate, are similar; aralkyl polyisocyanates such as xylene diisocyanate; aliphatic polyisocyanate, such as hexamethylene-1, 6-diisocyanate, lysine diisocyanate methylester and the like; and mixtures of those mentioned.
    Other “organic polyisocyanates include polymethylene polyphenylisocyanate, halogenated methylene diphenylisocyanate,
    m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-
    methoxyphenylene-2,4-diisocyanate, 4.4 "-biphenylene diisocyanate, 3.3" -dimethoxy-4.4 '"- biphenyl diisocyanate,
    3.3 "-dimethyl-4.4 '" - biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate.
    Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, isophorene diisocyanate, 4,4'-methylenebis (cyclohexyl) isocyanate), and the like; Typical aromatic polyisocyanates include m-, and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and
    * 20 2, 6-toluenediisocyanate, dianisin diisocyanate, bitoylene o isocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanatophenyl) methylene, bis (2-methyl-4-isocyanatophenyl) methane, and the like.
    Preferred polyisocyanates are polymethylene polyphenyl isocyanates,
    particularly mixtures containing from about 30 to about 85 wt% of methylenebis (phenyl isocyanate)
    “With the remainder of the mixture comprising polymethylene“ ““ polyphenyl polyisocyanates with greater functionality than - - These polyisocyanates are prepared by conventional methods known in the art. In the present invention, polyisocyanate and polyol are employed in amounts that will produce a stoichiometric NCO / OH ratio in the range of about 0.9 to about 5.0. In the present invention, the NCO / OH equivalence ratio is preferably about 1.0 or more and about 3.0 or less, with the ideal range being about 1.1 to about 2 , 5. Especially suitable organic polyisocyanates include polymethylene polyphenyl isocyanate, methylenebis (phenyl isocyanate), toluene diisocyanates, or combinations thereof.
    In the preparation of polyisocyanate foams, trimerization catalysts are used for the purpose of converting the mixtures together with excess component A to polyisocyanate-polyurethane foams. The trimerization catalysts used - 20 can be any catalyst known to a person skilled in the art, including, but not limited to, glycine salts, i tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal salts of carboxylic acids and mixtures of various types of catalysts. Preferred species within the classes are potassium acetate, potassium octoate, and N- (2-
    7 sodium hydroxy-5-nonylphenol) -methyl-N-methylglycinate.
    Conventional flame retardants can also be incorporated, preferably in an amount of no more than about 20 weight percent of the reagents.
    —Optional flame retardants include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2-chloroisopropyl) phosphate, tricresyl phosphate, tris (2,2-chloroisopropyl) phosphate, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dimethyl methylphosphonate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dicyclopropyl) phosphate, and tetra-kis- (2-chloroethyl) ethylene diphosphate, triethylphosphate, diamonium phosphate, various "halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, melamine, and the like. Other optional ingredients may include 0 to about 7 percent water, which chemically reacts with the isocyanate to produce carbon dioxide. This carbon dioxide acts as an auxiliary blowing agent. "20 formic acid is also used to produce carbon dioxide by reaction with the isocyanate and is optionally added to component" B ".
    In addition to the previously described ingredients, other ingredients such as dyes, fillers, pigments and the like, can be included in the preparation of foams. Dispersing and stabilizing agents
    'cells can be incorporated into the present mixtures. “T Conventional fillers for use here include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black and silica.
    The filler material, if used, is normally present in an amount, by weight, ranging from about 5 parts to 100 parts per 100 parts of polyol.
    A pigment that can be used here can be any conventional pigment, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chromium green, chromium yellow, iron blue siennas, molybdate oranges and organic pigments such as reds , benzidine yellow,
    toluidine reds, toners and phthalocyanines.
    Can the polyurethane or polyisocyanate foams produced vary in density from about 8.0 kg / m at about 961 kg / m (0.5 pounds per cubic foot to about 60 pounds per cubic foot), preferably about 16 kg / m at 320 kg / m (1.0-20.0 pounds per cubic foot), plus 20 preferably about 24 kg / m ”at 96 kg / M (1.5 to 6.0 lb per cubic foot). The density obtained is a function of how much of the blowing agent or blowing agent mixture in this invention plus the amount of auxiliary blowing agent, such as water or other blowing coagents, is present in components A and / or B, or alternatively added at the time the foam is being
    ' ready.
    These foams may be rigid, flexible or semi-rigid foams, and may have a closed cell structure, an open cell structure or a mixture of open and closed cells.
    These foams are used in a variety of well-known applications, including but not limited to thermal insulation, cushioning, flotation, packaging, adhesives, empty fill, decorative arts and crafts, and shock absorption.
    The following non-limiting examples serve to illustrate the invention
    Example 1 (Comparative Example)
    A polyol formulation (Component B) was made of 100 parts by weight of a polyol mixture, 1.5 parts by weight of Niax L6900 silicone surfactant, 1.5 parts by weight of water, 1.2 parts by weight of pentamethyldiethylene triamine catalyst (sold as Polycat 5 by Air Products and Chemicals), and 8 parts by weight of trans-1,3,3,3-tetrafluorpropene blowing agent.
    The total composition '20 of Component B, when freshly prepared and combined -. with 120.0 parts by weight of polymeric isocyanate Lupranate M20S produced a good quality foam with a fine and regular cell structure.
    Foam reactivity was typical of a spill on site.
    The total composition of Component B (112.2 parts) was then aged at 54.4 ºC (130 ºF) for 62 hours, and then
    º combined with 120.0 parts of polymeric isocyanate M20S “and to produce a foam. The foam was very poor in EM. - appearance with significant collapse of the cells. A significant yellowing of the polyol premix was noted during aging.
    Example 2 (Comparative example) A polyol (Component B) The formulation was made of 100 parts by weight of a polyol mixture, 1.5 parts by weight N69 silicone surfactant L6900, 1.5 parts by weight of water, 1, 2 parts by weight of pentamethyldiethylenetriamine catalyst (sold as Polycat 5 by Air Products and Chemicals) and 8 parts by weight blowing agent trans-1-chloro-3,3,3-trifluorpropene. The total composition of component B, when freshly rinsed and combined with 120.0 parts by weight of polymeric isocyanate Lupranate M20S, produced a good quality blade with a fine, regular cell structure. The reactivity of the foam was typical of the spill type at the site. The composition with Component B (112.2 parts) was then aged at 54.4 '20 "ºC (130" ºF) for 168 hours and then combined with 120.0 "* parts of polymeric isocyanate M20S to produce a foam The foam was very poor in appearance with significant cellular collapse, significant yellowing of the polyol premix was observed during aging.
    "Example 3 (foam test) o a polyol formulation (Component B) was produced It is 100 parts by weight of a polyol mixture, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5 parts by weight of water, 2.0 parts by weight of N, N-dichlorohexylmethylamine catalyst (sold as Polycat 12 by Air Products and Chemicals) (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight of a bismuth-based catalyst (sold as Dabco MB-20 from Air Products and Chemicals) and 8 parts by weight of trans-1,3,3,3-tetrafluorpropene blowing agent The total composition of Component B, when freshly prepared and combined with 120.0 parts by weight of polymeric isocyanate Lupranate M20S produced a good quality foam with a fine and regular cell structure.The foam reactivity was typical of that of the spill type on site. (114.75 parts) was then aged to 54.4 ºC (130 * F) for 336 hours and then combined r 20 with 120.0 parts of polymeric isocyanate M20S to produce a foam. The foam was excellent in appearance, with no evidence of cell collapse. There was no yellowing of the polyol premix observed during aging.
    Example 4 (foam test) A polyol formulation (Component B) was produced
    . 100 parts by weight of a polyol mixture, 1.5 parts by weight of Niax L6900 silicone surfactant, 0.5 parts by weight of water, 2.0 parts by weight of N, N- - dicyclohexylmethylamine catalyst (sold as Polycat 12 by Air Products and Chemicals) (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight of zinc 2-ethylhexanoate (sold as 30-3038 by Strem Chemicals) and 8 parts by weight of trans-1-chloro-3,3,3-trifluorpropene blowing agent. The total composition of Component B, when freshly prepared and combined with 103.0 parts by weight of polymeric isocyanate Lupranate M20S, produced a good quality foam with a fine and regular cell structure. The reactivity of the foam was typical of the spill type at the site. The total composition of Component B (113.75 parts) was then aged at 54.4 ºC (130 ºF) for 336 hours and then combined with 103.0 parts of polymeric isocyanate M20S to produce a foam. The foam was excellent in appearance, with no »20 evidence of cell collapse. It was not noticed: yellowing of the polyol premix during aging.
    Example 5 (foam test) A polyol formulation (Component B) was produced from 100 parts by weight of a polyol mixture, 1.5 parts by weight of Niax L6900 silicone surfactant, 1.0 part in
    "water weight, 2.0 parts by weight of catalyst N, N-“ dicyclohexylmethylamine (sold as Polycat 12 by AIE - Products and Chemicals) (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight of a potassium-based catalyst (sold as Dabco K15 by Air Products and Chemicals) and 8 parts by weight of the blowing agent trans-1-chloro-3,3,3- trifluorpropene.
    The total composition of Component B, when freshly prepared and combined with 112.0 parts by weight of Lupranate M20S polymeric isocyanate, produced a good quality foam with a fine and regular cell structure.
    The reactivity of the foam was typical of the spill type at the site.
    The total composition of Component B (114.75 parts) was then aged at 54.4 ºC (130 º * F) for 504 hours and then combined with 112.0 parts of polymeric isocyanate M20S to produce a foam.
    The foam was excellent in appearance, with no evidence of cell collapse.
    Slight yellowing of the polyol premix was noted during aging.
    权利要求:
    Claims (11)
    [1]
    - CLAIMS - O 1. FOAM COMPOSITION, characterized by: understanding: a. a hydroaloolefin blowing agent, b. one or more polyols, Cc. one or more surfactants, and d. a non-amine catalyst selected from the group consisting of an inorganometallic compound, an organometallic compound, a quaternary ammonium carboxylate catalyst, and combinations of those mentioned, wherein the inorganometallic compound or the organometallic compound independently comprises an organic salt selected from the group consisting of bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, magnesium, manganese, potassium, sodium, titanium, mercury, zinc, antimony, uranium, cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium , zirconium, and combinations thereof mentioned 2, Foamy composition, according to ”20 claim 1, characterized in that said catalyst the non-amine is selected from the group consisting of bismuth nitrate, lead 2-ethyloxate, benzoate lead, lead naphthenate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl acid salts carboxylics, potassium acetate, potassium octoate, 2-
    [2]
    ”Potassium ethyloxate, potassium salts of o or carboxylic acids, zinc salts of carboxylic acids, 2º | V zinc ethylexanocate, glycine salts, alkali metal carboxylic acid salts, N- (2-hydroxy-5- nonylphenol) - sodium methyl-N-methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, or combinations thereof.
    [3]
    Foamy composition according to claim 2, characterized in that said non-amine catalyst is present in an amount of about 0.25% w to about 3.0% w, by weight of the composition.
    [4]
    Foamy composition according to claim 1, characterized in that said non-amine catalyst is a quaternary ammonium carboxylate.
    [5]
    Foamy composition according to claim 4, characterized in that said non-amine catalyst is (2-hydroxypropyl) 2-ethylhexanoate - trimethylammonium or (2-hydroxypropyl) - trimethylammonium formate.
    [6]
    Foamy composition according to claim 5, characterized in that said non-amine catalyst is present in an amount of about 0.25% w to about 3.0% w, by weight of the composition.
    [7]
    Foamy composition according to claim 1, characterized in that said blowing agent additionally comprises a blowing coagent
    ”Selected from the group consisting of water, Ns fluorocarbon -. - .. hydrocarbon, -. . chlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, halogenated hydrocarbons, ether, ester, alcohol, aldehyde, ketone, organic acid, gas-generating material, and combinations thereof
    [8]
    Foamy composition according to claim 8, characterized in that said blowing agent comprises a hydroaloolefin selected from the group consisting of trifluorpropene, tetrafluorpropene, pentafluorpropane chlorotrifluorpropene, chlorodifluorpropene, chlorotrifluorpropene, chlorotetrafluorpropene, hexafluoropropene, hexafluoropropene, hexafluoropropene, and hexafluoropropene, hexafluoropropene, hexafluoropropene, and hexafluoropropene.
    [9]
    Ss, Edible composition according to claim 8, characterized in that said blowing agent is selected from the group consisting of 1,3,3,3-tetrafluorpropene (1234ze); 1,1,3,3-tetrafluorpropene; 1,2,3,3 pentafluorpropene, 3- (1225ye),, 20 1.1, 1-trifluorpropene; 1,2,3,3, 3-pentafluorpropene, 1,1,1,3,3-pentafluorpropene (122520) and 1,1,2,3,3-pentafluorpropene (1225yc); (2) -1,1,1,2,3-pentafluorpropene (1225yez); 1-chloro-3,3,3-trifluorpropene (1233zd), 1,1,1,4,4,4-hexafluorbut-2-ene (1336mzzm) or combinations thereof.
    [10]
    10. Foamy composition, according to
    claim 1, characterized in that additionally RW 0 comprises an amine catalyst. | 7 7 TS
    [11]
    Foamy composition according to claim 10, characterized in that the amine catalyst is Ss selected from the group consisting of N, N, N ', N "%, N" º "- pentamethyldiethyltriamine, N, N-dicyclohexylmethylamine, N, N-ethyldiisopropylamine, N, N-dimethylcyclohexylamine; N, N-dimethylisopropylamine; N-methyl-N-isopropylbenzylamine; N-methyl-N-cyclopentylbenzylamine; N-isopropyl-N-sec-butyl-trifluorethylamine, N, N-diethyl- (a-phenylethyl) -amine, N, N, N-tri-n-propylamine, dicyclohexylamine; t-butylisopropylamine, di-t-butylamine; cyclohexyl-t-butylamine, di-sec-butylamine, dicyclopentylamine, di- (a-trifluormethylethyl) -amine, di- (a-phenylethyl) -amine, triphenylmethylamine and 1,1-diethyl-n-propylamine; dimorpholinodiethylether; N-ethylmorpholine; N-methylmorpholine; bis ether (dimethylaminoethyl); imidizole; n-methylimidazole; 1,2-dimethylimidazole; dimorpholinodimethylether; N, N, N ', N', N ”, No.” - pentamethyldiethylenetriamine; N, N, N ', N', N%, No.- ”20 pentaethyldiethylenetriamine; N, N, N ', N', No., No.- pentamethyldipropylenetriamine; bis ether (diethylaminoethyl); bis ether (dimethylaminopropyl); and combinations of those mentioned.
    1 - ABSTRACT -; FOAM COMPOSITION | 7 7 TI EEE The invention provides polyurethane and polyisocyanurate foams and methods for their preparation.
    More particularly, the invention relates to closed cell polyurethane and polyisocyanate foams, and methods for their preparation.
    Foams are characterized by a thin, uniform cell structure and little or no foam collapse.
    The foams are produced with a polyol premix composition that comprises a combination of a hydroaloolefin blowing agent, a polyol, a silicone surfactant, and a non-amine catalyst used individually or in combination with an amine catalyst. + -.
    类似技术:
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    同族专利:
    公开号 | 公开日
    RU2015144564A3|2019-01-30|
    JP2016000820A|2016-01-07|
    CN106084163A|2016-11-09|
    US20110152392A1|2011-06-23|
    EP2513227A4|2014-12-03|
    EP2513227A2|2012-10-24|
    US20200048397A1|2020-02-13|
    CN104592468A|2015-05-06|
    CA2784583A1|2011-07-14|
    JP2017071781A|2017-04-13|
    JP2013514452A|2013-04-25|
    RU2012130294A|2014-01-27|
    WO2011084563A3|2011-10-20|
    CN102753624A|2012-10-24|
    US20180105633A1|2018-04-19|
    WO2011084563A2|2011-07-14|
    JP5810096B2|2015-11-11|
    KR20120115982A|2012-10-19|
    JP6072157B2|2017-02-01|
    MX2012006804A|2012-08-31|
    RU2015144564A|2018-12-28|
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