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    • 专利摘要:
    sealant composition, sealant product and method for repairing a cured sealant on a substrate, compositions are disclosed which include: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated silane containing sulfur. related products are also disclosed, such as sealants, which include polymers derived from such compositions.
    公开号:BR112013003328B1
    申请号:R112013003328
    申请日:2011-08-12
    公开日:2020-02-04
    发明作者:Virnelson Bruce；B Rao Chandra；Keledjian Raquel；Lin Renhe
    申请人:Prc Desoto Int Inc；
    IPC主号:
    专利说明:

    “COMPOSITION OF SEALING, SEALING PRODUCT AND METHOD FOR PREPARING A CURED SEALING ON A SUBSTRATE
    Field of the invention [0001] The present invention relates to compositions comprising: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane; and in some cases, one or more additional optional components, such as a photoinitiator. The present invention also relates to cured products, such as aerospace sealants, which comprise the reagent reaction product comprising: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane.
    Background of the invention [0002] Thiol-terminated compounds containing sulfur are known to be well suited for use in various applications, such as aerospace seal compositions, due in large part to their fuel-resistant nature after crosslinking. Other desirable properties for aerospace sealant compositions include: low temperature flexibility, short cure time (the time required to achieve a predetermined resistance), and high temperature resistance, among others. Sealant compositions showing at least some of these characteristics and containing thiol-terminated compounds containing sulfur are described, for example, in US Patent Nos. 2,466,963, 4,366,307, 4,609,762, 5,225,472, 5,912,319, 5,959,071, 6,172,179, 6,232,401, 6,372,849, and 6,509,418.
    [0003] Another important feature of aerospace sealant compositions is the strong adhesion to substrates
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    2/36 typical of aircraft, such as used fuel tank substrates. Exemplary materials for such substrates include metals, such as aluminum and aluminum alloys. As a result, aerospace sealant compositions often include adhesion-promoting ingredients, such as silanes with epoxy, thiol, or amino functionality, which are known to bind an organic composition, such as a sealant composition, to an inorganic substrate, such as certain metals, via a hydrolyzable group that forms a siloxane-metal (Si-O-metal) bond.
    [0004] Therefore, sealant compositions are desired which are stable when stored, but when applied to a substrate, can cure quickly to form a cured seal having the characteristics described above. Compositions that cure when exposed to actinic radiation, such as ultraviolet radiation, as may be the case with the reaction of thiol-functional compounds with ethylenically unsaturated compounds (sometimes referred to as enos), are candidates for such sealant compositions. Such compositions may include a photoinitiator that generates free radicals when exposed to ultraviolet radiation. These free radicals lead to cross-linking via a thiol / ene reaction, which can often be completed in seconds.
    [0005] It is believed that a disadvantage of using such compositions is that the rate of the crosslinking reaction can be so rapid that conventional adhesion promoting agents, such as epoxy, thiol, or amino-functional silanes mentioned above, do not have time enough to react with the substrate before the sealant cures, thereby reducing its effectiveness. As a result, it is desirable to provide
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    3/36 seals that exhibit good adhesion to aircraft substrates, such as fuel tank substrates, even when formed as a result of a very fast radiation curing mechanism.
    Summary of the invention [0006] In certain respects, the present invention relates to compositions, such as a package composition, comprising: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane.
    [0007] In other respects, the present invention relates to products, such as sealants, which comprise polymers comprising the reactant reaction product comprising: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane.
    [0008] The present invention also relates, among others, to methods for preparing such polymers and sealants.
    Detailed description of the invention [0009] For the purposes of the following detailed description, it will be understood that the invention may assume several sequences of steps and alternative variations, except where expressly specified to the contrary. In addition, different in any operational examples, or where otherwise indicated, all figures expressing, for example, quantities of ingredients used in the specification and in the claims will be understood to be modified in all cases by the term “about. Consequently, unless otherwise indicated, the numerical parameters presented in the following specification and in the appended claims are approximations that may vary depending on the desired properties to be obtained by
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    4/36 the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be constructed in the light of the reported number of significant figures and applying usual rounding techniques. [0010] Despite the fact that the numerical ranges and parameters presenting the wide scope of the invention are approximations, numerical values presented in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard variation found in their respective test measures.
    [0011] Likewise, it should be understood that any numerical range mentioned here intends to include all the sub-ranges contained therein. For example, a range of “1 to 10 is intended to include all sub-ranges between (and including) the mentioned minimum value of 1 and the maximum mentioned value of 10, that is, having a minimum value greater than or equal to 1 and a maximum value less than or equal to 10. For the purposes of the following detailed description, it will be understood that the invention may assume several sequences of steps and alternative variations, except where expressly specified to the contrary. Furthermore, different in any operational examples, or where otherwise indicated, all figures expressing, for example, quantities of ingredients used in the specification and in the claims will be understood to be modified in all cases by the term about. Consequently, unless otherwise indicated, the numerical parameters presented in the following specification and in the attached claims are approximations that
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    5/36 can vary depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be constructed in the light of the reported number of significant figures and applying usual rounding techniques. [0012] Despite the fact that the numerical ranges and parameters presenting the wide scope of the invention are approximations, numerical values presented in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard variation found in their respective test measures.
    [0013] Likewise, it should be understood that any numerical range mentioned here intends to include all the sub-ranges contained therein. For example, a range from 1 to 10 is intended to include all sub-ranges between (and including) the mentioned minimum value of 1 and the maximum mentioned value of 10, that is, having a minimum value greater than or equal to a maximum value less than or equal to to 10.
    [0014] As indicated, certain embodiments of the present invention relate to compositions comprising: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane. When used herein, polymer refers to oligomers and both homopolymers and copolymers. When used herein, thiol refers to a mercaptan group, that is, an SH group. A thiol-terminated polymer refers to a polymer comprising one or more thiol terminal groups that are reactive with other functional groups. [0015] In certain incorporations, the compositions are
    II —c — o—
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    6/36 substantially, or in some cases, completely free of any component comprising ester bonds. When used herein, the term substantially free means that the composition includes ester bonds, if at all, as an incidental impurity. Any incidental ester bonds are present in such an incidental amount that they do not affect the properties of the compositions or sealants of the present invention. When used herein, ester bond refers to a bond [0016] In certain embodiments, the thiol-terminated polymer comprises sulfur-containing bonds in the polymeric backbone, as is the case, for example, with polysulfide polymer and thioether polymers. When used herein, the term polysulfide refers to any compound that comprises a sulfur-sulfur bond (-S-S-). When used herein, the term polythioether refers to compounds comprising at least two thioether bonds, i.e., -C-S-C- bonds. Thiol-terminated polymers that comprise sulfur in the main polymer chain and methods for their production, and that are suitable for use in the compositions of the present invention include, for example, those disclosed in US Patent No. 4,366,307 in column 3, line 7 through column 9, line 51 and in US patent No. 6,172,179 in column 5, line 42 to column 12, line 7, the portions mentioned of which are incorporated herein by reference. Therefore, in certain embodiments, the thiol-terminated polythether comprises a polythether that includes a structure having the formula (I):
    -R 1 - [-S- (CH2) 2-O- [-R 2 -O-] m- (CH2) 2-SR 1 -] n (I)
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    7/36 in which: (1) each R 1 independently represents a C 2-10 n-alkylene group, a branched C 2-6 alkylene group, a C 6-8 cycloalkylene group, a cycloalkylene alkyl group of C6-10, - [(- CH2-) pX-] q - (- CH2) -) r- or - [(- CH2-) pX-] q- (CH 2 ) -) r - in which at least a CH2- unit is replaced with a methyl group, where: (I) each X is independently selected from O, S, and -NR 6 - where R 6 represents hydrogen or methyl; (II) p is an integer having a value ranging from 2 to 6; (III) q is an integer having a value ranging from 0 to 5; and (IV) r is an integer having a value ranging from 2 to 10; (2) each R 2 independently represents a C2-10 n-alkylene group, a branched C2-6 alkylene group, a C6-8 cycloalkylene group, a C6-10 cycloalkylene group, or - [( -CH2-) pX-] q- (CH2) -) r- in which: (I) each X is independently selected from O, S, and -NR 6 - where R 6 represents hydrogen or methyl; (II) p is an integer having a value ranging from 2 to 6; (III) q is an integer having a value ranging from 0 to 5; and (IV) r is an integer having a value ranging from 2 to 10; (3) m is a rational number from 0 to 10; and (4) n is an integer having a value ranging from 1 to 60. Such polyethers and methods for their production are described in US Patent No. 6,172,179 within the portion thereof incorporated herein by reference above.
    [0017] More particularly, in certain embodiments, the thiol-terminated polymer has a structure according to formula (II):
    HS-R 1 - [- S- (CH2) 2-O - [- R 2 -O-] m- (CH2) 2-SR 1 -] n-SH (II) in which R 1 , R 2 , men are as described above with
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    8/36 with respect to formula (I).
    [0018] In certain embodiments, the thiol-terminated polymer is polyfunctionalized. As a result, in certain embodiments, the thiol-terminated polymer has the structure according to formula (III):
    B— (A— [R 3 ] y —SH) z (III) in which: (1) A represents a structure according to formula (I); (2) y is zero or 1; (3) R 3 represents a single bond when y = 0 and -S- (CH2) 2 ~ [-OR 2 -] mO- when y = 1; (4) z is an integer from 3 to 6; and (5) B represents a z-valued residue of a polyfunctionalizing agent.
    [0019] Appropriate methods for preparing such polyfunctionalized polyether ethers polymers are disclosed, for example, in US Patent No. 6,172,179 in column 7, line 48 through column 12, line 7, the cited portion of which is incorporated herein by reference above.
    [0020] As indicated above, the compositions of the present invention comprise an ethylenically unsaturated sulfur containing sulfur. When used herein, the term sulfur-containing ethylenically unsaturated silane refers to a molecular compound comprising, within the molecule, (I) at least one sulfur atom (S), (II) at least one, in some cases at least two ethylenically unsaturated carbon-carbon bonds, such as carbon-carbon double bonds (C = C); and (III) at least one silane group (R i hx — Si (OR) x in which each of R and Ri independently represents an organic group (ex is 1, 2, or 3).
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    9/36 [0021] In certain embodiments, the sulfur-containing ethylenically unsaturated silane, which is suitable for use in the compositions of the present invention, itself comprises the reaction product of reagents comprising: (I) a mercaptosilane, and (II) a polyene. When used herein, the term mercaptosilane refers to a molecular compound comprising, within the molecule, (I) at least one mercapto group (-SH), and (II) at least one silane group (defined above). Suitable mercaptosilanes include, for example, those having a structure according to formula (IV):
    HS-R-Si (Ri) m (OR ') (3-m) (IV) in which: (I) R is a divalent organic group; (II) R 'is hydrogen or alkyl group; (III) R 1 is hydrogen or an alkyl group; and (IV) m is an integer from 0 to 2.
    [0022] Specific examples of mercaptosilanes, which are suitable for use in the preparation of ethylenically unsaturated sulfur-containing silanes suitable for use in the present invention, include, without limitation, γ-mercapto propyl trimethoxysilane, γ-mercapto propyl triethoxysilane, γmercapto propyl dimethoxysilane, γ -propyl methyl diethoxysilane mercapto, methyl trimethoxysilane mercapto, methyl triethoxysilane mercapto, and the like, including combinations thereof.
    [0023] When used here, the term polyene refers to a compound containing at least two carbonocarbon double bonds (C = C). In certain embodiments, the polyene used to prepare the sulfur-containing ethylenically unsaturated silanes suitable for use in the present invention comprises a triene, which refers to a compound containing three doubles
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    10/36 carbon-carbon bonds, as is the case with trialyl compounds, which are compounds comprising three allyl groups (C = CC), and which include, for example, trialyl cyanurate (TAC) and trialyl isocyanurate (TAIC ), including combinations thereof.
    [0024] The Examples here illustrate a method for producing the sulfur-containing ethylenically unsaturated silanes suitable for use in the present invention. In finished embodiments, the polyene comprises a triene, such as one or more of the previous trialyl compounds, and the mercaptosilane and triene react in relative amounts such that the resulting reaction product theoretically comprises an average of at least two ethylenically unsaturated groups per molecule.
    [0025] Furthermore, in certain embodiments, the compositions of the present invention further comprise a polyene in addition to the polyene used to prepare the sulfur-containing ethylenically unsaturated silane described above. Suitable polyenes include, without limitation, polyvinyl ethers and polyalkyl compounds, such as any of those described above with respect to the preparation of the sulfur-containing ethylenically unsaturated silane, including the trialyl compounds described above. However, in some cases, such polyenes comprise a diene. When used herein, the term diene refers to a compound that has two carbon-carbon double bonds. Non-limiting examples of dienes include pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadiene, icosadiene,
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    11/36 henesicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10 -undecadiene, 1,11dodecadiene, 1,12-tridecadiene, and low molecular weight polybutadiene (M w less than 100 g / mol). Exemplary non-limiting cyclic dienes include cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, di-cyclopentadiene or diolefins containing upper rings with or without substituents in various ring positions.
    [0026] However, in certain embodiments, the diene comprises a compound represented by the formula (V):
    CH2 = CH-O- (-R5-O-) m-CH = CH2 (V) where R5n in formula (V) is a C 2-6 n-alkylene group, a branched C2-6 alkylene group, a cycloalkylene group of C 6-8 , or - [(- CH2-) p -X-] q - (- CH2) -) r -, where p is an integer having a value ranging from 2 to 6, q is a integer having a value ranging from 1 to 5; er is an integer having a value ranging from 2 to 10.
    [0027] The materials of formula (V) are divinyl ethers. Suitable divinyl ethers include those compounds having at least one oxyalkylene group, such as 1 to 4 oxyalkylene groups, that is, those compounds in which m in formula (V) is an integer from 1 to 4. In some cases, m in formula (V) is an integer from 2 to 4. It is also possible to use mixtures of divinyl ethers commercially obtainable in the present invention. Such mixtures are characterized by an average non-integer value for the number
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    12/36 of oxyalkylene units per molecule. Consequently, m in formula (V) can have rational numerical values between 0 and 10.0, such as between 1.0 and 10.0, between 1.0 and 4.0, or between 2.0 and 4.0.
    [0028] Divinyl ether monomers suitable for use in the present invention include, for example, divinyl ether, ethylene glycol divinyl ether (EG-DVE) (R in formula (V) is ethylene in et 1), butanediol divinyl ether (BD- DVE) (R in formula (V) is butylene in is 1), hexanediol divinyl ether (HD-DVE) (R in formula (V) is hexylene in is 1), diethylene glycol divinyl ether (DEG-DVE) (R in formula (V) is ethylene in é 2), triethylene glycol divinyl ether (R in formula (V) is ethylene in é 3), tetraethylene glycol divinyl ether (R in formula (V) is ethylene in é 4), cyclohexane dimethanol divinyl ether, polytetrahydrofuryl divinyl ether and mixtures thereof. In some cases, trivinyl ether monomers, such as trimethylolpropane, trivinyl ether; tetrafunctional ethers monomers, such as pentaerythritol tetravinyl ether; and mixtures of two or more such monomers of polyvinyl ethers. The polyvinyl ether material may have one or more pendant groups selected from alkyl groups, hydroxyl groups, alkoxy groups and amine groups.
    [0029] Useful divinyl ethers in which R in formula (V) is a branched C2-6 alkylene can be prepared by reacting a polyhydroxy compound with acetylene. Exemplary compounds of this type include compounds in which R in formula (V) is an alkyl substituted methylene group such as -CH (CH 3 ) - (for example, PLURIOL® mixtures such as divinyl ether PLURIOL®E-200 (BASF Corp. Parsippany, NJ), for which R in formula (V) is ethylene and is 3.8) or a
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    13/36 alkyl substituted ethylene (e.g., -CH 2 CH (CH 3 ) -, such as polymeric DPE mixtures including DPE-2 and DPE-3 (International Specialty Products of Wayne, NJ).
    [0030] Other useful divinyl ethers include compounds in which R in formula (V) is polytetrahydrofuryl (poly-THF) or polyoxyalkylene, such as those having an average of about 3 monomer units.
    [0031] If wanted, can be used two or more monomers in divinyl ether of the formula (V). [0032] The Examples here describe methods and conditions appropriate to prepare the compositions gives gift invention.[0033] Certain incorporations of this invention refers to products, such as seals aerospace,
    comprising a polymer which is the reaction product of reagents comprising: (a) a thiol-terminated polymer, such as any of those described above; and (b) an ethylenically unsaturated sulfur-containing silane, as described above. Such polymers can be prepared under any desired condition appropriate to cause reaction of the thiol groups of the thiol-terminated polymer with the ethylenically unsaturated groups of the sulfur-containing ethylenically unsaturated silane and, if present, with any additional polyenes, such as, for example, any. of the divinyl ethers described above. Such a thio / ene reaction can be catalyzed by a free radical catalyst, such as azocomposites and organic peroxides.
    [0034] However, in some embodiments of the present invention, the aforementioned thiol / ene reaction, which forms the polymers of the present invention, is carried out by radiating a
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    14/36 composition of the present invention with actinic radiation. When used here, “actinic radiation includes radiation with electronic beam (EB), ultraviolet radiation (UV), and visible light. In many cases, the thiol / ene reaction is carried out by irradiating the composition with UV light, and in such cases, the composition often also comprises a photoinitiator. In addition, in many cases, such compositions further comprise a polyene in addition to the polyene used to prepare the sulfur-containing ethylenically unsaturated silane, such as one or more of the trialyl compounds and / or polyvinyl ethers described above. In addition, in certain embodiments, such compositions are “packaged” compositions, which refer to the storage of stable compositions in which all components of the composition are stored together in a single container. As a result, certain embodiments of the present invention relate to such compositions. In other embodiments, the compositions are “two-pack compositions in which the thiol-terminated polymer and the sulfur-containing ethylenically unsaturated silane are stored separately and then combined together at or near the time of use.
    [0035] In some incorporations, such irradiation with ultraviolet light occurs together with the manufacture of a cured seal on a substrate. As such, certain embodiments of the present invention refer to products, such as cured sealants (including aerospace sealants) that comprise the polymers of the present invention, which are sometimes prepared in relation to a method of preparing a cured sealant over a substrate comprising: (a) depositing an uncured sealant composition on a
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    15/36 substrate; and (b) exposing the uncured sealant composition to actinic radiation to provide a cured sealant comprising a polymer of the present invention, the uncured sealant composition comprising: (I) a thiol-terminated polymer, such as any one of those described above; and (II) an ethylenically unsaturated sulfur-containing silane as described above. In many cases, such compositions further comprise a photoinitiator and / or a polyene in addition to the polyene used to prepare the sulfur-containing ethylenically unsaturated silane, such as one or more of the trialyl compounds and / or the polyvinyl ethers described above, as well as other components typically used in aerospace seal applications, such as fillers and the like.
    [0036] The compositions of the present invention will often contain an essentially stoichiometric equivalent amount of thiol groups to eno groups in order to obtain a cured sealant in response to exposure of the composition to actinic radiation. When used here, the essentially stoichiometric equivalent expression means that the number of thiol groups and groups not present in the compositions does not differ from each other by more than 10%, in some cases not more than 5% or, in some cases not more than 1% or not more than 0.1%. In some cases, the number of thiol group and number of groups not present in the composition are the same. In addition, as will be understood, the source of eno groups in the compositions of the present invention includes the sulfur-containing ethylenically unsaturated silane as well as any additional polyene included in the composition (in addition to the polyene used to prepare the sulfur-containing ethylenically unsaturated silane). In certain incorporations, silane
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    16/36 ethylenically unsaturated sulfur-containing described above is present in an amount such that 0.1 to 30, such as 1 to 30, or, in some cases, 10 to 25 percent of the total number of ethylenically unsaturated groups present in the composition are part of of a sulfur-containing ethylenically unsaturated silane molecule, based on the number of ethylenically unsaturated groups in the composition.
    [0037] As indicated, in certain embodiments, particularly when the cured sealants of the present invention will be formed upon exposure of the composition described above to UV radiation, the compositions also comprise a photoinitiator. As those skilled in the art will understand, a photoinitiator absorbs ultraviolet radiation and turns into free radicals that initiate polymerization. Photoinitiators are classified into two major groups based on the mode of action, either one or both of which can be used in the compositions described here. Cleavage-type photoinitiators include acetophenones, α-amino alkyl phenones, benzoin ethers, benzoyl oximes, acyl phosphine oxides and bis acyl phosphine oxides and mixtures thereof. Abstraction-type photoinitiators include benzophenone, Michler's ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin and mixtures thereof.
    [0038] Specific non-limiting examples of photoinitiators that can be used in the present invention include benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzophenol, acetophenone, benzophenone, 4,4'-dichloro benzophenone, 4,4'-bis (N, N'-dimethylamino) benzophenone, dietoxy acetophenone, fluorones, for example, the H-Nu series of
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    17/36 initiators obtainable from Spectra Group Ltd., 2-hydroxy-2methyl-1-phenylpropan-1-one, 1-hydroxy cyclohexyl phenyl ketone, 2-isopropyl thioxanthone, α-amino alkyl phenone, for example 2- benzyl-2-dimethylamino-1- (4-morpholino phenyl) -1butanone, acyl phosphine oxides, eg 2,6-dimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis oxide (2,4,6-trimethyl benzoyl) phenyl phosphine, 2,6-dichloro benzoyl diphenyl phosphine oxide, and 2,6-dimethoxy benzoyl diphenyl phosphine, bis acyl phosphine oxides, for example, bis (2 , 6dimethoxy benzoyl) -2,4,4-trimethyl pentyl phosphine, bis (2,6-dimethyl benzoyl) -2,4,4-trimethyl pentyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) oxide -2,4,4-trimethyl pentyl phosphine, and bis (2,6-dichloro benzoyl) -2,4,4-trimethyl pentyl phosphine oxide, and mixtures thereof.
    [0039] In certain embodiments, the compositions described herein comprise from 0.01 to 15 percent by weight of photoinitiator or, in some embodiments, from 0.01 to 10 percent by weight, or in other embodiments, of 0.01 to 5 percent by weight of photoinitiator based on the total weight of the composition.
    [0040] In certain embodiments of the compositions of the present invention, payloads include those commonly used in the art, including conventional inorganic fillers, such as fumed colloidal silica, calcium carbonate (CaCO3), and carbon black, as well as light weight charges . In some embodiments, charges that are substantially transparent to ultraviolet radiation, such as fumed colloidal silica, may be particularly useful. Appropriate light weight loads
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    18/36 include, for example, those described in US patent No. 6,525,168 in column 4, lines 23-55, the cited portion of which is hereby incorporated by reference and those described in US patent application publication No. US2010 -0041839 A1 in [0016] to [0052], the portion cited of which is hereby incorporated by reference.
    [0041] In some embodiments, the compositions of the present invention include a photo-active charge. When used herein, the term "photo-active charge refers to a charge that comprises a material that is photo-excitable when exposed to, and absorption of, ultraviolet and / or visible radiation. A photo-active material is a material that, when exposed to light having energy greater than the energy interval between the conduction band and the valence band of the crystal, causes excitation of electrons in the valence band to produce a conduction electron leaving thus a hole behind the particular valence band. Exemplary, but not limiting, photo-active charges suitable for use in certain compositions described herein are metal oxides, such as, for example, zinc oxide, tin oxide, ferric oxide, dibismuth trioxide, tungsten trioxide, titanium dioxide (including crystalline forms of bruquita, anatase and / or rutile of titanium dioxide), and mixtures thereof.
    [0042] In certain embodiments, the compositions include from 5 to 60 percent by weight of the filler or combinations of fillers, such as from 10 to 50 percent by weight, based on the total weight of the composition, as long as the presence of such charges in such quantities do not cause significant detrimental effect on the performance of the composition.
    [0043] In addition to the above ingredients, certain
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    19/36 compositions of the invention may optionally include one or more of the following: colorants (including photoactive dyes), thixotropes, retardants, solvents and masking agents, among other components.
    [0044] When used here, the term coloring means any substance that imparts color and / or other opacity and / or other visual effect to the composition. The dye can be added to the coating in any appropriate form, such as discrete particles, dispersions, solutions and / or flakes. In the coatings of the present invention, a single colorant or a mixture of two or more colorants can be used.
    [0045] Examples of dyes include pigments, dyes and dyes, such as those used in the titan industry or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble but capable of moistening under conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. The dyes can be incorporated into the coatings using a grinding vehicle, such as an acrylic grinding vehicle, the use of which is familiar to those skilled in the art.
    [0046] Exemplary pigments and / or pigment compositions include, but are not limited to, crude carbazole dioxazin, azo, mono-azo, diazo, naphthol AS, salt type (flakes), benzimidazolone, isoindolinone, isoindoline and polycyclic phthalocyanine , quinacridone, perylene, perinone, diketopyrrole pyrrole, thio-indigo, anthraquinone, indantrone, anthrapyrimidine, flavantrone, pyrantrone, antanthrone, dioxazine, triaryl carbon, quinophthalone pigments,
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    20/36 pyrrole pyrrole dicet red (“DPPBO red), titanium dioxide, carbon black and mixtures thereof. The terms, “pigment and“ colored charge, can be used to allow for exchange and / or replacement.
    [0047] Exemplary dyes include, but are not limited to, those that are solvent based and / or aqueous such as green or phthalate blue, iron oxide, bismuth vanadate, anthraquinone, quinacridone and perylene.
    [0048] Exemplary dyes include, but are not limited to, pigments dispersed in water-based or water-miscible vehicles such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.
    [0049] As noted above, the colorant may be in the form of a dispersion including, but not limited to, a dispersion of nanoparticles. Nanoparticle dispersions can include one or more highly dispersed nanoparticle dyes and / or dye particles that produce a desired effect of visible color and / or opacity and / or visual effect. Dispersions of nanoparticles can include dyes such as pigments or dyes having a particle size less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by grinding stock organic or inorganic pigments with grinding media having a particle size less than 0.5 nm. Dispersions of nanoparticles and methods for preparing them are identified in U.S. Patent No. 6,875,800 B2, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, condensation of
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    21/36 gas phase, and chemical friction (ie, partial dissolution). In order to minimize the re-agglomeration of nanoparticles within the coating, a dispersion of resin coated nanoparticles can be used. When used herein, a dispersion of resin coated nanoparticles refers to a continuous phase in which discrete composite nanoparticles are dispersed that comprise a nanoparticle and a resin coating on the nanoparticle. Exemplary dispersions of nanoparticles coated with resin and methods for preparing them are identified in US Patent Application Publication No. 2005-0287348 A1, filed June 24, 2004, US Provisional Patent Application No. 60 / 482,167 filed June 24 of 2003, and serial US patent application No. 11 / 337,062 filed on January 20, 2006, which are also incorporated herein by reference.
    [0050] Exemplary special effect compositions that can be used in the compositions of the present invention include pigments and / or compositions that produce one or more appearance effects such as reflectance, perolescence, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and / or color change. Additional special effect compositions can provide other noticeable properties, such as opacity or texture. In a non-limiting embodiment, special effect compositions can produce a color change such that the color of the coating changes when the coating is viewed at different angles. Exemplary special effect compositions are identified in U.S. Patent No. 6,894,086, incorporated herein by reference. Additional color effect compositions may include clear coated mica and / or
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    22/36 synthetic mica, coated silica, coated alumina, transparent liquid crystal pigment, liquid crystal coating, and / or any composition in which the interference results from a refractive index differential within the material and not because of the differential refractive index between the material surface and the air.
    [0051] In general, the colorant can be present in any quantity sufficient to confer the desired visual and / or color effect. The dye can comprise from 1 to 65 weight percent of the compositions present, such as from 3 to 40 weight percent or from 5 to 35 weight percent, based on the total weight of the compositions.
    [0052] Photo-active dyes, which provide reversible or permanent photo-induced color change effects, are also suitable for use in the compositions described here. Appropriate photo-active dyes are commercially available from Spectra Group Limited, Inc., Millbury, Ohio.
    [0053] Thixotropes, for example, silica, are often used in an amount of 0.1 to 5 weight percent, based on the total weight of the composition.
    [0054] Retardants, such as stearic acid, are also often used in an amount of 0.1 to 5 weight percent, based on the total weight of the composition. Masking agents, such as pine fragrance or other fragrances, which are useful in covering any low odor in the composition, are often present in an amount of 0.1 to 1 percent by weight, based on the total weight of the composition. composition.
    [0055] In certain embodiments, the compositions comprise a plasticizer that, in at least some cases,
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    23/36 may allow the composition to include polymers that have a greater T g than would commonly be useful in an aerospace seal. That is, the use of a plasticizer can effectively reduce the Tg of the composition, and therefore, increase the low temperature flexibility of the cured composition beyond what would be expected based on the Tg of the polymer alone. Plasticizers that are useful in certain embodiments of the compositions of the present invention include, for example, phthalate esters, chlorinated paraffins, hydrogenated terphenyls. The plasticizer or combination of plasticizers often constitutes 1 to 40 weight percent, as well as 1 to 10 weight percent of the composition. In certain embodiments, depending on the nature and quantity of plasticizers used in the composition, polymers of the invention having Tg values of up to -50 ° C, such as up to -55 ° C, can be used.
    [0056] In certain embodiments, the compositions may further comprise one or more organic solvents, such as isopropyl alcohol, in an amount ranging, for example, from 0 to 15 weight percent based on the total weight of the composition, such as less than 15 percent by weight and, in some cases, less than 10 percent by weight. However, in certain embodiments, the compositions of the present invention are substantially free or, in some cases, completely free of any solvent, such as an organic solvent or an aqueous solvent, i.e., water. In certain embodiments, differently stated, the compositions of the present invention are substantially 100% solids.
    [0057] In certain incorporations, the polymer of
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    The present invention is present in the cured sealant of the present invention in an amount of at least 30 weight percent, such as at least 40 weight percent, or, in some cases, at least 45 weight percent, based on total seal weight. In certain embodiments, the polymer of the present invention is present in the cured sealant of the
    gift invention in a smaller amount or equal to 99 per percent in weight such as less than or equal to 95 per percent in Weight, or, in some cases, less than or equal to 90 per percent in Weight, with based on total seal weight. [0058]In certain incorporations, the seals gives
    The present invention has a Tg when cured less than or equal to -55 ° C, such as less than or equal to -60 ° C, or, in some cases, less than or equal to -65 ° C.
    [0059] Ultraviolet radiation from any suitable source that emits ultraviolet light having a wavelength ranging, for example, from 180 to 400 nm, can be used to initiate the thiol / ene reaction described above and thus form the polymers and cured seals of the present invention. Suitable sources of ultraviolet light are generally known and include, for example, mercury arcs, carbon arcs, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, spiral flow plasma arcs and ultraviolet light emitting diodes. Certain embodiments of the invention can exhibit an excellent degree of curing in air on exposure to relatively low energy in ultraviolet light.
    [0060] In fact, it has been surprisingly discovered that, in some cases, UV curing of compositions can be achieved
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    25/36 of the present invention at depths greater than or equal to 5.08 cm (2 inches). This means that cured seals having a thickness greater than or equal to 5.08 cm (2 inches), and having desirable sealing properties described herein, can be achieved by exposing the compositions described here to actinic radiation, such as ultraviolet radiation, in air in relatively low energy exposure.
    [0061] As indicated, certain embodiments of the present invention refer to compositions, such as compositions of sealants, coatings, and / or electrical encapsulation. When used herein, the term sealant composition refers to a composition that is capable of producing a film that has the ability to withstand atmospheric conditions, such as humidity and temperature and at least partially block the transmission of materials, such as water , fuel, and other liquids and gases. In certain embodiments, the seal compositions of the present invention are useful, for example, as aerospace seals and as coatings for fuel tanks. In certain embodiments, cured sealants comprise a polymer as described above in combination with other components, such as fillers and other additives described above.
    [0062] The compositions of the present invention can be deposited on any of a variety of substrates. Common substrates can include titanium, stainless steel, aluminum forms coated with chromate and coated with organic material, on prime and anodized from them, epoxy, urethane, graphite, fiberglass composite, KEVLAR®, acrylics and polycarbonates.
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    [0063] The compositions of the present invention can be deposited on the surface of a substrate or on an underlying layer, such as a primer layer or a previously applied sealant.
    [0064] In certain embodiments, the seals of the present invention are resistant to fuels. When used here, the term "fuel resistant" means that a product, such as a sealant, has a percentage of volumetric swelling less than or equal to 40%, in some cases less than or equal to 25%, in some cases less than or equal to 20 %, in other cases even less than or equal to 10%, after immersion for one week at 60 ° C (140 ° F) and ambient pressure in jet reference fluid (JRF) Type I according to methods similar to those described in ASTM D792 or AMS 3269, incorporated herein by reference. JRF Type I jet reference fluid, when used here to determine fluid resistance, has the following composition (see AMS 2629, published July 1, 1989), § 3.1.1 et seq., Obtainable from SAE (Society of Automotive Engineers, Warrendale, Pa.) (Which is incorporated by reference):
    Toluene 28 ± 1 2-1% in volume Cyclohexane (technical) 34 ± 1%1% in volume Isoctane 38 ± 1%1% in volume
    Ditherciobutyl disulfide 1 ± 0.005% by volume (sulfur removed) [0065] In certain embodiments, products of the present invention, such as sealants, have an elongation of at least 100% and a tensile strength of at least 1.7 MPa ( 250 psi) when measured according to the procedure described in AMS 3279, § 3.3.17.1, test procedure AS127 / 1, § 7.7.
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    27/36 [0066] In certain embodiments, the cured product of the present invention has a tensile strength of at least 17.96 kg / m (25 pounds per linear inch) (pli) or more when measured according to ASTM D624 Matrix Ç.
    [0067] As should be evident from the previous description, the present invention also relates to methods for sealing an opening using the composition of the present invention. These methods comprise: (a) applying a composition of the present invention to a surface to seal the opening; and (b) curing the composition by exposing it to actinic radiation. As will also be understood, the present invention also relates to aerospace vehicles comprising at least one seal formed as described herein.
    [0068] The following examples illustrate the invention, however, they should not be considered as limiting the invention for its details. Unless otherwise indicated, all parts and percentages in the following examples, as well as from the beginning to the end of the specification, are by weight.
    Examples
    Example 1: Synthesis of polythioether polymer [0069] A resin was prepared in the manner described in Example 1 of U.S. Patent No. 6,232,401. The polymer (of theoretical functionality = 2.2) had an equivalent mercaptan weight of 1640 and a viscosity of 70 poise.
    Example 2: Synthesis of polythioether polymer [0070] Trialyl cyanurate (TAC) (36.67 g, 0.15 mol) and dioxaoctane dimercapto (DMDO) (449.47 g, 2.47 moles) were loaded into a flask 1 L round bottom with 4 necks. The balloon was equipped with an agitator, a passage adapter
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    28/36 gas and thermometer. Agitation started. The flask was sprayed with dry nitrogen, a solution of potassium hydroxide (0.012 g, concentration: 50%) was added and the reaction mixture was heated to 76 ° C. A solution of VAZO-67 radical initiator (0.32 g) and diethylene glycol divinyl ether (316.44 g, 2.00 moles) was introduced into the reagent mixture over a period of 2 hours during which time a temperature of 66-76 ° C. After the addition of divinyl ether was completed, the temperature of the reaction mixture was increased to 84 ° C. The reaction mixture was cooled to 74 ° C and nine portions of VAZO-67 (of ~ 0.15 g each) were added over an interval of 1 hour during which the temperature was maintained at 74-77 ° C. The reaction mixture was heated to 100 ° C for 2 hours, cooled to 80 ° C, and evacuated to 68-80 ° C / 5-7 mm Hg for 1.75 h. The resulting polymer (of theoretical functionality = 2.8) had an equivalent mercaptan weight of 1566 and a viscosity of 140 poise.
    Example 3: Synthesis of ethylenically unsaturated silane containing sulfur [0071] TAC (121.00 g, 0.49 mol) and γ-mercapto propyl trimethoxysilane (SILQUEST) were added at room temperature (25 ° C, 77 ° F) ® 189, 95.25 g, 0.40 mol) in a 1 L round-bottomed flask with 4 necks, equipped with agitator, nitrogen inlet, and thermal probe. During the addition there was a small release of heat that raised the temperature to 40 ° C (104 ° F). The reaction was slowly heated to 70 ° C (158 ° F). Once the temperature of 70 ° C (158 ° F) was reached, VAZO-67 (0.026 g, 0.012% by weight) was added and the reaction was monitored by mercaptan titration (mercaptan titration indicating an equivalent of
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    29/36 mercaptana greater than 50,000 marked the end of the reaction). In a 6100 mercaptan equivalent, VAZO-67 (0.042 g, 0.019% by weight) was added and the reaction was stirred at 70 ° C (158 ° F) while it was monitored. In 16,335 mercaptan equivalent, VAZO-67 (0.036 g, 1.7%) was added. In 39,942 mercaptan equivalent, VAZO-67 (0.016 g, 0.007%) was added. In a mercaptan equivalent of 61,425 the reaction was considered complete and stopped.
    Example 4: Curing of polyether polymer with DVE / Adduct mixture [0072] The curing reaction was carried out in a 300 g plastic container with a lid. The polymer of Example 1 (120.00 g, 0.07 molar equivalent), DVE (4.28 g, 0.05 molar equivalent), and the adduct described in Example 3 (4.03 g, 0, 02 molar equivalent) in the 300 g container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2300 rpm. The container was opened and the IRGACURE® 2022 photoinitiator (a BASF phosphine / a-hydroxy ketone photoinitiator, BASF, 0.641 g, 0.5% by weight) was added, and the container was placed back in the mixer. high speed and mixed for 1 minute at 2300 rpm. The polymer was poured into a circular metallic cap (12.7 cm (5 inches) in diameter) (pretreated with VALSPAR 225 release agent), and placed under UV light for 15 seconds, after which the polymer appeared to have cured. Curing was achieved using a SUPER SIX curing unit, obtainable from Fusion Systems Inc. The curing unit was equipped with a 300 W H-bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of UV energy of
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    30/36
    3.103 J / cm 2 , measured by an energy meter disk, obtainable from EIT, Inc. of Sterling, VA. Up to 5.08 cm (2 inches) of cured polymer was obtained. The polymer was kept at room temperature for 4 days to ensure complete curing. The polymer was cut into seven 1.27 cm (½ inch) dog bones with a tensile strength template, and three of the specimens were used to measure elongation and dry tensile strength. The results (an average of the three) are as follows: 1.9 MPa (282 psi) (tensile strength), and 421% (elongation). Two of the 1.27 cm (½ inch) dog bones were placed in a glass jar, with a lid, and covered with jet fuel (JRF Type I) and placed in a 60 ° C water bath ( 140 ° F) for 7 days. The results (an average of the two) are as follows: 0.97 MPa (141 psi) (tensile strength), and 78% (elongation). Two of the 1.27 cm (½ inch) dog bones were placed in a glass jar, with a lid, and covered with tap water and placed in an oven at 93 ° C (200 ° F) for 2 days. The results are as follows: 36 Shore A (hardness), 0.92 MPa (134 psi) (tensile strength), and 50% (elongation) The tensile strength and elongation data were obtained according to ASTM D 412 and the hardness data was obtained according to ASTM D 2240.
    [0073] A portion of the polymeric composition was spread on an aluminum panel coated with MAS-C-27725 of 7.62 cm x 15.24 cm (3 x 6) and cured according to the curing method described previously. A cured polymer film approximately 0.31 cm (1/8) thick was obtained. The film was cut into two 25.4 cm (1 inch) strips and the strips were manually
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    31/36 180 ° angles. The percentage of adherence to the substrate was recorded and the results were shown in Table 3.
    Example 5: Curing of polyether polymer with DVE / Adduct mixture [0074] The curing reaction was carried out in a 300 g plastic container with a lid. The polymer of Example 1 (120.00 g, 0.07 molar equivalent), DEG-DVE (5.20 g, 0.066 molar equivalent), and the adduct described in Example 3 (1.60 g, 0.007 equivalent were added) molar) in the 300 g container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2300 rpm. The container was opened and IRGACURE® 2022 photoinitiator (0.63 g, 0.5% by weight) was added, and the container was placed back in the high speed mixer and mixed for 1 minute at 2300 rpm. The polymer was poured into a circular metallic cap (12.7 cm (5 inches) in diameter) (pretreated with VALSPAR 225 release agent) and placed under UV light for 15 seconds, after which the polymer appeared to have cured.
    Curing was achieved using a SUPER SIX curing unit, obtainable from Fusion Systems Inc. The curing unit was equipped with a 300 W H-bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of UV energy of
    3.103 J / cm 2 , measured by an energy meter disk, obtainable from EIT, Inc. of Sterling, VA. Up to 5.08 cm (2 inches) of cured polymer was obtained. The polymer was kept at room temperature for 4 days to ensure complete curing. The polymer hardness, measured by a durometer, was 30 Shore A. The polymer was cut into seven 1.27 cm (½ inch) dog bones with a tensile strength template, and three of the
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    32/36 specimens were used to measure elongation and resistance to dry traction. The results (an average of the three) are as follows: 1.7 MPa (251 psi) (tensile strength), and 559% (elongation). Two of the 1.27 cm (½ inch) dog bones were placed in a glass jar, with a lid, and covered with jet fuel (JRF Type I) and placed in a 60 ° C water bath ( 140 ° F) for 7 days. The results (an average of the two) are as follows: 1.4 MPa (202 psi) (tensile strength), and 351% (elongation). Two of the 1.27 cm (½ inch) dog bones were placed in a glass jar, with a lid, and covered with tap water and placed in an oven at 93 ° C (200 ° F) for 2 days. The results (an average of two) are as follows: 25 Shore A (hardness), 1.4 MPa (204 psi) (tensile strength), and 274% (elongation) the tensile strength and elongation data were obtained according to ASTM D 412 and the hardness data was obtained according to ASTM D 2240.
    [0075] A portion of the polymeric composition was spread on an aluminum panel coated with 7.62 cm x 15.24 cm (3 x 6) MAS-C-27725 and cured according to the curing method described above. A cured polymer film approximately 0.31 cm (1/8) thick was obtained. The film was further cut into two 2.54 cm (1 inch) strips and the strips were manually drawn back at 180 ° angles. The percentage of adhesion to the substrate was recorded and the results were shown in Table 3. Example 6: Sealant composition with adduct [0076] A sealant composition was prepared by mixing the polymer described in Example 1 and the adduct prepared according to Example 3 with triethylene glycol divinyl ether (TEG-DVE)
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    33/36 and other ingredients described in Table 1. Table 5
    Component Weight, in grams Polymer of Example 1 300.00 TEG-DVE 12.84 Adduct of Example 3 4.02 Calcium carbonate 9, 39 IRGACURE® 2022 1.62
    [0077] All the ingredients described in Table 1 were mixed intimately. A portion of the sealant composition was poured into a 5.08 cm (2) diameter paper cup and cured for 15 seconds using a SUPER SIX curing unit, obtainable from Fusion Systems Inc. The curing unit was equipped with a bulb -H 300 W, which produced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of UV energy of
    3.103 J / cm 2 , measured by an energy meter disk, obtainable from EIT, Inc. of Sterling, VA. Up to 3.81 cm (1.5 inches) of cured sealant was obtained.
    [0078] A portion of the polymeric composition was spread over an aluminum panel coated with MAS-C-27725 of 7.62 cm x 15.24 cm (3 x 6) and cured according to the curing method described previously. A cured polymer film approximately 0.31 cm (1/8) thick was obtained. The film was also cut into two strips (25.4 cm (1 inch) and the strips were manually recessed at 180 ° angles. The percentage of adhesion to the substrate was recorded and the results were shown in Table 3. Comparative Example 7 : Polythether polymer curing without adduct [0079] The curing reaction was carried out in a 100 g plastic container with a lid.
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    34/36 in Example 1 (50.00 g, 0.03 molar equivalent) and diethylene glycol divinyl ether (DEG-DVE) (2.0 g, 0.03 molar equivalent) in the 100 g container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 1 minute at 2300 rpm. The container was opened, and the IRGACURE® 2022 photoinitiator (0.540 g, 1% by weight) was added, and the container was placed back in the high speed mixer and mixed for 30 seconds at 2300 rpm. The polymer was poured into a circular metallic cap (12.7 cm (5 inches) in diameter) (pretreated with VALSPAR 225 release agent), and placed under UV light for 15 seconds, after which the polymer had completely cured. Curing was achieved using a SUPER SIX curing unit, obtainable from Fusion Systems Inc. The curing unit was equipped with a 300 W H-bulb that produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm 2 , measured by an energy meter disc, obtainable from EIT, Inc. of Sterling, VA, was applied to the polymer composition. Up to 5.08 cm (2 inches) of cured polymer was obtained. The hardness of the polymer, measured by a durometer, was 20 Shore A. The polymer was cut into six 1.27 cm (½ inch) dog bones with a tensile strength template, and three of the specimens were used to measure elongation and resistance to dry traction, via Instron. The results (an average of the three) are as follows: 1.7 MPa (250 psi) (tensile strength), and 1011% (elongation). One of the 1.27 cm (½ inch) dog bones was cut in half and placed in a small 20 ml vial with a lid and placed in an oven at 93 ° C (200 ° F). The sample was kept at 93 ° C (200 ° F) for two days after which the hardness check showed to be 10
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    35/36
    Shore A.
    [0080] A portion of the polymeric composition was spread over an aluminum panel coated with MAS-C-27725 of 7.62 cm x 15.24 cm (3 x 6) and cured according to the curing method described previously. A cured polymer film approximately 0.31 cm (1/8) thick was obtained. The film was further cut into two 25.4 cm (1 inch) strips and the strips were manually drawn back at 180 ° angles. The percentage of adherence to the substrate was recorded and the results were shown in Table 3.
    Comparative Example 8: Sealant composition without adduct [0081] A sealer was prepared by mixing the polymer described in Example 1 and the polymer described in Example 2 with diethylene glycol divinyl ether (DEG-DVE) and other ingredients described in Table 2.
    Table 2
    Component Weight, in grams Polymer of Example 1 240.00 Polymer of Example 2 60.00 DEG-DVE 14.28 SILQUEST A-189 1 0.77 Water 0.16 Calcium carbonate 9, 33 IRGACURE® 2022 1.62
    1 SILQUEST A-189 is mercapto propyl trimethoxysilane, obtainable from Momentive Performance Materials, Inc.
    [0082] All the ingredients described in Table 2 were mixed intimately. A portion of the sealant composition was poured into a 5.08 cm (2) diameter paper cup and cured for 15 seconds using a SUPER SIX curing unit, obtainable from Fusion Systems Inc. The curing unit was equipped with a bulb -H 300 W, which produced UV wavelengths ranging from 200 nm to 450 nm. Applied in
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    36/36 polymer composition a total dosage of UV energy of
    3.103 J / cm 2 , measured by an energy meter disk, obtainable from EIT, Inc. of Sterling, VA. Up to 3.81 cm (1.5 inches) of cured sealant was obtained.
    [0083] A portion of the polymeric composition was spread on an aluminum panel coated with MAS-C-27725 of 7.62 cm x 15.24 cm (3 x 6) and cured according to the curing method described previously. A cured polymer film approximately 0.31 cm (1/8) thick was obtained. The film was further cut into two strips of 25.4 cm (1 inch) and the strips were manually drawn back at 180 ° angles. The percentage of adherence to the substrate was recorded and the results were shown in Table 3.
    Table 3: Adherence of various polymeric compositions in aluminum coated with MAS-C-27725
    Composition Adherence Example 4 100% cohesive Example 5 100% cohesive Example 6 > 95% cohesive Comparative Example 7 0% cohesive Comparative Example 8 <50% cohesive
    [0084] Since embodiments of this invention have been described for illustrative purposes, it will become apparent to those skilled in the art that numerous variations of the details of the present invention can be made without departing from the invention defined in the appended claims.
    权利要求:
    Claims (15)
    [1]
    (1) each X is independently selected from O, S, and -NR 6 where R 6 is hydrogen or methyl;
    (iil) p is an integer having a value ranging from 2 to 6;
    (iii) q is an integer having a value ranging from 0 to 5; and (iv) r is an integer having a value ranging from 2 to 10;
    1. Sealant composition, characterized by the fact that it comprises: (a) a thiol-terminated polymer; and (b) an ethylenically unsaturated sulfur-containing silane, comprising within the molecule:
    (i) at least one sulfur atom (S), (ii) at least one ethylenically unsaturated carbon-carbon bond, and (iii) at least one silane group ( R 1) 3-x —Si (OR) x >
    in which each of R and Ri independently represents an organic group and x is 1, 2, or 3.
    [2]
    (2) each R 2 independently represents a C 2-10 alkylene group, a branched C 2-6 alkylene group, a C 6-8 cycloalkylene group, a C6-10 cycloalkylene group, or - [ (-CH2-) pX-] q - (- CH2) -) r- in which:
    (i) each X is selected, independently, from O, S, and -NR 6 where R 6 is hydrogen or methyl;
    (ii) p is an integer having a value ranging from 2 to 6;
    (iii) q is an integer having a value ranging from 0 to 5; and (iv) r is an integer having a value ranging from 2 to 10;
    2/4 of C6-10, - [(- CH2-) pX-] q - (- CH2) -) r- or - [(- CH2-) pX-] q - (- CH2)) r - in which at least one CH 2 unit - is replaced with a methyl group, where:
    2. Sealant composition according to claim 1, characterized in that the sealant composition is free of any component comprising ester bonds.
    [3]
    3/4 (ii) a polyene.
    (3) m is a rational number from 0 to 10; and (4) n is an integer having a value ranging from 1 to 60.
    Sealant composition according to claim 1, characterized in that the thiol-terminated polymer comprises sulfur-containing bonds in the polymeric main chain.
    [4]
    4/4 actinic.
    4. Sealant composition according to claim 3, characterized in that the sulfur-containing bonds comprise polyether ethers.
    [5]
    5. Sealant composition according to claim 4, characterized in that the thiol-terminated polymer comprises a structure having the formula:
    -R 1 - [-S- (CH2) 2-0- [-R 2 -0-] m- (CH 2 ) 2-SR 1 -] n in which (1) each R 1 independently represents a group n C2-io alkylene, a branched alkylene group of C 2 -6, a cycloalkylene group of C 6 cycloalkylene group an alkyl -8z
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    [6]
    6. Sealant composition according to claim 1, characterized in that the ethylenically unsaturated silane containing sulfur comprises an average of at least two ethylenically unsaturated groups per molecule.
    [7]
    7. Sealant composition according to claim 1, characterized in that the ethylenically unsaturated silane containing sulfur is the reaction product of reagents comprising:
    (i) a mercaptosilane; and
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    [8]
    Sealing composition according to claim 7, characterized in that the polyene comprises a trialyl compound comprising a cyanurate.
    [9]
    9. Sealant composition according to claim 1, characterized by the fact that it also comprises a photoinitiator.
    [10]
    10. Sealant composition according to claim 1, characterized in that it further comprises a polyene comprising a polyvinyl ether and / or a polyalyl compound.
    [11]
    11. Sealant composition according to claim 10, characterized in that the polyvinyl ether comprises a divinyl ether.
    [12]
    12. Sealant composition according to claim 10, characterized in that the ethylenically unsaturated silane containing sulfur is present in an amount such that 0.1 to 30 percent of the ethylenically unsaturated groups present in the sulfur containing ethylenically unsaturated silane, with based on the number of ethylenically unsaturated groups in the composition.
    [13]
    13. Sealing product, characterized by the fact that it comprises the reaction product of the sealing composition, as defined in any one of claims 1 or 5.
    [14]
    14. Method for preparing a cured sealant on a substrate, characterized by the fact that it comprises:
    (a) depositing an uncured sealant composition as defined in any of claims 1, 4-6, 10 and 12 on a substrate, and (b) exposing the uncured sealant composition to radiation
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    [15]
    15. Method according to claim 14, characterized in that the uncured sealant composition, as defined in claim 1, further comprises a photoinitiator and the actinic radiation comprises ultraviolet radiation.
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    JP2019019339A|2019-02-07|Methods for making cured sealants by actinic radiation and related compositions
    BR112017011874B1|2021-11-03|UNREACTED COMPOSITION, CURED SEALING AND METHOD FOR PREPARING A CURED SEALING
    同族专利:
    公开号 | 公开日
    CA2807816A1|2012-02-16|
    US20140186543A1|2014-07-03|
    CA2807816C|2015-11-24|
    EP2603561B1|2018-11-07|
    WO2012021793A1|2012-02-16|
    US8729198B2|2014-05-20|
    KR20130062335A|2013-06-12|
    KR101489103B1|2015-02-02|
    RU2540437C2|2015-02-10|
    BR112013003328A2|2016-07-05|
    AU2011289282A1|2013-02-28|
    HK1185371A1|2014-02-14|
    RU2013110826A|2014-09-20|
    ES2707283T3|2019-04-03|
    CN103119102A|2013-05-22|
    US9074117B2|2015-07-07|
    JP2013538890A|2013-10-17|
    MX341201B|2016-08-09|
    US20120040103A1|2012-02-16|
    JP5758492B2|2015-08-05|
    MX2013001755A|2013-06-05|
    CN103119102B|2015-04-15|
    AU2011289282B2|2014-02-06|
    EP2603561A1|2013-06-19|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-02-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/855,725|US8729198B2|2010-08-13|2010-08-13|Compositions comprising thiol-terminated polymers and sulfur-containing ethylenically unsaturated silanes and related cured sealants|
    PCT/US2011/047566|WO2012021793A1|2010-08-13|2011-08-12|Compositions comprising thiol-terminated polymers and sulfur-containing ethylenically unsaturated silanes and related cured sealants|
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