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    • 专利摘要:
    METHOD OF PRODUCTION OF AN INSULATION UNIT AND INSULATING UNIT. Embodiments of the invention include insulating units and methods of producing the insulating units. The insulating units include a first surface, a structural seal disposed in at least portions of the first surface, and a second surface disposed in the structural seal. The structural seal includes the product of the reaction of at least one first isocyanate, at least one reactive side with isocyanate, and at least one adhesion promoter including a product of the reaction of at least one secondary amino alkoxy silane with at least one second isocyanate.
    公开号:BR112013010666B1
    申请号:R112013010666-2
    申请日:2011-11-10
    公开日:2021-01-19
    发明作者:Bindushree Radhakrishnan；Laura A. Grier；Syed Z. Mahdi
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Field of invention
    [0001] Embodiments of the invention refer to insulating glass sealing units, more specifically to sealing units having polyurethane-based seals. Background of the invention
    [0002] The insulating (or insulating) glass sealing units (VI) comprise two parallel sheets of glass held apart by spacer bars. The cavity formed between the glass sheets is filled with an inert gas to help reduce the transmission of heat and sound. Typically, two different types of seals are used to attach the glass to the spacer bars. The innermost or primary seal joins the spacer bars with the glass sheets, and serves as a barrier against the escape or exit of the inert gas from the cavity, as well as a barrier against the entry or penetration of moisture vapor into the cavity. Thermoplastic polyisobutylene is a common primary sealant. However, this material has no mechanical strength and has comparatively less adhesion than the outer or secondary seal. As such, a function of the secondary seal is to provide mechanical resistance to the unit and to prevent rupture of the primary seal during the natural thermal cycles to which the unit is exposed.
    [0003] Due to its good mechanical properties, polyurethane, especially polyurethane which is based on a polyol based on hydrophobic polybutadiene, is a secondary seal commonly used. However, such polyurethanes may not have optimal characteristics of adhesion to glass under extreme environmental conditions. Therefore, there is a need for polyurethane-based seals that have better adhesion characteristics to glass. Summary of the invention
    [0004] Embodiments of the invention relate to polyurethane-based sealants that have better glass adhesion characteristics.
    [0005] The embodiments include methods of producing an insulating unit. The methods include the formation of at least one isocyanate-reactive side, which includes at least one hydrophobic polyol having an average functionality of about 2 to about 6, at least one chain extender with two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400, at least one filler (such as barium sulfate (BaSO4), aluminum oxide (Al2O3), aluminum hydroxide (Al (OH) 3), magnesium hydroxide (Mg (OH) 2), calcium carbonate (CaCO3), mica and talc). The at least one isocyanate-reactive side is contacted with at least one first isocyanate in the presence of at least one adhesion promoter. The at least one adhesion promoter includes at least the reaction product of at least one secondary aminoalkoxy silane and at least one second isocyanate, the reaction product having an average of at least one silane group and at least one isocyanate group per molecule. The at least one isocyanate reactive side contacted, the at least one first isocyanate, and the at least one adhesion promoter are applied between at least portions of a first surface and a second surface.
    [0006] The embodiments comprise insulating units, which include a first surface, a structural seal disposed in at least portions of the first surface, and a second surface disposed on the structural seal. The structural seal comprises the reaction product of at least one first isocyanate, at least one side reactive with isocyanate, and at least one adhesion promoter. The at least one isocyanate-reactive side includes at least one hydrophobic polyol having an average functionality of about 2 to about 6, at least one chain extender having two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group less than 400, and at least one filler (such as barium sulfate (BaSO4), aluminum oxide (Al2O3), aluminum hydroxide (Al (OH) 3), magnesium hydroxide (Mg (OH) 2) carbonate calcium (CaCO3), mica, and talc). The at least one adhesion promoter includes at least the reaction product of at least one secondary aminoalkoxy silane and at least one second isocyanate, the reaction product having an average of at least one silane group and at least one isocyanate group per molecule. Description of embodiments of the invention
    [0007] Embodiments of the invention provide methods for producing sealants that have better characteristics of adhesion to glass, while maintaining their physical, structural and mechanical properties. Embodiments of the seals comprise two-component polyurethane systems in which a first component includes at least one polyol and is reacted with a second component which includes at least one polyisocyanate. The first component and the second component are mixed immediately before application, and applied to a base material to be cured.
    [0008] The first component (also called an isocyanate reactive side) includes at least one hydrophobic polyol having an average functionality of about 2 to about 6. Between about 10 and about 55% by weight of the first component can include the at least one polyol. All individual values and sub-intervals between about 10 and about 55% by weight are included and disclosed here; for example, the amount can be from a lower limit of about 10, 15, 20, 25, 30, 35, 40, or 45% by weight to an upper limit of about 20, 25, 30, 35, 40, 45, 50, or 55% by weight.
    [0009] Suitable polyols can include at least one hydrophobic polyol such as a diol of a conjugated diolefin monomer, a polyisobutylene diol, a polyester polyol prepared from fatty diols and / or fatty diacids, or mixtures thereof. For example, the hydrophobic polyol can be prepared from dimeric fatty alcohols and / or dimeric fatty acids. The conjugated olefin monomer diols that can be used include hydrogenated polybutadienediols, and hydrogenated polyisoprene diol. Hydrogenated polybutadiene polyols are sold by Mitsubishi Chemical Corporation, under the trade name POLITAIL and Kraton polyols sold by Kraton Polimers of Houston, Texas.
    [0010] Polyester polyols of dimeric acids containing from about 18 to about 44 carbon atoms can also be used. Dimeric acids (and esters of these) are a well-known class of commercially available dicarboxylic acids (or esters). They are usually prepared by dimerizing long chain unsaturated aliphatic monocarboxylic acids, usually 13 to 22 carbon atoms, or their esters (alkyl esters). Dimerization (although we should not be bound by this theory) is thought to proceed through possible mechanisms that include Diels Alder mechanisms, free radicals and carbon dioxide. The dimeric acid material will generally contain 26 to 44 carbon atoms. Particularly, examples include dimeric acids (or esters) derived from C18 and C22 unsaturated monocarboxylic acids (or esters) which will produce, respectively, C36 and C44 dimeric acids (or esters). Dimeric acids derived from C18 unsaturated acids, which include acids such as linoleic and linolenic acids are particularly well known (producing C36 dimeric acids). For example, DELTA 9, 11 and DELTA 9, 12 linoleic acids can dimerize with an unsaturated cyclic structure (although this is only one possible structure; other structures, including acyclic structures are also possible). Dimeric acid products can also contain a proportion of trimeric acids (C54 acids when using C18 starting acids), possibly even higher oligomers and also small amounts of monomeric acids. Several different degrees of dimeric acids are available from commercial sources and these differ from each other mainly in the amount of monobasic and quarterly fractions and the degree of unsaturation. PRIPLAST polyester polyols are dimerized branched C36 fatty acids that are particularly useful as a hydrophobic polyol in the practice of this invention. PRIPLAST polyester polyols are commercially available in Uniqema de Gouda, The Netherlands. The hydrophobic can have an average molecular weight number that is within the range of about 1500 to about 4000, or in the range of about 2000 to about 3000.
    [0011] Suitable polyols also include polyols based on natural oils (NOBP). NOBP are polyols based on, or derived from, resources of renewable raw materials, such as oils from vegetable seeds of natural and / or genetically modified plants and / or fats from animal sources. Such oils and / or fats are generally composed of triglycerides, that is, fatty acids bound to glycerol. Preferred are vegetable oils that have at least about 70 percent unsaturated fatty acids in the triglyceride. Preferably, the natural product contains at least 85 percent by weight of unsaturated fatty acids. Examples of preferred vegetable oils include, but are not limited to, castor, soy, olive, peanut, rapeseed, corn, sesame, cotton, canola, safflower, flaxseed, palm, grape seed, black caraway, pumpkin seed, borage, wood germ, apricot kernel, pistachio seed oils, almond, macadamia nut, avocado, sea buckthorn, hemp, hazelnut, primrose, wild rose, thistle, walnut, sunflower, jatropha, or a combination of two or more of these oils. Examples of animal products include lard, tallow, fish oils and mixtures of two or more of these products. In addition, oils obtained from organisms such as algae can also be used. Combination of oils / fats based on plants, algae and animals can also be used.
    [0012] Polyols derived from modified natural oils can be obtained through a multi-step process, in which oils / fats of animal or vegetable origin are subjected to transesterification and the constituent fatty acids are recovered. This step is followed by hydroformylation of carbon-carbon double bonds in the constituent fatty acids to form hydroxymethyl groups. Suitable hydroformylation methods are described in USP 4,731,486 and 4,633,021, for example, and in U.S. Published Patent Application 2006/0193802. Hydroxymethylated fatty acids are "monomers", which form one of the building blocks for the polyol based on natural oil. The monomers can be of a single type of hydroxymethylated fatty acid and / or hydroxymethylated fatty acid methyl ester, such as hydroxymethylated oleic acid or methyl ester, hydroxymethylated linoleic acid or methyl ester thereof, hydroxymethylated linolenic acid or methyl ester thereof, α acid - and (-linolenic acid or methyl ester, myristoleic acid or methyl ester, palmitoleic acid or methyl ester, oleic acid or methyl ester, vaccenic acid or methyl ester, petroselinic acid or methyl ester, gadoleic acid or methyl ester of this, erucic acid or methyl ester of this, nervous acid or methyl ester of this, stearidonic acid or methyl ester of this, arachidonic acid or methyl ester of this, tymnodonic acid or methyl ester of this, clupanodonic acid or methyl ester of this, cervical acid or methyl ester of this , or hydroxymethylated ricinoleic acid or methyl ester thereof. In one embodiment, the monomer is met hydroformylated iloelate. Alternatively, the monomer may be the hydroformylation product of the fatty acid mixture recovered from the transesterification process of animal or vegetable oils / fats. In one embodiment, the monomer is hydrogenated soy fatty acid. In another embodiment the monomer is hydrogenated castor fatty acid. In another embodiment the monomer can be a mixture of selected hydroxymethylated fatty acids or methyl esters thereof.
    [0013] In one embodiment the NOBP is monomeric NOBP rich in monol. "Monol-rich monomer" and similar terms means a composition comprising at least 50, typically at least 75 and more typically at least 85 weight percent (% by weight) of monohydroxy functional fatty acid alkyl ester such as , but not limited to formula I:

    [0014] The length of the carbon skeleton of formula I may vary, e.g., C12-C20, but is typically C18, since the placement of the hydroxymethyl group may vary along its length. The monol-rich monomer used in the practice of this invention can comprise a mixture of monohydroxy functional fatty acid alkyl esters varying both in the length of the carbon backbone and in the placement of the hydroxy group along the length of the various carbon backbones. The monomer can also be an alkyl ester other than methyl, e.g., a C2-C8 alkyl ester. Other components of the composition include, but are not limited to, poly (e.g., di-, tri-, tetra-, etc.) alkyl esters of hydroxy functional fatty acids.
    [0015] The source of the monol-rich monomer can vary widely and includes, but is not limited to, oleic-rich raw material or distillation of a oleic-low raw material, eg, a natural seed oil, as, for example, revealed in the pending order "PURIFICATION OF HYDROFORMYLATED AND HYDROGENATED FATTY ALKYL ESTER COMPOSITIONS" by George Frycek, Shawn Feist, Zenon Lysenko, Bruce Pynnonen and Tim Frank, filed on 20 June 2008, PCT order number / US08 / 67585, published as WO 2009/009271. The use of NOBP made using a monomer not rich in alkyl esters of monohydroxy functional fatty acids results in a highly cross-linked system, which can lead to loss of mechanical properties. The sealing compositions require polymers with high elongation and, thus, the preference for monomeric NOBP rich in monol. Mono-functional monomers, such as those of formula (I), are used to synthesize the polyol.
    [0016] The monomeric NOBP rich in monol can be derived by first hydroformylating and hydrogenating the alkyl esters or fatty acids, followed by purification to obtain the monomer rich in monol. Alternatively, the alkyl esters or fatty acids can first be purified to obtain rich mono-unsaturated monomer and then hydroformylated and hydrogenated.
    [0017] In one embodiment NOBP is made from a monomer derived using epoxidation and ring opening of the fatty acids or methyl esters of natural oil fatty acids, as described in WO 2009/058367 and WO 2009/058368.
    [0018] The polyol is formed by reacting the monomer with an appropriate initiator compound to form a polyester or polyether / polyester polyol. Such a multi-step process is commonly known in the art, and is described, for example, in PCT Nos. WO 2004/096882 and 2004/096883. The multi-step process can result in the production of a polyol with both hydrophobic and hydrophilic moieties, which results in better miscibility with both water and conventional petroleum-based polyols.
    [0019] The initiator for use in the multi-step process for the production of polyols derived from natural oils can be any initiator used in the production of conventional petroleum-based polyols. Preferably, the primer is selected from the group consisting of neopentylglycol; 1,2-propylene glycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; aminoalcohols such as ethanolamine, diethanolamine and triethanolamine; alkanediols such as 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,5-hexanediol; ethylene glycol; diethylene glycol, triethylene glycol; bis-3-aminopropylmethylamine, ethylenediamine; diethylenetriamine; 9 (1) - hydroxymethyloctadecanol, 1,4-bis-hydroxymethylcyclohexane; 8,8-bis (hydroxymethyl) tricycle [5,2,1,02,6] decene; Dimerol alcohol (36-carbon diol available from Henkel Corporation); hydrogenated bisphenol; 9.9 (10.10) -bishydroxymethyloctadecanol; 1,2,6-hexanotriol and combination thereof. Preferably the initiator is selected from the group consisting of glycerol; ethylene glycol; 1,2-propylene glycol; trimethylolpropane; ethylenediamine; pentaerythritol; 1,4-cyclohexanedimethanol, diethylene triamine; sorbitol; sucrose; or any of those mentioned above in which at least one of the alcohol or amine groups present has reacted with ethylene oxide, propylene oxide or a mixture thereof; and combinations of these. Preferably, the initiator is glycerol, trimethylolpropane, pentaerythritol, 1,4-cyclohexanedimethanol, sucrose, sorbitol, and / or a mixture thereof. Other initiators include other linear and cyclic compounds containing an amine. Examples of polyamine initiators include ethylenediamine, neopentyldiamine, 1,6-diaminohexane; bisaminomethyltricyclodecane; bisaminocyclohexane; diethylenetriamine; bis-3-aminopropylmethylamine; triethylenetetramine various isomers of toluenediamine; diphenylmethanediamine; N-methyl-1,2-ethanediamine, N-methyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N-dimethylethanolamine, 3,3'-diamino-N-methyl-dipropylamine , N, N-dimethyldipropylenetriamine and aminopropylimidazole. The embodiments comprise a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol at a weight ratio of about 60:40 to about 5:95.
    [0020] In one embodiment the initiators are alkoxylated with ethylene oxide, propylene oxide, or a mixture of ethylene and at least one other alkylene oxide to give an alkoxylated initiator with a molecular weight between 200 and 6000, preferably between 500 and 5000. In one embodiment, the initiator has a molecular weight of 550, in another embodiment the molecular weight is 625, and in yet another embodiment the initiator has a molecular weight of 4600.
    [0021] In one embodiment, at least one initiator is a polyether initiator having an equivalent weight of at least 400 or an average of at least 9.5 ether groups per active hydrogen group, and such initiators are described in WO 2009/117630 .
    [0022] The ether groups of the polyether initiator can be in poly (alkylene oxide) chains, such as in poly (propylene oxide) or poly (ethylene oxide), or a combination of these. In one embodiment, the ether groups can be in a structure of poly (propylene oxide) diblocks protected with poly (ethylene oxide).
    [0023] In one embodiment, NOBP is a polyol comprising at least two portions of natural oils separated by a molecular structure having at least about 19 ether groups or separated by a polyether molecular structure having an equivalent weight of at least about 480.
    [0024] In one embodiment, a NOBP is made with an alkoxylated initiator or combination of alkoxylated initiators having an equivalent average weight of between 400 and 3000 per active hydrogen group. The equivalent average weight can be from a lower limit of 400, 450, 480, 500, 550, 600, 650, 700, 800, 900, 1000, 1200 or 1300 up to an upper limit of 1500, 1750, 2000, 2250 , 2500, 2750 or 3000 per active hydrogen group.
    [0025] Thus, in this embodiment, at least two of the monomers based on natural oils are separated by a molecular structure having an average molecular weight of between 1250 Daltons and 6000 Daltons. The average molecular weight can be from a lower limit of 1250, 1500, 1750, 2000, 2250, 2500, 2750, or 3000 Daltons to an upper limit of 3000, 3500, 4000, 4500, 5000, 5500, or 6000 Daltons .
    [0026] To form the polyether initiator, the active hydrogen groups can be reacted with at least one alkylene oxide, such as ethylene oxide or propylene oxide or a combination thereof; or a propylene oxide block followed by an ethylene oxide block, to form a polyether polyol by means within the skill of the art. The polyether initiator can be used as an initiator for reacting with at least one monomer based on natural oil. Alternatively, the initiator is reacted by means within the skill in the art to convert one or more hydroxyl groups to alternative active hydrogen groups, such as propylene oxide.
    Thus, in one embodiment the polyol based on natural oil can comprise at least two portions of natural oil separated by a molecular structure having at least 19 ether groups or having an equivalent weight of at least 400, preferably both. When the polyether initiator has more than 2 active hydrogen groups reactive with or derived from natural oil, each portion of natural oil is separated from each other by an average of at least 19 ether groups or a molecular weight structure of at least 400, preferably both.
    [0028] The functionality of the resulting polyols based on natural oils is greater than 1.5 and generally not greater than 6. In one embodiment the functionality is less than 4. The number of hydroxyls of the polyols based on natural oils can be less than 300 mg KOH / g, preferably between 20 and 300, preferably between 20 and 200. In one embodiment, the number of hydroxyls is less than 100.
    [0029] The first component also includes at least one chain extender. For purposes of the embodiments of the invention, a chain extender is a material having two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400 daltons. All individual values below 400 daltons are included and described here; for example, the equivalent weight per reactive group with isocyanate can be less than 150, 200, 250, 300, 350 or 400 daltons. Between about 0.5 and about 15% by weight of the first component can include at least one chain extender. All individual values and sub-ranges between about 0.5 and about 15% by weight are included here and are disclosed here; for example, the amount can be from a lower limit of about 0.5, 1, 2, 3, 4, 5, 7, 10, or 12% by weight to an upper limit of about 3, 4, 5, 7, 10, 12 or 15% by weight.
    Representative chain extenders include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3- or 1,4-butanediol, dipropylene glycol, 1,2- and 2,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, tripropylene glycol, 1,2-ethylhexyldiol, ethylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, 1,5-pentanediol, 1,6-hexanediol, 1,3-cyclohexandiol, 1,4-cyclohexanediol; 1,3-cyclohexanedimethanol, 1,4-cyclohexane-dimethanol, N-methylethanolamine, N-methyl-iso-propylamine, 4-aminocyclohexanol, 1,2-diaminoethane, 1,3-diaminopropane, hexylmethylenediamine, methylene-bis (aminocyclohexane) , isophorone-diamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, diethylenetriamine, 3,5-diethyl-toluene-2,4-diamine and 3,5-diethyl-toluene-2,6-diamine, and mixtures thereof. Suitable primary diamines include, for example, dimethylthiotoluenediamine (DMTDA) such as Ethacure 300 from Albermarle Corporation, diethyltoluenediamine (DETDA) such as Ethacure 100 Ethacure from Albermarle (a mixture of 3,5-diethyltoluene-2,4-diamine and 3,5 -diettyltoluene-2,6-diamine), isophorone-diamine (IPDA), and dimethylthiotoluenediamine (DMTDA).
    [0031] The first component also includes at least one filling. The filling materials can be organic or inorganic, and can be in the form of discrete, individual particles. Inorganic fillers include, for example, metal oxides, metal hydroxides, metal carbonates, metal sulfates, various types of clay, silica, alumina, powdered metals, glass microspheres, or particles containing void. Specific examples of inorganic fillers include calcium carbonate, barium sulfate, sodium carbonate, magnesium carbonate, magnesium sulfate, barium carbonate, kaolin, carbon, calcium oxide, magnesium oxide, magnesium hydroxide, aluminum, aluminum hydroxide, and titanium dioxide. Inorganic fillers also include, for example, those having higher proportions than particles, such as talc, mica and wollastonite. Organic fillers include, for example, latex particles, thermoplastic elastomer particles, pulp powders, wood powders, cellulose derivatives, chitin, chitosan powder, high melting, highly crystalline polymer powders, beads of highly cross-linked polymers, organo-silicon powders, and superabsorbent polymer powders or particles, such as polyacrylic acid and the like. Combinations of any of these fillers can also be used. Between about 5 and about 50% by weight of the first component can include the filler. All individual values and sub-intervals between about 5 and about 50 parts by weight are included and disclosed here; for example, the amount can be from a lower limit of about 5, 10, 15, 20, 25, 30, 35% by weight to an upper limit of about 20, 25, 30, 35, 40, 45, or 50% by weight.
    [0032] The average size of the filler particle can be from about 50 nanometers (nm) to about 3000 nm. All individual values and sub-intervals between about 50 nm and about 3000 nm are included and disclosed here; for example, the amount can be from a lower limit of about 50, 60, 70, 80, 90, 100, 200, 250, 300, 400, 500, 600, 750, 900, 1000, 1500, or 2000 nm up to an upper limit of about 200, 250, 300, 400, 500, 600, 750, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 2000, 2500, or 3000 nm. As used herein, particle size refers to the largest possible distance between two points on an individual particle; for example, for perfectly spherical particles, the particle size is equivalent to the diameter of the spherical particles.
    [0033] The at least one filler may include a first filler composition having an average particle size from about 1 nm to about 300 nm and a second filler composition having an average particle size from about 400 nm to about 1500 nm. The embodiments comprise a first filler composition having an average particle size from about 50 nm to about 100 nm and a second filler composition having an average particle size from about 500 nm to about 900 nm.
    [0034] The first component can optionally include at least one plasticizer. Suitable plasticizers are well known in the art and include abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromelitates, biphenyl derivatives, stearates, difuran diesters, fluoride-containing plasticizers, hydroxybenzoic acid esters, isocyanate adducts, multi-ring aromatic compounds natural products, nitriles, siloxane-based plasticizers, tar-based products, thioethers, seed oil or seed oil derivatives and combinations thereof. Phthalates include alkylbenzyl phthalate (e.g., alkyl is octyl), dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, and the like. The amount of plasticizer used is the amount sufficient to give the desired rheological properties and to disperse the components in the sealing composition, maintaining the desired mechanical properties of the final product. Between about 0.5 and about 30% by weight of the first component can include at least one plasticizer. All individual values and sub-ranges between about 0.5 and about 30% by weight are included and disclosed here; for example, the amount can be from a lower limit of about 0.5, 1, 2, 3, 4, 5, 7, 10, 12, 15, or 20% by weight to an upper limit of about 3, 4, 5, 7, 10, 12, 15, 20, 25, or 30% by weight.
    [0035] The first component can optionally include at least one thixotropic such as calcined clay or fumed silica that has been subjected to surface modification with polydimethylsiloxane. Between about 0.5 and about 15% by weight of the first component can include the at least one thixotropic. All individual values and sub-ranges between about 0.5 and about 15% by weight are included and disclosed here; for example, the amount can be from a lower limit of about 0.5, 1, 2, 3, 4, 5, 7, 10, or 12% by weight to an upper limit of about 3, 4, 5, 7, 10, 12 or 15% by weight.
    [0036] The first component is reacted with a second component that includes at least one isocyanate. Suitable isocyanates include a wide variety of organic mono- and polyisocyanates. Suitable monoisocyanates include benzyl isocyanate, toluene isocyanate, phenyl isocyanate and alkyl isocyanates in which the alkyl group contains 1 to 12 carbon atoms. Suitable polyisocyanates include aromatic, cycloaliphatic and aliphatic isocyanates. Examples of polyisocyanates include m-phenylene diisocyanate, toluene-2-4-diisocyanate, toluene-2-6-diisocyanate, isophorone diisocyanate, 1,3- and / or 1,4 - bis (isocyanatomethyl) cyclohexane (including cis or trans isomers of any one), hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, diisocyanate hexahydrotoluene, methylene bis (cyclohexanoisocyanate) (H12MDI), naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, diisocyanate 4, 4'-biphenylene, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4-4'-biphenyl diisocyanate, methane-4,4'-di- 3,3'-dimethyldiphenyl isocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, a polymethylene polyphenylisocyanate (PMDI), toluene-2,4,6-triisocyanate and 4,4'-dimethyldiphenylmethane- 2,2 ', 5,5'-tetraisocyanate. In some embodiments, the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, PMDI, to lueno-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof. Diphenylmethane-4,4'-methylenediphenyl isocyanate, diphenylmethane-2,4'-diisocyanate and mixtures thereof are generically referred to as MDI, and can all be used. Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and mixtures thereof are generically referred to as TDI, and can all be used. In one embodiment, 50 percent 4.4 'MDI, and 50 percent 2.4' MDI, such as ISONATE 50 OP available from The Dow Chemical Company, is used in combination with a polymeric MDI, such as PAPI 27 available from The Dow Chemical Company.
    [0037] Derivatives from any of the previous isocyanate groups that contain biuret, urea, carbodiimide, allophonate and / or isocyanurate groups can also be used. These derivatives have frequently increased the functionality of the isocyanate and are desirably used when a more highly cross-linked product is desired. The first component and the second component can react to isocyanate indices from 60 to 150. All individual values and sub-intervals between about 60 and about 150 are included and disclosed here; for example, the amount can be from a lower limit of about 60, 70, 80, 90, or 100, up to an upper limit of about 90, 100, 125, or 150.
    [0038] In addition, the first component and the second component are reacted in the presence of at least one adhesion promoter. The adhesion promoter can be introduced as a separate third component. Alternatively, the adhesion promoter can be included as part of the first component and / or as part of the second component. The level of adhesion enhancer in the seal compositions can be in the range of 0.5% by weight to 10% by weight of the total weight of the materials used in the polyurethane seal system. All individual values and sub-intervals between about 0.5% by weight and about 10% by weight are included and disclosed herein; for example, the amount can be from a lower limit of about 0.5, 1, 2, 3, 4, or 5, to an upper limit of about 2, 3, 5, 6, 7, 8, 9, or 10% by weight.
    [0039] The at least one adhesion promoter comprises at least the reaction product of at least one secondary aminoalkoxy silane and at least one second isocyanate, so that the reaction product has an average of at least one silane group and at least one isocyanate group per molecule.
    [0040] The at least one adhesion promoter can be a reaction product of a secondary amino- or mercaptoalkoxy silane and a polyisocyanate, having an average of at least one silane group and at least one isocyanate group per molecule (hereinafter " adduct "), as described for example in U.S. Pat. No. 5,623,044. The embodiments encompass adducts having at least 1.5 isocyanate groups and at least one silane group per molecule, and adducts having at least two isocyanate groups and at least one silane group per molecule.
    [0041] The adduct can be prepared by any suitable method, such as, for example, by reacting an amino- or secondary mercaptoalkoxy silane with a polyisocyanate compound. Polyisocyanates suitable for use in the preparation of the adduct include those described above as suitable for use in the second component. Suitable secondary aminoalkoxy silanes correspond to the following
    formula: where R is a divalent organic group, preferably C 1-4 alkylene, R ', R ", R 1 and Ra are hydrogen or alkyl, preferably C 1-4 alkyl, m represents an integer from 0 to 2. Examples of such compounds include: N, N-bis [(3-triethoxysilyl) propyl] amine; N, N-bis [(3-tripropoxysilyl) propyl] amine; N- (3-trimethoxysilyl) propyl-3- [N- ( 3-trimethoxysilyl) -propylamino] propionamide; N- (3-triethoxysilyl) propyl-3- [N-3-triethoxyethyl) - propylamino] propionamide; N- (3-trimethoxyethyl) propyl-3- [N-3-triethoxysilyl) -propylamino] propionamide; 3-trimethoxysilylpropyl-3- [N- (3-trimethoxysilyl) -propylamino] -2-methyl; 3-triethoxysilylpropyl-3- [N- (3-triethoxysilyl) -propylamino] -2 -methyl; 3-trimethoxysilylpropyl-3- [N- (3-tri-30-methoxysilyl) -propylamino] - 2-methyl propionate, and the like.
    [0042] The silane and polyisocyanate reagents can be combined so that the ratio of isocyanate groups to secondary amine or groups in the reaction mixture to prepare the adduct is at least about 1.5: 1, 2.0: 1, or 2.5: 1; and can be less than about 6.0: 1, 5.5: 1, or 5.0: 1. The adduct can be prepared by any suitable method, as described in U.S. Patent No. 5,623,044.
    [0043] In addition to the components described above, the compositions may also include other ingredients, such as preservatives, antioxidants, and catalysts.
    [0044] The catalysts commonly used in the two-component sealing compositions of the present invention include those known to be useful in facilitating the production of polyurethane. Catalysts include metallic and non-metallic catalysts. Examples of the metal portion of the metal catalysts useful in the present invention include compounds of tin, titanium, zirconium, lead, iron, cobalt, antimony, manganese, bismuth and zinc. In one embodiment, tin compounds useful for facilitating cross-linking in the sealing compositions include: tin compounds such as tin dimethyldineodecanoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, tin octate, isobutyltin trichideate, dibutyltide oxide solubilized dibutyltin oxide, dibutyltin bis-diisooctyl phthalate, bis-tripropoxysilyldioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tin tristate, isobutyltinate dihydrate, tarate dihydrate, tinate dihydrate triethyl tin, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexylhexoate, and tin butyrate, and the like.
    [0045] The sealing compositions incorporated herein can be prepared by procedures well known in the art, e.g., melt mix, extrusion mix, solution mix, dry mix, etc., in or out of the presence of moisture , to provide a substantially homogeneous mixture. The sealing compositions incorporated herein are used in the same way as the known seals for VI units.
    [0046] The insulating glass (VI) units are well known, and Figure 1a of WO 2009/060199 is illustrative. Unit VI is of known and conventional construction, and includes two panels kept in parallel, in a relationship spaced by one or more separating bars, thus forming a cavity between the panels. A primary gas seal is present between each spacer bar and each panel, adjacent to the cavity. A secondary gas seal is present between each panel and each spacer bar, not adjacent to the cavity. The sealing composition of the above embodiments can be either or both of the primary and secondary gas seals, although it is typically the secondary seal. The cavity between the panels is filled with an insulating gas or gas, such as air, carbon dioxide, sulfur hexafluoride, nitrogen, argon, krypton, xenon and the like. A bite is typically positioned between the panels and the window frame. The panels can be manufactured from any of a variety of materials, such as glass, e.g., colorless float glass, annealed glass, tempered glass, solar glass, colored glass and low energy glass; acrylic resin; polycarbonate resin; and the like.
    [0047] The cured sealing compositions incorporated herein provide better gas barrier characteristics and moisture leak characteristics compared to known and conventional gas seals. As a result, the cured sealing composition provides longer lasting service performance of insulating glass units of all types of construction. In addition, the sealing compositions incorporated herein provide better resistance properties over known and conventional gas seals. For example, the sealing compositions incorporated here have better resistance to UV light and moisture.
    [0048] While embodiments of the sealing compositions may serve as a primary gas seal, the primary gas seal typically comprises any of a number of polymeric materials known in the art as useful to serve as a primary seal, including, but not limited to , rubber-based materials such as polyisobutylene, butyl rubber, polysulfide, EPDM rubber, nitrile rubber and the like. Other useful materials include polyisobutylene / polyisoprene copolymers, polyisobutylene polymers, brominated olefin polymers, polyisobutylene and para-methylstyrene copolymers, polyisobutylene and para-methyl styrene copolymers, polyisobutylene and copolymers for polyisobutylene and brominated methylstyrene, isobutylene and isoprene butyl rubber copolymer, ethylene-propylene polymers, polysulfide polymers, polyurethane polymers, styrene-butadiene polymers, and the like. In addition, the sealing composition of this invention can be used as the primary gas seal.
    [0049] The primary gas sealing member can be manufactured from a material such as polyisobutylene which has very good sealing properties. The bite is a sealant that is sometimes referred to as the glass bed and can be provided in the form of a silicone or butyl rubber. Desiccant can be included in the continuous spacer to remove moisture from the cavity or space between the panels occupied with insulating gas. Useful desiccants are those that do not adsorb the insulating gas / gases by filling the interior of the insulating glass unit.
    The following examples are illustrative of certain embodiments of the present invention. All parts and percentages are based on weight, unless otherwise stated. EXAMPLES
    The following examples are provided to illustrate embodiments of the invention, but are not intended to limit its scope. All parts and percentages are by weight, unless otherwise indicated.
    [0052] Tensile strength and elongation at break are measured according to the ASTM D1708 standard. The elongation at break is measured according to the ASTM D1708 standard.
    [0053] The following materials are used: Polyol
    [0054] A polyol based on natural oil, produced by combining monol rich natural oil monomer (1351.76 g) with 1,4-cyclohexanedimethanol (48.02 g). The monol rich natural oil monomer has an average of 1.0 hydroxyl groups per fatty acid and is derived from fractionated fatty acids producing a distribution of about 1 weight percent (% by weight) of saturated monomer, about 93 % by weight of monohydroxyl monomer, about 3% by weight of dihydroxyl monomer, and about 1% by weight of cyclic ethers. The distribution of the monomer is obtained using the method disclosed in the co-pending application published as WO 2009/009271. The mixture is heated and maintained between 70 ° C and 90 ° C for 30 minutes with stirring and removal of nitrogen, in a three-necked flask. Stannous octoate (0.88 g) is then added to the mixture and the temperature is increased to 195 ° C. The mixture is stirred at a reaction temperature of 195 ° C with nitrogen removal for 6 hours and then cooled to room temperature. The resulting polyol is then distributed in the air through the reactor bottom drain valve and stored in an HDPE plastic container. 1,4-Butanediol
    [0055] Available at International Specialty Products. PALATINOL-N
    [0056] A phthalate plasticizer available in BASF SE. SUPER PFLEX 200 pcc
    [0057] A precipitated calcium carbonate filler (average particle size of 0.7 micrometers), the surface of which is treated with stearic acid for a surface treatment level of 2%, available from Minerals Technologies Inc. ULTRA PFLEX
    [0058] A treated surface precipitated calcium carbonate filler (average particle size of 0.07 micrometers), available from Minerals Technologies Inc. CAB-O-SIL TS-720
    [0059] A medium surface area pyrogenic silica that has undergone surface modification with polydimethylsiloxane, available from Cabot Corporation. Isocyanatosilane
    [0060] An isocyanatosilane adduct made according to the method of Example 1 (B) of Pat. No. 5,623,044. The isocyanatosilane adduct is prepared by adding 485 g of Desmodur N-100 (2.59 equivalents) (available from Bayer MaterialScience, a solvent-free aliphatic polyisocyanate resin based on hexamethylenediisocyanate), and 225 g of phthalate plasticizer from Palatinol N alkyl (available in BASF SE) to a resin boiler equipped with a mechanical stirrer, a thermometer, an N2 intake adapter and an addition funnel. The mixture is well mixed and purged of N2 atmosphere. About 300 g of (N, N-bis [(3-trimethoxysilyl) -propyl] amine (0.88 equivalents) (available from Momentive Performance Materials Inc.) is slowly added to the mixture. The adduct has an isocyanate content of 7.0 percent SILQUEST A-187
    [0061] Gamma-glycidoxypropyltrimethoxysilane available from Momentive Performance Materials Inc. SANTICIZER 278
    [0062] A high molecular weight benzyl phthalate plasticizer, available from Ferro Corporation. ISONATE * 143L
    [0063] A polycarbodiimide-modified diphenylmethane diisocyanate, available from The Dow Chemical Company. DABCO T-12
    [0064] A dibutyltin dilaurate catalyst available from Air Products. FOMREZ UL-28
    [0065] A tin dimethyldineodecanoate catalyst available from Momentive Performance Materials Inc. * ISONATE is a registered trademark of Dow Chemical Company. Examples E1-E3 and Comparative Example EC1
    [0066] A “Polyol side” is prepared by combining Polyol, 1,4-Butanediol, PALATINOL, SUPER P-FLEX, ULTRA P-FLEX, CAB-O-SIL TS-720, and DABCO T-12 in the quantities indicated in Table 1. An “isocyanate side” is prepared by combining ISONATE * 143L and adhesion promoter (SILQUEST A-187 (comparative example EC1) or Isocyanatosilane (Examples E1-E3)) in the quantities indicated in Table 1. Table 1

    [0067] The Isocyanate and Polyol sides are then combined and the mixture is stirred for 10 seconds at 800 RPM and then for 15 seconds at 2350 RPM. Samples are prepared for shear measurements by applying an uncured sealant cord approximately 6.3 mm wide by 8 mm high along the width of a 2.54 x 15.24 x 0.63 glass plate cm (1 "x6" x1 / 4 "). A 2.54 x 10.16 x 0.08 cm (1" x4 "x1 / 32") stainless steel substrate is immediately placed on the seal so that 5, 08 cm (2 "(2 inches) of the glass plate and the stainless steel substrate overlap. The sample is left to cure at 23 ° C and 50 percent relative humidity for 7 days. The sample is then separated by pulling in a plane parallel to the cord with an Instron machine at a speed of 2.5 cm / min (1 inch / minute).
    [0068] For the comparative example EC1 a shear strength of 920.45 kPa (133.5 psi) is obtained. For example E1, which has half the amount (by weight) of the EC1 adhesion promoter, a shear strength of 141.5 is obtained. For example E2-E3, substrate (glass) failures occur before the determination of shear strength is obtained. Substrate failures occur at about 1185.90 kPa (172 psi). Example E4
    [0069] A “Polyol Side” is prepared by first combining Polyol (30 g), 1,4-Butanediol (1.05 g), and Isocyanatosilane (0.6 g) and mixing for 15 seconds at 800 RPM and then for 45 seconds at 2350 RPM. ISONATE * 143L (7.95 g) is added to the Polyol side and the mixture is stirred for 10 seconds at 800 RPM and then for 15 seconds at 2350 RPM. Then, FOMREZ UL-28 (50 ppm) is added and the mixture is stirred again for 10 seconds at 800 RPM and then for 15 seconds at 2350 RPM. The mixture is then placed in a 10.16 cm x 10.16 cm (4 "x4") mold with a 50 mil thick sample. The sample is cured in a press at 206842.72 kPa (30000 psi) and 50 ° C for 30 minutes. Example E4 has a tensile strength of 2806.17 kPa (407 psi), and an elongation at break of 312%. Example E5
    [0070] A "Polyol side" is prepared by first combining Polyol (30 g), 1,4-Butanediol (1.05 g), Isocyanate-silane (0.6 g), and SANTICIZER 278, and mixing for 15 seconds at 800 RPM and then for 45 seconds at 2350 RPM. Then SUPER P-FLEX (25.5 g), ULTRA P-FLEX (12 g) is added and mixed for 15 seconds at 800 RPM and then for 45 seconds at 2350 RPM. Then, CAB-O-SIL TS-720 (0.9 g) is added and mixed for 15 seconds at 800 RPM and then for 45 seconds at 2350 RPM. ISONATE * 143L (7.95 g) is added to the Polyol side and the mixture is then stirred for 10 seconds at 800 RPM and then for 15 seconds at 2350 RPM. Then, FOMREZ UL-28 (50 ppm) is added and the mixture is stirred again for 10 seconds at 800 rpm and then for 15 seconds at 2350 RPM. The mixture is then placed in a 10.16 cm x 10.16 cm (4 "x4") mold and a sample thickness of 50 mil. The sample is cured in a press at 206842.72 kPa (30000 psi) and 50 ° C for 30 minutes. Example E5 has a tensile strength of 4433.33 kPa (643 psi), and an elongation at break of 429%.
    [0071] While the foregoing addresses embodiments of the present invention, other and more embodiments of the invention can be designed without departing from its basic scope, and its scope is thereby determined by the claims that follow.
    权利要求:
    Claims (15)
    [0001]
    1. Method for producing an insulating glass sealing unit based on polyurethane, said method being characterized by the fact that it comprises: - forming a first component which includes: - at least one hydrophobic polyol derived from a fatty acid alkyl ester and having an average functionality of 2 to 6 and a hydroxyl number below 300 mg KOH / g; - at least one chain extender having two reactive isocyanate groups per molecule and an equivalent weight per reactive isocyanate group of less than 400; and - at least one filler, the at least one filler being at least one of barium sulfate (BaSO4), aluminum oxide (Al2O3), aluminum hydroxide (Al (OH) 3), magnesium hydroxide (Mg ( OH) 2), calcium carbonate (CaCO3), mica, and talc; providing a second component that includes at least one first isocyanate; - contacting the first component with at least the second component in the presence of at least one adhesion promoter to form a reaction mixture, the at least one adhesion promoter including the reaction product of at least one secondary aminoalkoxy silane and at least one second isocyanate, and the reaction product having an average of at least one silane group and at least one isocyanate group per molecule; and - applying at least the reaction mixture, between at least portions of a first surface and a second surface included in the sealing unit.
    [0002]
    2. Polyurethane-based insulating glass sealing unit, characterized by the fact that it comprises: - a first surface; - a structural seal disposed on at least portions of the first surface, the structural seal comprising the reaction product of at least: (1) a first component which includes: - at least one hydrophobic polyol derived from an alkyl ester of acid fatty and having an average functionality of 2 to 6 and a hydroxyl number below 300 mg KOH / g; - at least one chain extender having two reactive isocyanate groups per molecule and an equivalent weight per reactive isocyanate group of less than 400; and - at least one filler, the at least one filler being at least one of barium sulfate (BaSO4), aluminum oxide (Al2O3), aluminum hydroxide (Al (OH) 3), magnesium hydroxide (Mg ( OH) 2), calcium carbonate (CaCO3), mica, and talc; (2) a second component that includes at least one first isocyanate; and (3) at least one adhesion promoter, so that the first component is contacted with the second component in the presence of at least one adhesion promoter to form a reaction mixture, the at least adhesion promoter including the reaction product at least one secondary aminoalkoxy silane and at least one second isocyanate, and the reaction product having an average of at least one silane group and at least one isocyanate group per molecule; and - a second surface disposed on the structural seal.
    [0003]
    Method according to claim 1 or a sealing unit according to claim 2, characterized in that at least one first component further comprises at least one plasticizer.
    [0004]
    4. Sealing method or unit according to any one of claims 1 to 3, characterized in that the at least one first component further comprises at least one thixotropic, the at least one thixotropic being at least one of pyrogenic silica and calcined clay.
    [0005]
    Sealing method or unit according to any one of claims 1 to 4, characterized in that the at least one first component comprises at least one catalyst.
    [0006]
    6. Sealing method or unit according to claim 5, characterized in that the catalyst comprises tin dimethyldineodecanoate.
    [0007]
    Sealing method or unit according to any one of claims 1 to 6, characterized in that at least one of the first surface and the second surface comprises a glass surface.
    [0008]
    Sealing method or unit according to any one of claims 1 to 6, characterized in that the first surface and the second surface comprise glass.
    [0009]
    9. Sealing method or unit according to any one of claims 1 to 8, characterized in that the at least one secondary aminoalkoxy silane corresponds to the following formula:
    [0010]
    10. Sealing method or unit according to claim 9, characterized in that R is an alkyl group of 3 linear carbons, m is 0, and R 'and R "are methyl groups.
    [0011]
    Sealing method or unit according to any one of claims 1 to 10, characterized in that the at least one first isocyanate comprises a polycarbodiimide-modified diphenylmethane diisocyanate.
    [0012]
    12. Sealing method or unit according to any one of claims 1 to 11, characterized in that the at least one second isocyanate comprises an aliphatic polyisocyanate resin based on hexamethylenediisocyanate.
    [0013]
    13. Sealing method or unit according to any one of claims 1 to 12, characterized in that the at least one hydrophobic polyol is derived using a fatty acid alkyl ester composition comprising at least 75 weight percent of alkyl ester of monohydroxy functional fatty acid.
    [0014]
    Sealing method or unit according to claim 13, characterized in that the composition of fatty acid alkyl esters comprising at least 75 percent by weight of monohydroxy functional fatty acid alkyl ester is reacted with 1,4-cyclohexanedimethanol.
    [0015]
    Sealing method or unit according to any one of claims 1 to 14, characterized in that the at least one filler comprises a first filler having an average particle size 300 nm and a second filler composition average size particle from 400 nm to 1500 nm.
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    同族专利:
    公开号 | 公开日
    EP2638090A1|2013-09-18|
    EP2638090B1|2015-02-11|
    BR112013010666A2|2016-08-09|
    US9032692B2|2015-05-19|
    US20130216840A1|2013-08-22|
    DK2638090T3|2015-05-04|
    RU2013126621A|2014-12-20|
    CN103314029B|2015-05-13|
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    WO2012064971A1|2012-05-18|
    PL2638090T3|2015-07-31|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-01-14| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-08-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-11-17| B09A| Decision: intention to grant|
    2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US41252510P| true| 2010-11-11|2010-11-11|
    US61/412,525|2010-11-11|
    PCT/US2011/060210|WO2012064971A1|2010-11-11|2011-11-10|Polyurethane based insulated glass sealant|
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