EP3063244A2 - Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof - Google Patents

Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof

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Publication number
EP3063244A2
EP3063244A2 EP14793756.9A EP14793756A EP3063244A2 EP 3063244 A2 EP3063244 A2 EP 3063244A2 EP 14793756 A EP14793756 A EP 14793756A EP 3063244 A2 EP3063244 A2 EP 3063244A2
Authority
EP
European Patent Office
Prior art keywords
group
adhesion promoting
certain embodiments
formula
adduct
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP14793756.9A
Other languages
German (de)
English (en)
French (fr)
Inventor
Chandra B. Rao
Jun Deng
Renhe Lin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PRC Desoto International Inc
Original Assignee
PRC Desoto International Inc
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Filing date
Publication date
Priority claimed from US14/065,521 external-priority patent/US9303149B2/en
Application filed by PRC Desoto International Inc filed Critical PRC Desoto International Inc
Publication of EP3063244A2 publication Critical patent/EP3063244A2/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents

Definitions

  • the present disclosure relates to adhesion promoting adducts containing adhesion promoting groups and metal ligands.
  • the adhesion promoting adducts may be used as additives in polymer compositions or may be copolymerized to a sulfur-containing polymer backbone to provide improved surface adhesion to metal surfaces.
  • Compositions including adhesion promoting adducts and sulfur-containing prepolymers useful in aerospace sealant applications are also disclosed.
  • Sealants useful in aerospace and other applications must satisfy demanding mechanical, chemical, and environmental requirements.
  • the sealants can be applied to a variety of surfaces including metal surfaces, primer coatings, intermediate coatings, finished coatings, and aged coatings.
  • Adhesion promoters are typically added to sealant formulations to enhance adhesion of the various components to each other and to the surfaces to which the sealant is applied. Ways to provide improve surface adhesion while maintaining other advantageous properties of a sealant are continuously desired.
  • Sulfur-containing polymers such as polythioethers and polysulfides are useful in aerospace applications.
  • suitable polythioethers and polysulfides are disclosed, for example, in U.S. Publication Nos. 2005/0010003, 2006/0270796,
  • Adhesion promoting adducts useful in improving adhesion to metal surfaces are disclosed.
  • adhesion promoting adducts comprising an adhesion promoting group and a metal ligand are provided.
  • compositions comprising adhesion promoting adducts comprising an adhesion promoting group and a metal ligand are provided.
  • cured sealants formed from sealant compositions comprising adhesion promoting adducts comprising an adhesion promoting group and a metal ligand are provided.
  • FIG. 1 illustrates the reaction described in Example 1.
  • FIG. 2 illustrates the reaction described in Example 2.
  • FIG. 3 is a table showing calculated energies for the interaction of ligands with aluminum (III) surfaces described in Example 4.
  • any numerical range recited herein is intended to include all sub-ranges encompassed therein.
  • a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of about 1 and the recited maximum value of about 10, that is, having a minimum value equal to or greater than about 1 and a maximum value of equal to or less than about 10.
  • the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
  • a dash (“-") that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms.
  • -CONH2 is bonded to another chemical moiety through the carbon atom.
  • Alkanediyl refers to a diradical of a saturated, branched or straight- chain, acyclic hydrocarbon group, having, for example, from 1 to 18 carbon atoms (CMS), from 1-14 carbon atoms (C1-14), from 1 -6 carbon atoms (CM), from 1 to 4 carbon atoms (CM), or from 1 to 3 hydrocarbon atoms (C1-3). It can be appreciated that a branched alkanediyl has a minimum of three carbon atoms.
  • the alkanediyl is C2-14 alkanediyl, C2-10 alkanediyl, C2-8 alkanediyl, C2-6 alkanediyl, C2-4 alkanediyl, and in certain embodiments, C2-3 alkanediyl.
  • alkanediyl groups include methane-diyl (-CH2-), ethane- 1,2- diyl (-CH2CH2-), propane- 1, 3 -diyl and iso-propane-l,2-diyl (e.g., -CH2CH2CH2- and - CH(CH 3 )CH 2 -), butane- 1,4-diyl (-CH2CH2CH2CH2-) , pentane- 1,5 -diyl (- CH2CH2CH2CH2CH2-), hexane-l,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane- 1,7-diyl, octane- 1,8 -diyl, nonane-l,9-diyl, decane-l,10-diyl, dodecane-l,12-diyl, and the like.
  • Alkanecycloalkane refers to a saturated hydrocarbon group having one or more cycloalkyl and/or cycloalkanediyl groups and one or more alkyl and/or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl, and alkanediyl are defined herein.
  • each cycloalkyl and/or cycloalkanediyl group(s) is C3-6, C5-6, and in certain embodiments, cyclohexyl or cyclohexanediyl.
  • each alkyl and/or alkanediyl group(s) is Ci-6, C , CM, and in certain embodiments, methyl, methanediyl, ethyl, or ethane- 1,2-diyl.
  • the alkanecycloalkane group is C4-18
  • alkanecycloalkane examples include 1,1,3,3- tetramethylcyclohexane and cyclohexylmethane.
  • alkanecycloalkanediyl refers to a diradical of an alkanecycloalkane group.
  • the alkanecycloalkanediyl group is C4-18
  • alkanecycloalkanediyl C4-16 alkanecycloalkanediyl, C4-12 alkanecycloalkanediyl, C4-8 alkanecycloalkanediyl, Ce-n alkanecycloalkanediyl, Ce-io alkanecycloalkanediyl, and in certain embodiments, Ce-9 alkanecycloalkanediyl.
  • alkanecycloalkanediyl groups include l,l,3,3-tetramethylcyclohexane-l,5-diyl and cyclohexylmethane-4,4'-diyl.
  • each R may be selected from, for example, hydrogen and C1-3 alkyl.
  • Alkoxy refers to a -OR group where R is alkyl as defined herein.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.
  • the alkoxy group is Ci-s alkoxy, Ci-6 alkoxy, C alkoxy, and in certain embodiments, C1-3 alkoxy.
  • Alkyl refers to a monoradical of a saturated, branched or straight-chain, acyclic hydrocarbon group having, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms.
  • the alkyl group is C2-6 alkyl, C2-4 alkyl, and in certain embodiments, C2-3 alkyl.
  • alkyl groups include methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like.
  • the alkyl group is C2-6 alkyl, C2-4 alkyl, and in certain embodiments, C2-3 alkyl. It can be appreciated that a branched alkyl group has a minimum of three carbon atoms.
  • Cycloalkanediyl refers to a diradical saturated monocyclic or polycyclic hydrocarbon group.
  • the cycloalkanediyl group is C3-12 cycloalkanediyl, C3-8 cycloalkanediyl, C3-6 cycloalkanediyl, and in certain embodiments, C5-6 cycloalkanediyl.
  • Examples of cycloalkanediyl groups include cyclohexane-l,4-diyl, cyclohexane-l,3-diyl, and cyclohexane-l,2-diyl.
  • Cycloalkyl refers to a saturated monocyclic or polycyclic hydrocarbon monoradical group.
  • the cycloalkyl group is C3-12 cycloalkyl, C3-8 cycloalkyl, C3-6 cycloalkyl, and in certain embodiments, C5-6 cycloalkyl.
  • each R 10 is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, where the one or more substituent groups is -OH.
  • a substituent group is -OH.
  • bis(sulfonyl)alkanol group has the structure -CH 2 -CH 2 -S(O)2-R 10 -CH(-OH)-R 10 -S(O)2- CH2-CH2- and in certain embodiments, the structure, -R 9 -S(O)2-R 10 -CH(-OH)-R 10 -S(O) 2 - R 9 - where each R 9 is an organic moiety; and each R 10 is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, wherein the one or more substituent groups is - OH.
  • a "bis(sulfonyl)alkanol group” can be a monovalent bis(sulfonyl)alkanol group or a divalent bis(sulfonyl)alkanol group.
  • a monovalent bis(sulfonyl)alkanol can be a terminal bis(sulfonyl)alkanol group such as a "l -(ethylenesulfonyl)-n-(vinylsulfonyl)alkanol group.”
  • bis(sulfonyl)alkanol group can be derived from the reaction of a bis(sulfonyl)alkanol and can have a terminal moiety with the general structure -R 9 -S(O)2-R 10 -CH(-OH)-R 10 -S(O) 2 -R 8 where R 9 is a moiety derived from the reaction of a bis(sulfonyl)alkanol with a compound having a group reactive with the bis(sulfonyl)alkanol; each R 10 is independently selected from Ci-3 alkanediyl, and substituted C1-3 alkanediyl, wherein the one or more substituent groups is -OH.
  • a bis(sulfonyl)alkanol group can also be divalent such as when the group is incorporated into the backbone of a prepolymer such as the polythioethers disclosed in U.S. Application No. 13/923,903.
  • a divalent bis(sulfonyl)alkanol group can have the general structure -R 9 -S(0)2-R 15 -CH(-OH)- R 15 -S(0) 2 -R 9 -; in certain embodiments, -CH2-CH 2 -S(0)2-R 15 -CH(-OH)-R 15 -S(0)2-CH 2 - CH 2 -, in certain embodiments, -R 9 -S(0)2-CH 2 -CH(-OH)-CH 2 -S(0)2-R 9 -, and in certain embodiments, -CH 2 -CH2-S(0)2-CH2-CH(-OH)-CH2-S(0)2-CH2-CH 2 -, where R 9 and R 15 are as defined herein.
  • each R 9 is an ethane - diyl group and/or each R 15 is methane-diyl.
  • a "bis(sulfonyl)alkanol” refers to a compound of the general formula R 8 - S(0)2-R 15 -CH(-OH)-R 15 -S(0)2-R 8 where each R 8 is a moiety having a terminal reactive group; and each R 10 is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, wherein the one or more substituent groups is -OH.
  • each R 8 comprises a terminal group reactive with a thiol group such as, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • a thiol group such as, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • a thiol group such as, for example, an alkenyl group, an epoxy group,
  • a bis(sulfonyl)alkanol may be a bis(vinylsulfonyl)alkanol comprising terminal alkenyl groups.
  • a bis(sulfonyl)alkanol may be a
  • a bis(vinylsulfonyl)alkanol is l,3-bis(vinylsulfonyl)-2-propanol.
  • a bis(sulfonyl)alkanol containing compound can be prepared by reacting a bis(vinylsulfonyl)alkanol with a compound having a reactive terminal functional group and a terminal group reactive with the terminal alkenyl groups of the
  • the bis(sulfonyl)alkanol such as a thiol group or an epoxy group.
  • the bis(sulfonyl)alkanol can have the structure R 9 -CH 2 -CH 2 -S(0)2-R 15 -CH(-OH)-R 15 -S(0)2- CH2-CH2-R 9 where each R 9 is a moiety derived from the reaction of the compound with the terminal alkenyl groups of the bis(vinylsulfonyl)alkanol.
  • a "bis(sulfonyl)alkanol-containing" polymer, prepolymer, or adduct refers to polymer, prepolymer, or adduct in which one or more divalent bis(sulfonyl)alkanol groups are incorporated into the backbone of the polymer, prepolymer, or adduct.
  • a divalent bis(sulfonyl)alkanol group can be incorporated in a prepolymer by reacting, for example, in a suitable ratio, a polythiol monomer or prepolymer of Formula (2) with a bis(sulfonyl)alkanol of Formula (3):
  • R is an organic moiety
  • w is an integer of at least 2 and each R 8 comprises a terminal group that is reactive with a thiol group such as, for example, an alkenyl group, and epoxy group, or a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), - OSO2-C6H4-CH3 (tosylate), etc.
  • a bis(sulfonyl)alkanol of Formula (3) may be a bis(vinylsulfonyl)alkanol having the structure of Formula (4):
  • R 10 is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, wherein the one or more substituent groups is -OH.
  • bis(sulfonyl)alkanol may be l,3-bis(vinylsulfonyl)-2-propanol.
  • a bis(sulfonyl)alkanol may be l,3-bis(vinylsulfonyl)-2-propanol.
  • a bis(sulfonyl)alkanol may be l,3-bis(vinylsulfonyl)-2-propanol.
  • bis(sulfonyl)alkanol group can be incorporated into a prepolymer backbone by reacting, in a suitable ratio, a thiol-capped bis(sulfonyl)alkanol of Formula (5) with a reactant of Formula (6):
  • each R 20 is a divalent moiety
  • each R 10 is as defined herein
  • each R 21 comprises a terminal group that is reactive with a thiol group such as, for example, an alkenyl group, an epoxy group, or a group consisting of a saturated carbon bearing a leaving group that are well known for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • a thiol group such as, for example, an alkenyl group, an epoxy group, or a group consisting of a saturated carbon bearing a leaving group that are well known for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • one or more bis(sulfonyl)alkanol groups can be incorporated into a prepolymer as either a chain segment, as part of a terminal bearing a reactive group, or both.
  • bis(vinylsulfonyl)alkanol can be used to introduce one or more l,n-bis(ethylenesulfonyl)alkanol groups into the backbone of a prepolymer chain, one or more terminal l-(ethylenesulfonyl)-n-(vinylsulfonyl)alkanol groups, or both.
  • bis(vinylsulfonyl)-2-propanol can be reacted with thiol-capped monomers/polymers to incorporate l,3-bis(ethylenesulfonyl)-2-propanol groups into the polymer chain.
  • bis(vinylsulfonyl)-2-propanol can be reacted with thiol-capped monomers/polymers to provide l -(ethylenesulfonyl)-3-(vinylsulfonyl)-2- propanol terminal groups, where the terminal alkenyl group is a well-recognized Michael acceptor.
  • a moiety derived from the reaction of a bis(sulfonyl)alkanol with a thiol group refers to the reaction product a thiol group and a moiety containing a terminal group reactive with the thiol group.
  • terminal groups reactive with thiol groups include epoxy groups, alkenyl groups, Michael acceptor groups, and groups comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • a moiety derived from the reaction of a bis(sulfonyl)alkanol with a thiol group has the structure: -CH2-CH2-R- -CH(-OH)-CH 2 -R- -CH 2 -CH(-OH)-R- or
  • R refers to a covalent bond or an organic moiety bonded to a sulfonyl group.
  • a moiety derived from the reaction of a bis(sulfonyl)alkanol with a thiol group also refers to a moiety R 9 , which is derived from the reaction of group R 8 with a thiol group, where R 8 comprises a terminal group reactive with a thiol group.
  • R 9 is derived from the reaction of a
  • R 9 is derived from the reaction of a bis(vinylsulfonyl)alkanol with a compound having a terminal group reactive with a thiol group and a group reactive with an alkenyl group.
  • R 9 may have the structure: -CH 2 -CH2-R'-CH2-CH 2 -, -CH(-OH)-CH 2 -R'-CH2-CH 2 -, -CH 2 -CH(-OH)-R'-CH2-CH 2 -, or -CH2-CH2-SO2-R -CH2-CH2- where R' is an organic moiety derived from the reaction of the compound used to cap the
  • bis(ethylenesulfonyl)alkanol with a functional group such as an alkenyl group, an epoxy group, a Michael acceptor group, or a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, - OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • R 9 is selected from C2-10 alkanediyl, substituted C2-10 alkanediyl, C2-10 heteroalkanediyl, substituted C2-10 heteroalkanediyl, C4-14
  • alkanecycloalkanediyl substituted C4-14 alkanecycloalkanediyl, C4-14
  • heteroalkanecycloalkanediyl substituted C4-14 heteroalkanecycloalkanediyl, C4-14
  • R 9 is ethane-diyl.
  • R 9 is selected from C2-10 alkyl, substituted C2-10 alkyl, C2-10 heteroalkyl, substituted C2-10 heteroalkyl, C4-14 alkanecycloalkyl, substituted C4-14 alkanecycloalkyl, C4-14 heteroalkanecycloalkyl, substituted C4-14 heteroalkanecycloalkyl, C4-14 alkanearyl, substituted C4-14 alkanearyl, C4-i4 heteroalkanearyl, and substituted C4-14 heteroalkanearyl.
  • acetylacetonate group refers to a group having the structure of Formula (1):
  • an acetylacetonate refers to a metal chelating agent comprising an acetylacetonate group and one or more reactive functional groups.
  • Haldroxypyridinone groups comprise groups such as 3-hydroxy-4- pyridinone and 3-hydroxy-2-pyridinone having the structure of Formula (8a) or Formula (8b), respectively:
  • a hydroxypyridinone metal chelating agent comprises a hydroxypyridinone group and one or more reactive functional groups such as terminal thiol groups.
  • Examples of quinones include 1,2-benzoquinone, 1 ,4-benzoquinone, 1 ,4-naphthaloquinone, and 9,10- anthraquinone.
  • Quinone groups can be metal ligands.
  • a "metal ligand” refers to an ion or molecule that binds to a metal atom and potentially other atoms to form a coordination complex.
  • the bonding between the metal and or atoms generally involves donation of one or more electron pairs to the metal and the nature of the bonding can be, for example, covalent, ionic, or by hydrogen bonding.
  • Metal ligands provided by the present disclosure are capable of forming coordination complexes to aerospace surfaces such as aluminum and titanium surfaces, which may be oxidized. In the case of oxidized surfaces a metal ligand may form a coordination complex with a metal such as Al(III) and oxygen atoms.
  • the coordination complex can enhance the adhesion to the metal or oxidized metal surface.
  • Metal ligands may be incorporated into the backbone of a prepolymer as provided by the present disclosure.
  • the metal ligand will comprise, or will be derivatized to comprise at least two groups that are reactive with a group of a subunit of a prepolymer.
  • Such reactive metal ligands may be commercially available or may be derivatized to include appropriate reactive substituent groups using methods known to those skilled in the ar.
  • Heteroalkanediyl refers to an alkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S, or P.
  • a heteroatom such as N, O, S, or P.
  • heteroalkanediyl the heteroatom is selected from N and O.
  • Heterocycloalkanediyl refers to a cycloalkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S, or P. In certain embodiments of heterocycloalkanediyl, the heteroatom is selected from N and O.
  • a “Michael acceptor” refers to an activated alkene, such as an alkenyl group proximate to an electron-withdrawing group such as a ketone, nitro, halo, nitrile, carbonyl, or nitro group.
  • Michael acceptors are well known in the art.
  • a “Michael acceptor group” refers to an activated alkenyl group and an electron-withdrawing group.
  • a Michael acceptor group is selected from a vinyl ketone, a vinyl sulfone, a quinone, an enamine, a ketimine, an aldimine, an oxazolidine, and an acrylate.
  • Michael acceptors include acrylate esters, acrylonitrile, acrylamides, maleimides, alkyl methacrylates, cyanoacrylates.
  • Other Michael acceptors include vinyl ketones, ⁇ , ⁇ - unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, certain azo compounds, ⁇ -keto acetylenes and acetylene esters.
  • a "Michael acceptor” refers to substituted alkene/alkyne compounds in which at least one alkene/alkyne group is directly attached to one or more electron- withdrawing group such as carbonyl (-CO), nitro (-NO2), nitrile (-CN), alkoxycarbonyl (-COOR), phosphonate (-PO(OR) 2 ), trifluoromethyl (-CF3), sulfonyl (-SO2-),
  • Michael acceptors trifluormethanesulfonyl (-S0 2 CF3), p-toluenesulfonyl (-S0 2 -C6H4-CH3), etc.
  • Types of compounds that function as Michael acceptors are vinyl ketones, quinones, nitroalkenes, acrylonitriles, acrylates, methacrylates, cyanoacrylates, acrylamides, maleimides, dialkyl vinylphosphonate, and vinylsulfones.
  • Michael acceptors are disclosed in Mather et al., Prog. Polym. Sci. 2006, 31, 487-531. Michael acceptor compounds having more than one Michael acceptor group are also well known.
  • a Michael acceptor group has the structure of Formula (9a) or Formula (9b):
  • each R 15 is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, wherein the one or more substituent groups is -OH.
  • a “Michael acceptor compound” refers to a compound comprising at least one terminal Michael acceptor group.
  • a Michael acceptor compound is a bis(vinylsulfonyl)alkanol
  • a "polyalkoxysilyl group” refers to a group having the structure of Formula (10):
  • each R 7 is independently selected from C alkyl.
  • p is 0, p is 1 , and in certain embodiments, p is 2.
  • each R 7 is independently selected from ethyl and methyl.
  • each R 7 is ethyl, and in certain embodiments, each R 7 is methyl.
  • the group is selected from -Si(-OCH 2 CH 3 ) 3 , -Si(-OCH 3 ) 3 , -Si(-CH 3 )(-OCH 3 ) 2 , -Si(- CH 3 ) 2 (-OCH 3 ), -Si(-CH 3 )(-OCH 2 CH 3 ) 2 , -Si(-CH 3 ) 2 (-OCH 2 CH 3 ), -Si(-CH 2 CH 3 )(-OCH 3 ), and -Si(-CH 2 CH 3 ) 2 (-OCH 3 ).
  • a "polyalkoxysilane” refers to a compound comprising a polyalkoxysilyl group. Polyalkoxysilyl groups are adhesion promoting groups and therefore
  • polyalkoxysilanes are adhesion promoters.
  • a polyalkoxysilane has the formula R u -P-R 12 where P is the core of the polyalkoxysilane, R 11 comprises a polyalkoxysilyl group, and R 12 comprises a reactive functional group.
  • polymer refers to oligomers, homopolymers, and copolymers. Unless stated otherwise, molecular weights are number average molecular weights for polymeric materials indicated as "Mn” as determined, for example, by gel permeation chromatography using a polystyrene standard in an art-recognized manner.
  • Mn number average molecular weights for polymeric materials indicated as "Mn” as determined, for example, by gel permeation chromatography using a polystyrene standard in an art-recognized manner.
  • prepolymer is also used to refer to polymeric components of a composition that when cured form a cured polymer.
  • Substituted refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituent(s).
  • the substituent is chosen from -OH, -NH2, and C1-3 alkyl.
  • Adhesion promoting adducts provided by the present disclosure include an adhesion promoting group and a metal ligand.
  • Groups that promote adhesion to metal surfaces are well-known in the art. Examples of groups that promote adhesion include polyalkoxysilyl groups, phosphonate groups, amine groups, including primary and secondary amines, carboxylic acid groups, and phosphonic acid groups.
  • an adhesion promoting group may be a polyalkoxysilyl group, which may have the structure -Si(R 4 ) y i(OR 5 ) Y 2 wherein yl is selected from 0, 1, and 2; y2 is selected from 1, 2, and 3; and the sum of yl and y2 is 3; each R 4 is independently selected from C alkyl; and each R 5 is independently C alkyl.
  • an adhesion promoting group may be a phosphonate group, which may have the structure wherein each R 6 is independently selected from CM alkyl.
  • an adhesion promoting group may be a phosphonic acid group, which has the structure wherein each R 6 is hydrogen.
  • an adhesion promoting group may be a primary amine, and in certain embodiments, a secondary amine.
  • an adhesion promoting group may be a carboxylic acid group.
  • Typical aerospace vehicle surfaces include, for example, aluminum, anodized aluminum, Al(III), Alodine®, and titanium.
  • a metal chelating agent coordinate with aluminum, aluminum oxide, Alodine®, titanium, and titanium oxide.
  • a metal ligand comprises a moiety capable of forming a coordination complex to one of or more of these aerospace surfaces.
  • other transition metals or elements such as oxygen may be involved in the coordination complex either through covalent, ionic, or hydrogen bonding interactions.
  • an appropriate metal ligand can be selected.
  • Basic donor groups effective in forming multidentate coordination complexes with aluminum (III) include aliphatic monohydroxy acid anions, catecholates, aromatic hydroxy acid anions, 3-hydroxy-4- pyridinones, hydroxamates, and 3-hydroxy-2-pyridinones.
  • Stable aluminum (III) complexes are with multidentate ligands having negative oxygen electron donors.
  • a metal ligand may form a multidentate complex such as a bidentate complex or a tridentate complex with the metal.
  • a metal ligand functional group is derived from a metal chelating agent selected from a bis(sulfonyl)alkanol, a benzoquinone, a
  • Examples of aluminum, aluminum oxide, and/or Al(III) ligands include 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy-2- pyridinone, 2-2'-dihyrdroxyazobenzene, 8-hydroxyquinoline, oxylate, malonate, citrate, inimodiacetic acid, picolinic acid, maltol, kojic acid, ⁇ , ⁇ '-diacetic acid (EDTA), N-(2- hydroxy)ethylenediamenetriacetic acid (HEDTA), ethylenediamine-N,N'-bis(2- hydroxyphenylacetic acid (EDDHA), and N,N'-bis(hydroxybenzyl)ethylenediamine-N,N'- diacetic acid (HBED), acetoacetate, and quinone.
  • Other aluminum and aluminum oxide chelators are disclosed, for example, in Yokel, Coordination Chemistry Reviews 2002, 228, 97-113; and Martell
  • DTPA diethylenetriamine pentaacetic acid
  • NTA nitrile triacetic acid
  • salicylic acid lactic acid
  • acetylacetonate
  • a metal ligand comprises a structure of Formula (12a), Formula (12b), Formula (12c), Formula (12d), Formula (12e), and a combination of any of the foregoing:
  • each X is independently selected from -C(O)- and -S(0) 2 -; n is an integer from 1 to 3; and R 5 is C alkanediyl.
  • a metal ligand comprises a bis(sulfonyl)alkanol, a hydroxypyridinone, a quinone, an acetylacetonate, or a combination of any of the foregoing.
  • Adhesion promoting adducts may also contain a reactive group that is reactive with a polyfunctionalizing agent or with a functional group of a prepolymer.
  • the reactive group may be reactive with a terminal group of a polyfunctionalizing agent and used to prepare a polyvalent adhesion promoting adduct, a copolymerizable adhesion promoting adduct, or a copolymerizable sulfur-containing adhesion promoting adduct as disclosed herein.
  • the reactive group may be reactive with a functional group of a multifunctional sulfur-containing prepolymer such as a polythioether or a polysulfide, and/or may be reactive with a curing agent. In either case, the reactive group can be useful for grafting the adhesion promoting adduct to the backbone of a cured polymer, which is useful for improving the adhesion strength of a composition.
  • an adhesion promoting adduct comprises the reaction product of reactants comprising an adhesion promoter comprising an adhesion promoting group and a functional group, and a metal chelating agent comprising a metal ligand and a functional group reactive with the functional group of the adhesion promoter.
  • an adhesion promoting adduct comprises the reaction product of reactants comprising an adhesion promoter of formula R U -P-R 12 and a metal chelating agent of formula R 13 -M-R 14 , where R 1 1 comprises an adhesion promoting group, P comprises a core of an adhesion promoter, M comprises a metal ligand, R 12 and R 13 comprise mutually reactive functional groups, and R 14 is selected from a non-reactive group, a reactive functional group, or is absent.
  • an adhesion promoting adduct has a structure of Formula (13):
  • R 11 comprises an adhesion promoting group
  • P comprises a core of an adhesion promoter
  • M comprises a metal ligand
  • R 12 and R 13 represent moieties derived from the reaction of R 12 and R 13 of an adhesion promoter R 1 '-P-R 12 and a metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 is selected from a non- reactive group, a reactive functional group, or is absent.
  • an adhesion promoter comprises an alkenyl group, a thiol group or an amine group that is reactive with a group of the metal chelating agent. In certain embodiments, an adhesion promoter comprises a thiol-terminate polyalkoxysilane.
  • polyalkoxysilyl- containing adhesion promoters having a reactive amine or thiol group include amine - functional adhesion promoters such as N-( -aminoethyl) ⁇ -aminopropyltrimethoxysilane (Silquest® A-l 120) and thiol-functional adhesion promoters such as ⁇ - mercaptopropyltrimethoxysilane (Silquest® A-l 89).
  • an adhesion promoter has a structure of Formula (14a), a structure of Formula (14b), a structure of Formula (14c), or a combination of any of the foregoing:
  • each R 16 is independently selected from C1-3 alkyl, and each R 17 is selected from hydrogen and C1-3 alkyl.
  • a metal chelating agent comprises an aluminum or aluminum oxide chelating agent and is selected from a bis(sulfonyl)alkanol, a quinone, an acetylacetonate, a hydroxypyridinone, and a combination of any of the foregoing.
  • aluminum chelating agents include acetylacetonates such as 2- (methylacyrloyloxy) ethyl acetoacetate (2-MEAA), hydroxypyridinones such as 3-hydroxy-4- pyridinone and 3-hydroxy-2-pyridinone, and bis(sulfonyl)alkanols such as bis(vinylsulfonyl)- 2-propanol.
  • acetylacetonates such as 2- (methylacyrloyloxy) ethyl acetoacetate (2-MEAA)
  • hydroxypyridinones such as 3-hydroxy-4- pyridinone and 3-hydroxy-2-pyridinone
  • bis(sulfonyl)alkanols such as bis(vinylsulfonyl)- 2-propanol.
  • a thiol-terminated adhesion promoter such as ⁇ - mercaptopropyltrimethoxysilane may be reacted with a bis(sulfonyl)alkanol such as 1,3- bis(vinylsulfonyl)-2-propanol to provide a adhesion promoting adduct of Formula (15):
  • each R 16 is independently selected from methyl and ethyl.
  • the mutually reactive functional groups of the adhesion promoter and the metal chelating agent may be terminal functional groups or may comprise the core of the adhesion promoter or metal chelating agent.
  • the moieties -P- and -M- may comprise one or more reactive functional groups.
  • an adhesion promoting adduct comprises one or more reactive functional groups. These reactive functional groups may be reacted with another compound to form an extended adhesion promoting adduct.
  • an adhesion promoting adduct comprises the reaction products of reactants comprising an adhesion promoting adduct, comprising a first reactive functional group, such as the adhesion promoting adduct of Formula (13); and a compound having a second reactive functional group reactive with the first reactive functional group.
  • the adhesion promoting adduct may be reacted with a polyamine such as a diamine, or a polythiol such as a dithiol.
  • a compound having a functional group reactive with an adhesion promoting adduct may have the structure of Formula (17):
  • each R 30 is independently selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 6 ) s -X-] q -(CHR 6 ) r -;
  • each R 6 is independently selected from hydrogen and methyl
  • each X is independently selected from -0-, -S-, and -NR- wherein R is selected from hydrogen and methyl;
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10;
  • an adhesion promoting adduct may be reacted with a reactive functional group of a prepolymer to provide an adhesion promoting adduct- functional or -terminated prepolymer.
  • the prepolymer may be a sulfur-containing prepolymer such as any of those disclosed herein including polythioether prepolymers.
  • adhesion promoting adducts are polyvalent in which more than one adhesion promoting adduct is bonded to a polyvalent common core.
  • Polyvalent adhesion promoting adducts may be formed by reacting an adhesion promoting adduct having a reactive group with a reactive group of a
  • a polyvalent adhesion promoting adduct comprises the reaction product of reactants comprising a z-valent polyfunctionalizing agent comprising terminal functional groups reactive with the functional group of the adhesion promoting adduct and an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a functional group.
  • an adhesion promoting adduct having a reactive group useful for reacting with a polyfunctionalizing agent include bis(sulfonyl)alkanol derived adhesion promoting adducts such as the adduct of Formula (13), which have a terminal alkenyl group that may reacted with, for example, thiol groups of a polyfunctionalizing agent.
  • polyfunctionalizing agents suitable for use in preparing such polyvalent adhesion promoting adducts include trifunctionalizing agents, that is, compounds where z is 3.
  • Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), 1,2,3-propanetrithiol, isocyanurate -containing trithiols, as disclosed in U.S. Publication No. 2010/0010133 at paragraphs [0102]-[0105], the cited portion of which is incorporated herein by reference.
  • Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether, and the polythiols described in U.S. Patent. Nos. 4,366,307; 4,609,762; and 5,225,472. Mixtures of polyfunctionalizing agents may also be used.
  • polyfunctionalizing agents may have the structure B(-V) z where B represents the core of the z-valent polyfunctionalizing agent, z is an integer from 3 to 6, and each -V is a moiety comprising a terminal group that is reactive with the functional group of the adhesion promoting adduct. In certain embodiments, z is 3, z is 4, z is 5, and in certain embodiments z is 6. In certain embodiments, a polyfunctional compound is trifunctional. In certain embodiments, a polyfunctional compounds is triallyl cyanurate (TAC) where B has the structure:
  • polyfunctional compound B(-V) z has a molecular weight less than 800 Daltons, less than 600 Daltons, less than 400 Daltons and in certain embodiments, less than 200 Daltons.
  • Polyfunctional compounds B(-V) z in which z is at least 3 may be any of the polyfunctionalizing agents useful in polymer chemistry.
  • Polyfunctionalizing agents having mixed functionality i.e., agents that include moieties (typically separate moieties), that react with both thiol and vinyl groups, may also be employed.
  • Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether, and the polythiols described in U.S. Patent No. 4,366,307, U.S. Patent No. 4,609,762, and U.S. Patent No. 5,225,472, each of which is incorporated by reference in its entirety. Combinations of polyfunctionalizing agents having the same terminal groups such as thiol groups or allyl groups may also be used.
  • a polyvalent adhesion promoting adduct has a structure of Formula (18):
  • R 11 comprises an adhesion promoting group
  • P comprises a core of an adhesion promoter
  • M comprises a metal ligand
  • R 12 and R 13 represent moieties derived from the reaction of R 12 and R 13 of adhesion promoter R u -P-R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a reactive functional group.
  • R 14 represents a moiety derived from the reaction of R 14 and V;
  • B represents a core of a z-valent polyfunctionalizing agent B(-V) z wherein: z is an integer from 3 to 6;
  • each -V is a group comprising a group reactive with R 14 ; and each -V- is derived from the reaction of -V with R 14 .
  • a polyvalent adhesion promoting adduct may be formed by reacting an adhesion promoting adduct of Formula (13) with a polyfunctionalizing agent B(-V) z where the adhesion promoting adduct comprises a functional group such as R 4 that is reactive with a functional group of -V.
  • a polyvalent adhesion promoting adduct comprises the reaction product of reactants comprising a polyfunctionalizing agent of formula B(-V) z , wherein, B represents a core of the z-valent polyfunctionalizing agent; z is an integer from 3 to 6; and each -V is a group comprising a first reactive functional group; and an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a second functional group reactive with the first reactive functional group of the
  • the ratio of adhesion promoting adduct to polyfunctionalizing agent may be adjusted to provide a range of functionalities.
  • an adhesion promoting adduct is a polyvalent sulfur-containing adhesion promoting adduct having the structure of Formula (19); BC-V'-S-R'-S- R 14 '-M-R 13 '-R 12 '-P-R u ) z (19) wherein
  • z is an integer from 1 to 6;
  • each R 1 is independently selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 3 ) s -X-] q -(CHR 3 ) r -;
  • each R 3 is independently selected from hydrogen and methyl
  • each X is independently selected from -0-, -S-, and -NR- wherein R is selected from hydrogen and methyl;
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10;
  • R 11 comprises an adhesion promoting group
  • P comprises a core of an adhesion promoter
  • M comprises a metal ligand
  • R 12 and R 13 represent moieties derived from the reaction of R 12 and R 13 of adhesion promoter R u -P-R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a reactive functional group.
  • R 14 represents a moiety derived from the reaction of R 14 and a thiol group
  • B represents a core of a z-valent polyfunctionalizing agent B(-V) z wherein: z is an integer from 3 to 6;
  • each -V is a group comprising a group reactive with a thiol group
  • each -V- is derived from the reaction of -V with a thiol group.
  • a polyvalent sulfur-containing adhesion promoting adduct comprises the reaction products of reactants comprising: (a) a
  • the reaction products comprise one or more compounds of Formula (19).
  • each or some of the arms of the polyfunctionalizing agent can be terminated in an adhesion promoting adduct.
  • at least one arm is reactive with a copolymer and/or curing agent.
  • a polyfunctional compound having terminal groups reactive with thiol groups has the structure B(-V) z where z is an integer from 3 to 6, and B and -V are as defined herein. [099] In certain embodiments of B(-V) z , each -V comprises a terminal alkenyl group.
  • a dithiol has the structure of Formula (20):
  • R 1 is selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 3 ) s -X-] q -(CHR 3 ) r -; wherein:
  • each R 3 is independently selected from hydrogen and methyl
  • each X is independently selected from -0-, -S-, and -NR- wherein R is selected from hydrogen and methyl;
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -.
  • X is selected from -O- and -S-, and thus -[-(CHR 3 ) s -X-] q -(CHR 3 ) - in Formula (20) is -[(-CH 2 -) P -0- ] q-(CH2)r- or -[(-CH2-)p-S-] q-(CH2)r-
  • p and r are equal, such as where p and r are both two.
  • R 1 is selected from C2-6 alkanediyl and -[- (CHR 3 ) s -X-] q -(CHR 3 ) r -.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -, and in certain embodiments X is -0-, and in certain embodiments, X is -S-.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -
  • p is 2, r is 2, q is 1
  • X is -S-; in certain embodiments, wherein p is 2, q is 2, r is 2, and X is -0-; and in certain embodiments, p is 2, r is 2, q is 1 , and X is -0-.
  • each R 3 is hydrogen, and in certain embodiments, at least one R 3 is methyl.
  • each R 1 is the same, and in certain embodiments, at least one R 1 is different.
  • dithiols examples include, for example, 1 ,2-ethanedithiol, 1,2- propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, l,3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl- substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, l,5-dimercapto-3-oxapentane, and a combination
  • a polythiol may have one or more pendant groups selected from a lower (e.g., Ci- e) alkyl group, a lower alkoxy group, and a hydroxyl group.
  • Suitable alkyl pendant groups include, for example, Ci-6 linear alkyl, C3-6 branched alkyl, cyclopentyl, and cyclohexyl.
  • Suitable dithiols include dimercaptodiethylsulfide (DMDS) (in Formula (20), R 1 is -[(-CH 2 -) p -X-] q -(CH 2 ) -, wherein p is 2, r is 2, q is 1, and X is -S-); dimercaptodioxaoctane (DMDO) (in Formula (20), R 1 is -[(-CH 2 -) p -X-] q -(CH 2 ) - , wherein p is 2, q is 2, r is 2, and X is -0-); and l,5-dimercapto-3-oxapentane (in Formula (20), R 1 is -[(-CH 2 -)p-X-]q-(CH 2 ) r -, wherein p is 2, r is 2, q is 1, and X is -0-).
  • DMDS dimercaptodiethylsul
  • dithiols that include both heteroatoms in the carbon backbone and pendant alkyl groups, such as methyl groups.
  • Such compounds include, for example, methyl- substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CH 2 CH 2 -SH, HS-CH(CH 3 )CH 2 -S- CH 2 CH 2 -SH and dimethyl substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CHCH 3 CH 2 -SH and HS-CH(CH 3 )CH 2 -S-CH 2 CH(CH 3 )-SH.
  • methyl- substituted DMDS such as HS-CH 2 CH(CH 3 )-S-CH 2 CH 2 -SH, HS-CH(CH 3 )CH 2 -S- CH 2 CH 2 -SH and dimethyl substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CHCH 3 CH 2 -SH and HS-CH(CH 3 )CH 2
  • Polyvalent sulfur-containing adhesion promoting adducts can impart additional flexibility to the polyvalent adhesion promoting groups that lead to enhanced surface adhesion.
  • polyvalent sulfur-containing adhesion promoting adducts can be prepared by first reacting a polyfunctionalizing agent with a sulfur-containing compound to provide a polyfunctionalizing agent having sulfur-containing groups. This intermediate may then be reacted with an adhesion promoting adduct such as an adduct of Formula (13) having functional groups reactive with the sulfur-containing groups. The sulfur-containing polyfunctionalizing agent and the adhesion promoting adduct may be reacted in a ratio such that all or some of the arms of are terminated with an adhesion promoting adduct.
  • Adhesion promoting adducts that can be directly polymerized to a sulfur- containing polymer backbone can improve the adhesion of a composition such as a sealant composition.
  • a copolymerizable adhesion promoting adduct includes adhesion promoting groups and metal ligands that provide surface adhesion and reactive groups that are reactive with terminal groups of a copolymer and/or curing agent.
  • a copolymerizable adhesion promoting adduct may include groups that are reactive with the copolymer.
  • a copolymerizable adhesion promoting adduct comprises the reaction product of reactants comprising an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a reactive functional group; and a z-valent polyfunctionalizing agent comprising functional groups reactive with the functional group of the adhesion promoting adduct; wherein the copolymerizable adhesion promoting adduct comprises from 1 to z-1 terminal adhesion promoting adducts.
  • a copolymerizable adhesion promoting adduct has the structure of Formula (21):
  • R 11 comprises an adhesion promoting group
  • P comprises a core of an adhesion promoter
  • M comprises a metal ligand
  • R 12 and R 13 represent moieties derived from the reaction of R 12 and R 13 of adhesion promoter R u -P-R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a reactive functional group;
  • B represents a core of a z-valent polyfunctionalizing agent of Formula (22): (-Y l ) zl (-Y 2 ) z - Zl (22) wherein,
  • z is an integer from 3 to 6;
  • zl is an integer from 1 to z-1 ;
  • each -V 1 is a group comprising a first reactive functional group; and at least one -V 2 comprises a second reactive functional group; and each R 14 represents a moiety derived from the reaction of R 14 and -V 1 ; and each -V 1 - represents a moiety derived from the reaction of -V 1 with R 14 .
  • a copolymerizable adhesion promoting adduct comprising the reaction product of reactants comprising:
  • B represents a core of a z-valent polyfunctionalizing agent B(-V) z wherein:
  • z is an integer from 3 to 6;
  • zl is an integer from 1 to z-1 ; each -V 1 is a group comprising a first reactive functional group; and at least one -V 2 comprises a second reactive functional group; and an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a third functional group reactive with the first reactive functional group.
  • V 1 and V 2 are the same and in certain embodiments, V 1 and V 2 are different. In certain embodiments, V 1 and V 2 comprise the same reactive functional group, and in certain embodiments, V 1 and V 2 comprise different reactive functional groups. In certain embodiments, each V 2 is selected to be reactive with a curing agent, a prepolymer, or a combination thereof. In certain embodiments, each V 2 comprises the same reactive group as a prepolymer forming a composition.
  • Copolymerizable adhesion promoting adducts include at least some groups that are reactive with a curing agent or copolymer such as from 2 to 5 groups that are reactive with a curing agent and/or copolymer.
  • a copolymerizable adhesion promoting adduct can be a copolymerizable sulfur-containing adhesion promoting adduct.
  • Copolymerizable sulfur-containing adhesion promoters are disclosed in U.S. Application No. 13/529,183. These copolymerizable sulfur-containing adhesion promoting adducts contain a sulfur- containing group bound to a polyfunctional core where at least some of the sulfur-containing groups are terminated with a group reactive with either the curing agent or a prepolymer, with other groups terminated with an adhesion promoting adduct.
  • Embodiments of the present disclosure include copolymerizable adhesion promoters analogous to those disclosed in U.S. Application No. 13/529,183 in which an adhesion promoting adduct of the present disclosure replaces at least some or all of the adhesion promoters disclosed therein.
  • a copolymerizable sulfur-containing adhesion promoting adduct comprises the reaction product of reactants comprising a dithiol; a polyfunctionalizing agent comprising functional groups reactive with thiol groups; and an adhesion promoting adduct comprising an adhesion promoting group, a metal ligand, and a group reactive with a thiol group.
  • compounds other than dithiols can be used to introduce sulfur-containing groups into the adduct.
  • a copolymerizable sulfur-containing adhesion promoting adduct has the structure of Formula (23); (23) wherein
  • each R 1 is independently selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 3 ) s -X-] q - (CHR 3 ) r -;
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10;
  • R 11 comprises an adhesion promoting group
  • P comprises a core of an adhesion promoter
  • M comprises a metal ligand
  • R 12 and R 13 represent moieties derived from the reaction of R 12 and R 13 of adhesion promoter R u -P-R 12 and metal chelating agent R 13 -M-R 14 , wherein R 12 and R 13 comprise mutually reactive functional groups, and R 14 comprises a reactive functional group.
  • R 14 represents a moiety derived from the reaction of R 14 and a thiol group
  • B represents a core of a z-valent polyfunctionalizing agent B(-V) z wherein: z is an integer from 3 to 6;
  • zl is an integer from 1 to z-1 ;
  • each -V is a group comprising a group reactive with a thiol group
  • each -V- is derived from the reaction of -V with a thiol group.
  • a copolymerizable sulfur-containing adhesion promoting adduct comprising the reaction product of reactants comprising a dithiol; a polyfunctionalizing agent comprising functional groups reactive with thiol groups; and the adhesion promoting adduct of claim 1 comprising functional groups reactive with thiol groups.
  • copolymerizable adhesion promoting adducts provided by the present disclosure can be copolymerized to the backbone of a sulfur- containing polymer such as a thiol-terminated sulfur-containing polymer, including, for example, thiol-terminated polythioethers and thiol-terminated polysulfides.
  • a sulfur- containing polymer such as a thiol-terminated sulfur-containing polymer, including, for example, thiol-terminated polythioethers and thiol-terminated polysulfides.
  • an adhesion promoting adduct can be copolymerized to a thiol-terminated polythioether polymer.
  • thiol-functional polythioethers are disclosed, for example, in U.S. Patent No. 6,172,179.
  • a thiol-functional polythioether comprises Permapol® P3.1E, available from PRC-DeSoto International Inc., Sylmar, CA.
  • an adhesion promoting adduct can be copolymerized to a polysulfide polymer.
  • a polysulfide polymer can be any of the polymers disclosed, for example, in U.S. Patent No. 4,623,711.
  • Compounds of Formula (21) and (23) comprise at least one terminal adhesion promoting adduct and at least two terminal thiol groups.
  • the at least one adhesion promoting adduct provides adhesion to a surface and/or other constituent of a formulation of which it is a part, and the terminal thiol-groups react with a curing agent to form a polymer network.
  • z2 is at least 2, and in certain embodiments, z2 is 2, 3, 4, and in certain embodiments z2 is 5.
  • zl is 1, 2, 3, and in certain embodiments, zl is 4.
  • a compound of Formula (21) and (17) is trivalent, such that z is 3, in certain embodiments, a compound of Formula (21) and (23) is tetravalent such that z is 4, and in certain embodiments, z is 5, and in certain embodiments, z is 6.
  • R 1 is selected from C2-6 alkanediyl and -[-(CHR 3 ) s -X-] q -(CHR 3 ) -.
  • R 1 is -[-(CHR 3 ) S -X- ] q-(CHR 3 ) r -, and in certain embodiments X is -O- and in certain embodiments, X is -S-.
  • R 1 is -[- (CHR 3 )s-X-] q-(CHR 3 ) r -, p is 2, r is 2, q is 1, and X is -S-; in certain embodiments, p is 2, q is 2, r is 2, and X is -0-; and in certain embodiments, p is 2, r is 2, q is 1 , and X is -0-.
  • each R 3 is hydrogen, and in certain embodiments, at least one R 3 is methyl.
  • each R 1 is the same, and in certain embodiments, at least one R 1 is different.
  • the terminal group that is reactive with a thiol group in compound A is selected from an alkenyl group, an isocyanate group, an epoxy group, a Michael acceptor group, and a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • the terminal group that is reactive with a thiol group in compound A is an alkenyl group, an isocyanate group, an epoxy group, a Michael acceptor group, and in certain embodiments, , a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • a terminal group that promotes adhesion is selected from a polyalkoxysilyl, a phosphonate, an amine, a carboxylic acid, and a phosphonic acid.
  • a terminal group that promotes adhesion is a polyalkoxysilyl group, a phosphonate group, an amine group, a carboxylic acid group, and in certain embodiments, a phosphonic acid group.
  • a metal ligand is selected from any of those disclosed herein.
  • -V is a moiety comprising a terminal group that is reactive with a thiol group.
  • -V is a moiety comprising a terminal group that is reactive with a thiol group.
  • -V is
  • R 10 is selected from Ci-6 alkanediyl, substituted Ci-6 alkanediyl, Ci-6 heteroalkanediyl, and substituted C 1-6 heteroalkanediyl.
  • the structure of -V is not limited. In certain embodiments, each -V may be the same, and in certain embodiments, at least one -V may be different.
  • each adhesion promoting adduct group is the same and is selected from Formula (24a), Formula (24b), Formula (24c), and Formula (24d):
  • each R 10 is C2-8 alkanediyl, yl is selected from 0, 1, and 2; y2 is selected from 1, 2, and 3; wherein the sum of yl and y2 is 3; each R 5 and R 6 is independently selected from C alkyl; and R 8 is selected from hydrogen and C alkyl.
  • each - A' is the same and is a moiety of Formula (24a), a moiety of Formula (24b), a moiety of Formula (24c), and in certain embodiments, a moiety of Formula (24d).
  • B represents a core of a z-valent, polyfunctional compound B(-V)z, where z is an integer from 3 to 6. In certain embodiments, z is 3, z is 4, z is 5, and in certain embodiments z is 6. In certain embodiments, a polyfunctional compound is trifunctional. In certain embodiments, a polyfunctional compounds is triallyl cyanurate (TAC) where B has the structure:
  • each -V has the structure -O-CH2-CF CH2.
  • polyfunctional compound B(-V) z has a molecular weight less than 800 Daltons, less than 600 Daltons, less than 400 Daltons and in certain embodiments, less than 200 Daltons.
  • Polyfunctional compounds B(-V) z in which z is at least 3 may be any of the polyfunctionalizing agents useful in polymer chemistry.
  • Polyfunctionalizing agents having mixed functionality i.e., agents that include moieties (typically separate moieties), that react with both thiol and vinyl groups, may also be employed.
  • Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether, and the polythiols described in U.S. Patent No. 4,366,307, U.S. Patent No. 4,609,762, and U.S. Patent No. 5,225,472, each of which is incorporated by reference in its entirety.
  • Combinations of polyfunctionalizing agents having the same terminal groups such as thiol groups or allyl groups may also be used.
  • each -V is a moiety comprising a terminal group that is reactive with a thiol group such as, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or a group comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, - OSO2CH3 (mesylate), -OSO2-C6H4-CH3 (tosylate), etc.
  • each -V is the same, and in certain embodiments, at least one -V is different.
  • - V is selected from C3-8 alkene-l-yl and C3-8 heteroalkene-l-yl, where the one or more hetero groups is selected from -O- and -S-.
  • Each -V- represents a moiety formed by the reaction of a moiety -V with a thiol group.
  • -V comprises a terminal alkenyl group selected from C3-8 alkene-l -yl and C3-8 heteroalkene-l-yl, and V is selected from C3-8 alkanediyl and C3-8 heteroalkanediyl.
  • a polyfunctionalizing agent having terminal groups reactive with thiol groups has the structure B(-V) z where z is an integer from 3 to 6, and B and -V are as defined herein.
  • each -V comprises a terminal alkenyl group.
  • a copolymerizable sulfur-containing adhesion promoter of Formula (23) comprises the reaction product of (a) a polyfunctionalizing agent having terminal groups that are reactive with thiol groups; (b) a dithiol; and (c) an adhesion promoting adduct having a functional group reactive with a thiol group.
  • the reaction products comprise one or more compounds of Formula (23).
  • the polyfunctionalizing agent and the adhesion promoting adduct may be, for example, any of those disclosed herein and the dithiol may be a dithiol of Formula (20).
  • a dithiol has the structure of Formula (20):
  • R 1 is selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 3 ) s -X-] q -(CHR 3 ) r -; wherein:
  • each R 3 is independently selected from hydrogen and methyl
  • each X is independently selected from -0-, -S-, and -NR- wherein R is selected from hydrogen and methyl;
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -.
  • X is selected from -O- and -S-, and thus -[-(CHR 3 ) s -X-] q -(CHR 3 ) - in Formula (20) is -[(-CH 2 -) P -0- ] q-(CH2)r- or -[(-CH2-)p-S-] q-(CH2)r-
  • p and r are equal, such as where p and r are both two.
  • R 1 is selected from C2-6 alkanediyl and -[- (CHR 3 ) s -X-] q -(CHR 3 ) r -.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -, and in certain embodiments X is -0-, and in certain embodiments, X is -S-.
  • R 1 is -[-(CHR 3 ) s -X-] q -(CHR 3 ) -
  • p is 2, r is 2, q is 1
  • X is -S-; in certain embodiments, wherein p is 2, q is 2, r is 2, and X is -0-; and in certain embodiments, p is 2, r is 2, q is 1 , and X is -0-.
  • each R 3 is hydrogen, and in certain embodiments, at least one R 3 is methyl.
  • each R 1 is the same, and in certain embodiments, at least one R 1 is different.
  • dithiols include, for example, 1 ,2-ethanedithiol, 1 ,2- propanedithiol, 1 ,3-propanedithiol, 1 ,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1 ,3-pentanedithiol, 1 ,5-pentanedithiol, 1 ,6-hexanedithiol, l ,3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl- substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, l ,5-dimercap
  • EHDT
  • a polythiol may have one or more pendant groups selected from a lower (e.g., Ci- e) alkyl group, a lower alkoxy group, and a hydroxyl group.
  • Suitable alkyl pendant groups include, for example, Ci-6 linear alkyl, C3-6 branched alkyl, cyclopentyl, and cyclohexyl.
  • Suitable dithiols include dimercaptodiethylsulfide (DMDS) (in Formula (20), R 1 is -[(-CH 2 -) p -X-] q -(CH 2 ) -, wherein p is 2, r is 2, q is 1, and X is -S-); dimercaptodioxaoctane (DMDO) (in Formula (20), R 1 is -[(-CH 2 -) p -X-] q -(CH 2 ) - , wherein p is 2, q is 2, r is 2, and X is -0-); and l ,5-dimercapto-3-oxapentane (in Formula (20), R 1 is -[(-CH 2 -)p-X-]q-(CH 2 ) r -, wherein p is 2, r is 2, q is 1 , and X is -0-).
  • DMDS dimercaptodiethy
  • dithiols that include both heteroatoms in the carbon backbone and pendant alkyl groups, such as methyl groups.
  • Such compounds include, for example, methyl- substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CH 2 CH 2 -SH, HS-CH(CH 3 )CH 2 -S- CH 2 CH 2 -SH and dimethyl substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CHCH 3 CH 2 -SH and HS-CH(CH 3 )CH 2 -S-CH 2 CH(CH 3 )-SH.
  • methyl- substituted DMDS such as HS-CH 2 CH(CH 3 )-S-CH 2 CH 2 -SH, HS-CH(CH 3 )CH 2 -S- CH 2 CH 2 -SH and dimethyl substituted DMDS, such as HS-CH 2 CH(CH 3 )-S-CHCH 3 CH 2 -SH and HS-CH(CH 3 )CH 2
  • the polyfunctionalizing agent and the dithiol may be reacted to form a thiol-terminated intermediate.
  • the molar ratios of the reactants are appropriately selected.
  • one mole of a trifunctional compound such as TAC can be reacted with three moles of a dithiol such as DMDO to provide a trifunctional, thiol- terminated intermediate.
  • a trifunctional, thiol-terminated intermediate may subsequently be reacted with a compound comprising a group that is reactive with a thiol group and a group that promotes adhesion.
  • the molar ratio of the intermediate and a compound comprising a group that is reactive with a thiol group and a group that promotes adhesion may be selected to provide a polyfunctional compound having a desired average sulfur-containing adhesion promoting adduct functionality.
  • a polyfunctional compound having a desired average sulfur-containing adhesion promoting adduct functionality For example, to obtain an average adhesion promoter functionality of about one, about one mole of polyfunctional intermediate is reacted with about one mole of a compound comprising a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion.
  • the compounds comprise at least one terminal group that promotes adhesion and at least two terminal groups such as terminal thiol groups, capable of reacting with a curing agent and thereby be incorporated into the backbone of the polymer network, e.g., copolymerized.
  • the sulfur-containing compound comprises, on average, a single adhesion promoting group per molecule, and in certain embodiments, an average of two adhesion promoting groups per molecule.
  • a copolymerizable sulfur-containing adhesion promoting adduct comprises the reaction products of reactants comprising triallycyanurate, DMDO, and an adhesion promoting adduct provided by the present disclosure.
  • Adhesion promoting adducts provided by the present disclosure may be used in polymer compositions, such as compositions formulated as sealants useful in the aerospace industry.
  • Adhesion promoting adducts such as those represented by Formula (13), Formula (18), Formula (19), Formula (21), Formula (23), or a combination of any of the foregoing may be used as adhesion promoting additives in a compositions.
  • an adhesion promoting adduct comprises, for example, from 1 wt% to 50 wt%, from 5 wt% to 30 wt%, or from 1 wt% to 10 wt%, of a composition.
  • adhesion promoting adduct is copolymerizable such as those represented by Formula (21) and (23), wherein the copolymerizable adhesion promoting adduct is included with a copolymer and/or curing agent having a suitable chemistry to incorporated the copolymerizable adhesion promoting adduct into cured polymer.
  • compositions may also contain a combination of one or more adhesion promoting adducts and/or copolymerizable adhesion promoting adducts provided by the present disclosure.
  • a composition can comprise a sulfur- containing polymer.
  • a sulfur-containing prepolymer comprises a thiol-terminated sulfur-containing prepolymer selected from a thiol-terminated polythioether prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated sulfur-containing polyformal prepolymer, and a combination of any of the foregoing.
  • a sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer.
  • a thiol-terminated sulfur-containing polymer comprises a thiol-terminated polythioether.
  • a thiol-terminated polythioether may comprise a mixture of different polythioethers and the polythioethers may have the same or different functionality of thiol groups.
  • a thiol-terminated polythioether has an average functionality from 2 to 6, from 2 to 4, from 2 to 3, and in certain embodiments, from 2.05 to 2.8.
  • a thiol-terminated polythioether may be selected from a difunctional sulfur-containing polymer, a trifunctional sulfur-containing polymer, and a combination thereof.
  • thiol-functional polythioethers are disclosed, for example in U.S. Patent No. 6,172,179.
  • a thiol-functional polythioether comprises Permapol® P3.1E available from PRC-DeSoto International Inc., Sylmar, CA.
  • a thiol-terminated polythioether comprises (a) a backbone comprising a structure having the Formula (25):
  • each R 1 is independently selected from a C2- 10 n- alkanediyl group, a C3-6 branched alkanediyl group, a Ce-8 cycloalkanediyl e group, a Ce-io alkanecycloalkanediyl group, a heterocyclic group, a -[(-CH2-) P -X-] q -(CH2) - group, and a -[(-CH2-) P -X-] q -(CH2) - group in which at least one -CH2- unit is substituted with a methyl group; (ii) each R 2 is independently selected from a C2-10 n- alkanediyl group, a C3-6 branched alkanediyl group,
  • a thiol-terminated polythioether is selected from a thiol-terminated polythioether of Formula (26a), a thiol-terminated polythioether of Formula (26b), and a combination thereof:
  • each R 1 independently is selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[(-CHR 3 -) s -X-] q -(- CHR 3 -) -, where:
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10;
  • each R 3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S, and -NHR-, where R is selected from hydrogen and methyl;
  • each R 2 is independently selected from Ci-10 alkanediyl, Ce-8 cycloalkanediyl, Ce- 14 alkanecycloalkanediyl, and -[(-CHR 3 -) s -X-] q -(-CHR 3 -) r -, wherein s, q, r, R 3 , and X are as defined above;
  • n is an integer from 0 to 50;
  • n is an integer from 1 to 60;
  • p is an integer from 2 to 6;
  • B represents a core of a z-valent, a polyfunctional compound B(-V) z wherein:
  • z is an integer from 3 to 6;
  • each -V is a moiety comprising a terminal group that is reactive with a thiol group
  • each -V- represents a moiety formed by the reaction of each -V with a thiol group.
  • R 1 in Formula (26a) and in Formula (26b) is -[(- CH2-)p-X-] q-(CH2)r-, where p is 2, X is -0-, q is 2, r is 2, R 2 is ethanediyl, m is 2, and n is 9.
  • R 1 is selected from C2-6 alkanediyl and -[-(CHR 3 ) s -X-] q -(CHR 3 ) -.
  • R 1 is -[- (CHR 3 )s-X-] q-(CHR 3 ) r -, and in certain embodiments X is -O- and in certain embodiments, X is -S-.
  • R 1 is -[-(CHR 3 )s-X-] q-(CHR 3 ) r -, p is 2, r is 2, q is 1, and X is -S-; in certain embodiments, wherein p is 2, q is 2, r is 2, and X is -0-; and in certain embodiments, p is 2, r is 2, q is 1 , and X is -0-.
  • each R 3 is hydrogen, and in certain embodiments, at least one R 3 is methyl.
  • each R 1 is the same, and in certain embodiments, at least one R 1 is different.
  • thiol-functional polythioethers examples include difunctional, that is, linear polymers having two thiol end groups, or polyfunctional, that is, branched polymers have three or more thiol end groups.
  • Suitable thiol-functional polythioethers are commercially available, for example, as
  • Suitable thiol-functional polythioethers may be produced by reacting a divinyl ether or mixtures of divinyl ethers with an excess of dithiol or a mixtures of dithiols.
  • dithiols suitable for use in preparing such thiol-functional polythioethers include those having Formula (20), other dithiols disclosed herein, or combinations of any of the dithiols disclosed herein.
  • Suitable divinyl ethers include, for example, divinyl ethers have Formula
  • R 2 in Formula (27) is selected from a C2-6 n- alkanediyl group, a C3-6 branched alkanediyl group, a Ce-8 cycloalkanediyl group, a Ce-io alkanecycloalkanediyl group, and -[(- CH2-)p-0-]q-(-CH2-)r-, where p is an integer ranging from 2 to 6, q is an integer from 1 to 5, and r is an integer from 2 to 10.
  • R 2 is a C2-6 n-alkanediyl group, a C3-6 branched alkanediyl group, a Ce-8 cycloalkanediyl group, a Ce-io alkanecycloalkanediyl group, and in certain embodiments, -[(-CH2-) P -0-] q - (-CH 2 -) r -.
  • Suitable divinyl ethers include, for example, compounds having at least one oxyalkanediyl group, such as from 1 to 4 oxyalkanediyl groups, i.e., compounds in which m in Formula (27) is an integer ranging from 1 to 4. In certain embodiments, m in Formula (27) is an integer ranging from 2 to 4. It is also possible to employ commercially available divinyl ether mixtures that are characterized by a non-integral average value for the number of oxyalkanediyl units per molecule. Thus, m in Formula (27) can also take on rational number values ranging from 0 to 10.0, such as from 1.0 to 10.0, from 1.0 to 4.0, or from 2.0 to 4.0.
  • Suitable divinyl ethers include, for example, divinyl ether, ethylene glycol divinyl ether (EG-DVE) (R 2 in Formula (27) is ethanediyl and m is 1), butanediol divinyl ether (BD-DVE) (R 2 in Formula (27) is butanediyl and m is 1), hexanediol divinyl ether (HD-DVE) (R 2 in Formula (27) is hexanediyl and m is 1), diethylene glycol divinyl ether (DEG-DVE) (R 2 in Formula (27) is ethanediyl and m is 2), triethylene glycol divinyl ether (R 2 in Formula (27) is ethanediyl and m is 3), tetraethylene glycol divinyl ether (R 2 in Formula (27) is ethanediyl and m is 4), cyclohexanedim
  • divinyl ethers in which R 2 in Formula (27) is C3- 6 branched alkanediyl may be prepared by reacting a polyhydroxy compound with acetylene.
  • divinyl ethers of this type include compounds in which R 2 in Formula (27) is an alkyl-substituted methanediyl group such as -CH(Ci3 ⁇ 4)- (for example Pluriol® blends such as Pluriol®E-200 divinyl ether (BASF Corp., Parsippany, NJ), for which R 2 in Formula (27) is ethanediyl and m is 3.8) or an alkyl-substituted ethanediyl (for example - ⁇ 3 ⁇ 40 ⁇ ( ⁇ 3 ⁇ 4)- such as DPE polymeric blends including DPE-2 and DPE-3 (International Specialty Products, Wayne, NJ)).
  • R 2 in Formula (27) is polytetrahydrofuryl (poly-THF) or polyoxyalkanediyl, such as those having an average of about 3 monomer units.
  • Two or more types of polyvinyl ether monomers of Formula (27) may be used.
  • two dithiols of Formula (20) and one polyvinyl ether monomer of Formula (27), one dithiol of Formula (20) and two polyvinyl ether monomers of Formula (27), two dithiols of Formula (20) and two divinyl ether monomers of Formula (27), and more than two compounds of one or both formulas may be used to produce a variety of thiol-functional polythioethers.
  • a polyvinyl ether monomer comprises 20 to less than 50 mole percent of the reactants used to prepare a thiol-functional polythioether, and, in certain embodiments, 30 to less than 50 mole percent.
  • relative amounts of dithiols and divinyl ethers are selected to yield terminal thiol groups.
  • a dithiol of Formula (20) or a mixture of at least two different dithiols of Formula (20) are reacted with of a divinyl ether of Formula (27) or a mixture of at least two different divinyl ethers of Formula (27) in relative amounts such that the molar ratio of thiol groups to vinyl groups is greater than 1 : 1, such as 1.1 to 2.0: 1.0.
  • the reaction between compounds of dithiols and divinyl ethers may be catalyzed by a free radical catalyst.
  • Suitable free radical catalysts include, for example, azo compounds, for example azobisnitriles such as azo(bis)isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and t-butyl peroxide; and inorganic peroxides such as hydrogen peroxide.
  • the catalyst may be a free-radical catalyst, an ionic catalyst, or ultraviolet radiation. In certain embodiments, the catalyst does not comprise acidic or basic compounds, and does not produce acidic or basic compounds upon decomposition.
  • free-radical catalysts examples include azo-type catalyst, such as Vazo®-57 (Du Pont), Vazo®-64 (Du Pont), Vazo®-67 (Du Pont), V-70® (Wako Specialty Chemicals), and V-65B® (Wako Specialty Chemicals).
  • azo-type catalyst such as Vazo®-57 (Du Pont), Vazo®-64 (Du Pont), Vazo®-67 (Du Pont), V-70® (Wako Specialty Chemicals), and V-65B® (Wako Specialty Chemicals).
  • alkyl peroxides such as t- butyl peroxide.
  • the reaction may also be effected by irradiation with ultraviolet light either with or without a cationic photoinitiating moiety.
  • Thiol-functional polythioethers provided by the present disclosure may be prepared by combining at least one compound of Formula (20) and at least one compound of Formula (27) followed by addition of an appropriate catalyst, and carrying out the reaction at a temperature from 30°C to 120°C, such as 70°C to 90°C, for a time from 2 to 24 hours, such as 2 to 6 hours.
  • thiol-terminated polythioethers may comprise a polyfunctional polythioether, i.e., may have an average functionality of greater than 2.0.
  • Suitable polyfunctional thiol-terminated polythioethers include, for example, those having the structure of Formula (28): wherein: (i) A comprises a structure of Formula (28), (ii) B denotes a z-valent residue of a polyfunctionalizing agent; and (iii) z has an average value of greater than 2.0, and, in certain embodiments, a value between 2 and 3, a value between 2 and 4, a value between 3 and 6, and in certain embodiments, is an integer from 3 to 6.
  • polyfunctional thiol-functional polymers include trifunctionalizing agents, that is, compounds where z is 3.
  • Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), 1,2,3-propanetrithiol, isocyanurate -containing trithiols, and combinations thereof, as disclosed in U.S. Publication No. 2010/0010133 at paragraphs [0102]-[0105], the cited portion of which is incorporated herein by reference.
  • Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether, and the polythiols described in U.S. Patent. Nos. 4,366,307; 4,609,762; and 5,225,472. Mixtures of polyfunctionalizing agents can also be used.
  • trifunctionalizing agents may afford average functionalities from 2.05 to 3.0, such as from 2.1 to 2.6. Wider ranges of average functionality may be achieved by using tetrafunctional or higher functionality polyfunctionalizing agents. Functionality may also be affected by factors such as stoichiometry, as will be understood by those skilled in the art.
  • Thiol-functional polythioethers having a functionality greater than 2.0 may be prepared in a manner similar to the difunctional thiol-functional polythioethers described in U.S. Publication No. 2010/0010133.
  • polythioethers may be prepared by combining (i) one or more dithiols described herein, with (ii) one or more divinyl ethers described herein, and (iii) one or more polyfunctionalizing agents. The mixture may then be reacted, optionally in the presence of a suitable catalyst, to afford a thiol- functional polythioether having a functionality greater than 2.0.
  • a thiol-terminated polythioether comprises the reaction product of reactants comprising:
  • R 1 is selected from C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and -[-(CHR 3 ) s -X-] q - (CHR 3 ) -; wherein:
  • s is an integer from 2 to 6;
  • q is an integer from 1 to 5;
  • r is an integer from 2 to 10;
  • each R 2 is independently selected from Ci-10 alkanediyl, Ce-8 cycloalkanediyl, Ce-i4 alkanecycloalkanediyl, and -[(-CHR 3 -) s -X-] q -( CHR 3 -) -, wherein s, q, r, R 3 , and X are as defined above; m is an integer from 0 to 50;
  • n is an integer from 1 to 60;
  • p is an integer from 2 to 6.
  • the reactants comprise (c) a polyfunctional compound such as a polyfunctional compound B(-V) z , where B, -V, and z are as defined herein.
  • Thiol-terminated polythioethers provided by the present disclosure represent thiol-terminated polythioethers having a molecular weight distribution.
  • thiol-terminated polythioethers useful in compositions can exhibit a number average molecular weight ranging from 500 Daltons to 20,000 Daltons, in certain
  • thiol-terminated polythioethers useful in compositions provided by the present disclosure exhibit a polydispersity (M w /M n ; weight average molecular weight/number average molecular weight) ranging from 1 to 20, and in certain embodiments, from 1 to 5.
  • the molecular weight distribution of thiol-terminated polythioethers may be characterized by gel permeation chromatography.
  • Curable compositions may further include a curing agent.
  • Compositions may further include additives, catalysts, fillers, and/or other sulfur-containing prepolymers including for example, polythioethers, sulfur-containing polyformals, and/or polysulfides.
  • a suitable curing agent is selected to be reactive with the terminal groups of the bis(sulfonyl)alkanol-containing polythioether and optional sulfur-containing prepolymers.
  • a suitable curing agent is a polyepoxide.
  • suitable polyepoxies include, for example, polyepoxide resins such as hydantoin diepoxide, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, Novolac ® type epoxides such as DENTM 438 (Dow Chemical Company), certain epoxidized unsaturated resins, and combinations of any of the foregoing.
  • a polyepoxide refers to a compound having two or more reactive epoxy groups.
  • an epoxy curing agent is selected from EPONTM 828 (Momentive Specialty Chemicals, Inc), DENTM 431 (Dow Chemical Company), and a combination thereof.
  • EPONTM 828 Momentive Specialty Chemicals, Inc
  • DENTM 431 Density Polymer 431
  • useful curing agents that are reactive with thiol groups include diepoxides.
  • amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diethylaminopropylamine (DEAPA), N- aminoethylpiperazine (N-AEP), isophoronediamine (IPDA), m-xylenediamine,
  • DTA diethylenetriamine
  • TTA triethylenetetramine
  • TEPA tetraethylenepentamine
  • DEAPA diethylaminopropylamine
  • N-AEP N- aminoethylpiperazine
  • IPDA isophoronediamine
  • diaminodiphenylmethane DDM
  • diaminodiphenylsulfone DDS
  • aromatic amines ketimine
  • polyamines polyamides
  • phenolic resins anhydrides such phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride; polymercaptans; polysulfides; and other curing agents known to those skilled in the art.
  • a polyepoxy curing agent comprises an epoxy- functional polymer.
  • suitable epoxy-functional polymers include the epoxy- functional sulfur-containing polyformal polymers disclosed in U.S. Patent Application No. 13/050,988 and epoxy-functional polythioether polymers disclosed in U.S. Patent No.
  • an epoxy-functional polymer when used as a curing agent, has a molecular weight less than about 2,000 Daltons, less than about 1,500, Daltons, less than about 1,000 Daltons, and in certain embodiments, less than about 500 Daltons.
  • a polyepoxy may comprise about 0.5 wt% to about 20 wt % of the composition, from about 1 wt % to about 10 wt%, from about 2 wt % to about 8 wt%, from about 2 wt % to about 6 wt %, and in certain embodiments, from about 3 wt % to about 5 wt %, where wt % is based on the total solids weight of the composition.
  • a suitable curing agent is an unsaturated compound such as an acrylic or methacrylic ester of a polyol, unsaturated synthetic or naturally occurring resin compounds, triallyl cyanurate, and olefin terminated derivatives of sulfur-containing compound such as polythioethers.
  • compositions provided by the present disclosure may comprise an isocyanate curing agent such as a diisocyanate and/or triisocyanate curing agent.
  • isocyanate curing agents include toluene diisocyanate, and combinations of any of the foregoing.
  • Isocyanate curing agents are commercially available and include, for example, products under the tradenames Baydur ® (Bayer MaterialScience), Desmodur ® (Bayer MaterialScience), Solubond ® (DSM), ECCO (ECCO), Vestanat ® (Evonik), Irodur ® (Huntsman), RhodocoatTM (Perstorp), and Vanchem ® (V.T. Vanderbilt).
  • a polyisocyanate curing agent comprises isocyanate groups that are reactive with thiol groups and that are less reactive with Michael acceptor groups.
  • Examples of useful curing agents that are reactive with amine groups include polymeric polyisocyanates, non-limiting examples of which include polyisocyanates having backbone linkages chosen from urethane linkages (-NH-C(O)-O-), thiourethane linkages (-NH-C(O)-S-), thiocarbamate linkages (-NH-C(S)-O-), dithiourethane linkages (-NH-C(S)-S-), and combinations of any of the foregoing.
  • polymeric polyisocyanates non-limiting examples of which include polyisocyanates having backbone linkages chosen from urethane linkages (-NH-C(O)-O-), thiourethane linkages (-NH-C(O)-S-), thiocarbamate linkages (-NH-C(S)-O-), dithiourethane linkages (-NH-C(S)-S-), and combinations of any of the foregoing.
  • an isocyanate curing agent comprises an isocyanate-functional polymer.
  • suitable isocyanate-functional polymers include the isocyanate-functional sulfur-containing polyformal polymers disclosed in U.S. Patent Application No. 13/051,002.
  • an isocyanate-functional polymer when used as a curing agent, has a molecular weight less than about 2,000 Daltons, less than about 1,500, Daltons, less than about 1,000 Daltons, and in certain embodiments, less than about 500 Daltons.
  • an isocyanate curing agent may comprise about 0.5 wt % to about 20 wt % of the composition, from about 1 wt % to about 10 wt%, from about 2 wt % to about 8 wt %, from about 2 wt% to about 6 wt %, and in certain embodiments, from about 3 wt% to about 5 wt % of the composition, where wt% is based on the total solids weight of the composition.
  • compositions provided by the present disclosure comprise an amine curing agent.
  • useful curing agents that are reactive with isocyanate groups include diamines, polyamines, polythiols, and polyols, including those disclosed herein.
  • compositions provided by the present disclosure comprise a curing agent selected from a monomeric thiol, a polythiol, a polyamine, and a blocked polyamine.
  • Curing agents useful in compositions provided by the present disclosure include compounds that are reactive with the terminal groups of the bis(sulfonyl)alkanol- containing polythioether, such as compounds that are reactive with hydroxyl groups, alkenyl groups, epoxy groups, thiol groups, amine groups, or isocyanate groups.
  • Examples of useful curing agents that are reactive with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are disclosed herein.
  • Examples of useful curing agents that are reactive with alkenyl groups include dithiols and polythiols, examples of which are disclosed herein.
  • polythioethers provided by the present disclosure can hydrolyze in the presence of water inducing self-polymerization via condensation.
  • Catalysts for use with polyalkoxysilyl- terminated bis(sulfonyl)alkanol-containing polythioether include organotitanium compounds such as tetraisopropoxy titanium, tetra-tert-butoxy titanium, titanium
  • organic tin compounds dibutyltin dilaurate, dibutyltin bisacetylacetoacetate, and tin octylate; metal dicarboxylates such as lead dioctylate; organozirconium compounds such as zirconium tetraacetyl acetonate; and organoaluminum compounds such as aluminum triacetyl-acetonate.
  • Suitable catalysts for moisture curing include diisopropoxy bis(ethyl acetoacetonate)titanium, diisopropoxy bis(acetyl acetonate)titanium, and dibutoxy bis(methyl acetoacetonate)titanium. It can be appreciated that because the curing agent for
  • polyalkoxysilyl-terminated bis(sulfonyl)alkanol-containing polythioether can be atmospheric moisture, it is not necessary to include a curing agent to a curable composition containing polyalkoxysilyl-terminated bis(sulfonyl)alkanol-containing polythioether. Therefore, compositions comprising polyalkoxysilyl-terminated bis(sulfonyl)alkanol-containing polythioether and a curing agent for the polyalkoxysilyl group refer to atmospheric moisture.
  • compositions provided by the present disclosure may contain from about 90% to about 150% of the stoichiometric amount, from about 95% to about 125%), and in certain embodiments, from about 95% to about 105%> of the amount of the selected curing agent(s).
  • compositions provided by the present disclosure comprise, in addition to a bis(sulfonyl)alkanol-containing polythioether or prepolymer thereof, or a reaction product of any one of the reactions disclosed herein, or a combination of any of the foregoing, one or more additional sulfur-containing polymers.
  • a sulfur-containing polymer can be any polymer having at least one sulfur atom in the repeating unit, including, but not limited to, polymeric thiols, polythiols, thioethers, polythioethers, sulfur-containing polyformals, and polysulfides.
  • a “thiol,” as used herein, refers to a compound comprising a thiol or mercaptan group, that is, an "SH” group, either as the sole functional group or in combination with other functional groups, such as hydroxyl groups, as is the case with, for example, thioglycerols.
  • a polythiol refers to such a compound having more than one SH group, such as a dithiol or higher functionality thiol. Such groups are typically terminal and/or pendant such that they have an active hydrogen that is reactive with other functional groups.
  • a polythiol can comprise both a terminal and/or pendant sulfur (-SH) and a non- reactive sulfur atom (-S- or -S-S-).
  • the term polythiol generally encompasses polythioethers and polysulfides.
  • compositions provided by the present disclosure include, for example, those disclosed in U.S. Patent Nos. 6,172,179, 6,509,418, and 7,009,032.
  • compositions provided by the present disclosure comprise a polythioether having the structure of Formula (29):
  • R 1 is selected from a C2-6 alkanediyl, Ce-8 cycloalkanediyl, Ce-io cycloalkanealkanediyl, -[(-CH 2 -) s -X-] q -(-CH 2 -) -, and -[(-CH 2 -)s-X-]q-(-CH 2 -) - in which at least one -CH 2 - unit is substituted with a methyl group;
  • R 2 is selected from C 2 _6 alkanediyl, Ce-8 cycloalkanediyl, C6-10 cycloalkanealkanediyl, and -[(-CH 2 -) s -X-] q -(-CH 2 -
  • the one or more additional sulfur-containing polymers may be difunctional or multifunctional, for example, having from 3 to 6 terminal groups, or a mixture thereof.
  • compositions provided by the present disclosure comprise from about 10 wt % to about 90 wt % of a sulfur-containing polymer provided by the present disclosure, from about 20 wt% to about 80 wt%, from about 30 wt% to about 70 wt%, and in certain embodiments from about 40 wt % to about 60 wt %, where wt % is based on the total weight of all non-volatile components of the composition (i.e., the dry weight).
  • polysulfide refers to a polymer that contains one or more sulfide linkages, i.e., -S x - linkages, where x is from 2 to 4, in the polymer backbone and/or in pendant positions on the polymer chain.
  • the polysulfide polymer will have two or more sulfur-sulfur linkages.
  • Suitable polysulfides are commercially available, for example, from Akzo Nobel and Toray Fine Chemicals under the names Thiokol-LP and Thioplast ® .
  • Thioplast ® products are available in a wide range of molecular weights ranging, for example, from less than 1,100 to over 8,000, with molecular weight being the average molecular weight in grams per mole. In some cases, the polysulfide has a number average molecular weight of 1,000 Daltons to 4,000 Daltons.
  • the crosslink density of these products also varies, depending on the amount of crosslinking agent used.
  • the -SH content, i.e., thiol or mercaptan content, of these products can also vary.
  • the mercaptan content and molecular weight of the polysulfide can affect the cure speed of the polymer, with cure speed increasing with molecular weight.
  • the sulfur-containing polymer is selected from a polythioether and a polysulfide, and a combination thereof.
  • a sulfur- containing polymer comprises a polythioether
  • a sulfur- containing polymer comprises a polysulfide.
  • a sulfur-containing polymer may comprise a mixture of different polythioethers and/or polysulfides, and the polythioethers and/or polysulfides may have the same or different functionality.
  • a sulfur- containing polymer has an average functionality from 2 to 6, from 2 to 4, from 2 to 3, and in certain embodiments, from 2.05 to 2.5.
  • a sulfur-containing polymer can be selected from a difunctional sulfur-containing polymer, a trifunctional sulfur-containing polymer, and a combination thereof.
  • a curing agent may be selected that is reactive with the terminal groups of the sulfur-containing polymer and the sulfur-containing compound.
  • a sulfur-containing polymer and a sulfur-containing compound provided by the present disclosure comprise the same groups reactive with the curing agent.
  • both a sulfur-containing polymer and a sulfur-containing compound provided by the present disclosure comprise reactive thiol groups
  • the curing agent comprises reactive alkenyl groups, epoxy groups, isocyanate groups, Michael acceptor groups, or groups comprising a saturated carbon bearing a leaving group that are well suited for nucleophilic substitution such as, for example, -CI, -Br, -I, -OSO2CH3 (mesylate), - OSO2-C6H4-CH3 (tosylate), etc.
  • Compositions provided by the present disclosure may include one or more catalysts.
  • a catalyst can be selected as appropriate for the curing chemistry employed. In certain embodiments, for example, when curing thiol-terminated bis(sulfonyl)alkanol- containing polythioethers or prepolymers and polyepoxides, the catalyst is an amine catalyst.
  • a cure catalyst may be present in an amount from 0.1 to 5 weight percent, based on the total weight of the composition.
  • Suitable catalysts include 1,4- diazabicyclo[2.2.2]octane (DABCO ® , commercially available from Air Products, Chemical Additives Division, Allentown, Pa.) and DMP-30 ® (an accelerant composition including 2,4,6-tris(dimethylaminomethyl)phenol.
  • DABCO ® 1,4- diazabicyclo[2.2.2]octane
  • DMP-30 an accelerant composition including 2,4,6-tris(dimethylaminomethyl)phenol.
  • compositions provided by the present disclosure comprise one or more than one adhesion promoters.
  • a one or more additional adhesion promoter may be present in amount from 0.1 wt% to 15 wt% of a composition, less than 5 wt%, less than 2 wt%, and in certain embodiments, less than 1 wt%, based on the total dry weight of the composition.
  • adhesion promoters include phenolics, such as Methylon ® phenolic resin, and organosilanes, such as epoxy, mercapto or amino functional silanes, such as Silquest ® A- 187 and Silquest ® A-l 100.
  • Other useful adhesion promoters are known in the art.
  • a composition provided by the present disclosure comprises an ethylenically unsaturated silane, such as, for example, a sulfur-containing ethylenically unsaturated silane, which can improve the adhesion of a cured sealant to a metal substrate.
  • an ethylenically unsaturated silane such as, for example, a sulfur-containing ethylenically unsaturated silane, which can improve the adhesion of a cured sealant to a metal substrate.
  • Examples of ethylenically unsaturated silanes are disclosed in U.S. Publication No. 2012/0040104, which is incorporated by reference in its entirety.
  • compositions may include, in addition to an adhesion promoting adduct provided by the present disclosure, and one or more sulfur-containing polymers such as thiol- terminated sulfur-containing polymers, a polyene such as a polyvinyl ether including, for example, a polyvinyl ether of Formula (27).
  • sulfur-containing polymers such as thiol- terminated sulfur-containing polymers
  • a polyene such as a polyvinyl ether including, for example, a polyvinyl ether of Formula (27).
  • compositions provided by the present disclosure comprise one or more curing agents such as an epoxy, an isocyanate, and a combination thereof.
  • compositions provided by the present disclosure may include one or more catalysts.
  • compositions provided by the present disclosure may comprise one or more different types of filler.
  • suitable fillers include those commonly known in the art, including inorganic fillers, such as carbon black and calcium carbonate (CaCC ), silica, polymer powders, and lightweight fillers.
  • Suitable lightweight fillers include, for example, those described in U.S. Patent No. 6,525,168.
  • a composition includes 5 wt% to 60 wt% of the filler or combination of fillers, 10 wt% to 50 wt%, and in certain embodiments, from 20 wt% to 40 wt%, based on the total dry weight of the composition.
  • compositions provided by the present disclosure may further include one or more colorants, thixotropic agents, accelerators, fire retardants, adhesion promoters, solvents, masking agents, or a combination of any of the foregoing.
  • fillers and additives employed in a composition may be selected so as to be compatible with each other as well as the polymeric component, curing agent, and or catalyst.
  • compositions provided by the present disclosure include low density filler particles.
  • low density when used with reference to such particles means that the particles have a specific gravity of no more than 0.7, in certain embodiments no more than 0.25, and in certain embodiments, no more than 0.1.
  • Suitable lightweight filler particles often fall within two categories - microspheres and amorphous particles.
  • the specific gravity of microspheres may range from 0.1 to 0.7 and include, for example, polystyrene foam, microspheres of polyacrylates and polyolefins, and silica microspheres having particle sizes ranging from 5 to 100 microns and a specific gravity of 0.25 (Eccospheres ® ).
  • a low density filler comprises less than 2 wt% of a composition, less than 1.5 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.75 wt%, less than 0.7 wt% and in certain embodiments, less than 0.5 wt% of a composition, where wt % is based on the total dry solids weight of the composition.
  • compositions provided by the present disclosure comprise at least one filler that is effective in reducing the specific gravity of the composition.
  • the specific gravity of a composition is from 0.8 to 1, 0.7 to 0.9, from 0.75 to 0.85, and in certain embodiments, is 0.8.
  • the specific gravity of a composition is less than about 0.9, less than about 0.8, less than about 0.75, less than about 0.7, less than about 0.65, less than about 0.6, and in certain embodiments, less than about 0.55.
  • a thiol-terminated sulfur-containing polymer including a combination of thiol-terminated sulfur-containing polymers comprises from about 50 wt% to about 90 wt% of a composition, from about 60 wt% to about 90 wt%, from about 70 wt% to about 90 wt%, and in certain embodiments, from about 80 wt% to about 90 wt% of the composition, where wt% is based on the total dry solids weight of the composition.
  • a thiol-terminated polythioether including a combination of thiol-terminated polythioethers comprises from about 50 wt% to about 90 wt % of a composition, from about 60 wt% to about 90 wt%, from about 70 wt% to about 90 wt%, and in certain embodiments, from about 80 wt% to about 90 wt% of the composition, where wt % is based on the total dry solids weight of the composition.
  • compositions provided by the present disclosure may be used, for example, in sealants, coatings, encapsulants, and potting compositions.
  • a sealant includes a composition capable of producing a film that has the ability to resist operational conditions, such as moisture and temperature, and at least partially block the transmission of materials, such as water, fuel, and other liquid and gases.
  • a coating composition includes a covering that is applied to the surface of a substrate to, for example, improve the properties of the substrate such as the appearance, adhesion, wettability, corrosion resistance, wear resistance, fuel resistance, and/or abrasion resistance.
  • a potting composition includes a material useful in an electronic assembly to provide resistance to shock and vibration and to exclude moisture and corrosive agents.
  • sealant compositions provided by the present disclosure are useful, e.g., as aerospace sealants and as linings for fuel tanks.
  • compositions such as sealants
  • multi-pack compositions such as two-pack compositions, wherein one package comprises one or more thiol-terminated polythioethers provided by the present disclosure and a second package comprises one or more polyfunctional sulfur-containing epoxies provided by the present disclosure.
  • Additives and/or other materials may be added to either package as desired or necessary. The two packages may be combined and mixed prior to use.
  • the pot life of the one or more mixed thiol-terminated polythioethers and epoxies is at least 30 minutes, at least 1 hour, at least 2 hours, and in certain embodiments, more than 2 hours, where pot life refers to the period of time the mixed composition remains suitable for use as a sealant after mixing.
  • compositions, including sealants, provided by the present disclosure may be applied to any of a variety of substrates.
  • substrates to which a composition may be applied include metals such as titanium, stainless steel, and aluminum, any of which may be anodized, primed, organic-coated or chromate-coated; epoxy; urethane; graphite; fiberglass composite; Kevlar ® ; acrylics; and polycarbonates.
  • compositions provided by the present disclosure may be applied to a coating on a substrate, such as a polyurethane coating.
  • compositions provided by the present disclosure may be applied directly onto the surface of a substrate or over an underlayer by any suitable coating process known to those of ordinary skill in the art.
  • methods for sealing an aperture utilizing a composition provided by the present disclosure comprise, for example, applying a composition provided by the present disclosure to a surface to seal an aperture, and curing the composition.
  • a method for sealing an aperture comprises applying a sealant composition provided by the present disclosure to defining surface of an aperture and curing the sealant, to provide a sealed aperture.
  • a composition may be cured under ambient conditions, where ambient conditions refers to a temperature from 20 °C to 25 °C, and atmospheric humidity. In certain embodiments, a composition may be cured under conditions encompassing a temperature from a 0°C to 100°C and humidity from 0% relative humidity to 100% relative humidity. In certain embodiments, a composition may be cured at a higher temperature such as at least 30 °C, at least 40 °C, and in certain embodiments, at least 50 °C. In certain embodiments, a composition may be cured at room temperature, e.g., 25 °C. In certain embodiments, a composition may be cured upon exposure to actinic radiation, such as ultraviolet radiation. As will also be appreciated, the methods may be used to seal apertures on aerospace vehicles including aircraft and aerospace vehicles.
  • the composition achieves a tack-free cure in less than about 2 hours, less than about 4 hours, less than about 6 hours, less than about 8 hours, and in certain embodiments, less than about 10 hours, at a temperature of less than about 200 °F.
  • curable compositions of the present disclosure develop adhesion strength within 24 hours to 30 hours, and 90% of full adhesion strength develops from 2 days to 3 days, following mixing and application to a surface.
  • full adhesion strength as well as other properties of cured compositions of the present disclosure becomes fully developed within 7 days following mixing and application of a curable composition to a surface.
  • Cured compositions disclosed herein exhibit properties acceptable for use in aerospace applications.
  • sealants used in aviation and aerospace applications exhibit the following properties: peel strength greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS) 3265B substrates determined under dry conditions, following immersion in JRF Type I for 7 days, and following immersion in a solution of 3% NaCl according to AMS 3265B test specifications; tensile strength between 300 pounds per square inch (psi) and 400 psi; tear strength greater than 50 pounds per linear inch (pli); elongation between 250% and 300%>; and hardness greater than 40 Durometer A.
  • AMS Aerospace Material Specification
  • compositions of the present disclosure used in aviation and aircraft applications exhibit a percent volume swell not greater than 25% following immersion for one week at 60 °C (140 °F) and ambient pressure in JRF Type I.
  • Other properties, ranges, and/or thresholds may be appropriate for other sealant applications.
  • compositions provided by the present disclosure are fuel-resistant.
  • fuel resistant means that a composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that exhibits a percent volume swell of not greater than 40%, in some cases not greater than 25%, in some cases not greater than 20%, in yet other cases not more than 10%, after immersion for one week at 140 °F (60 °C) and ambient pressure in Jet Reference Fluid (JRF) Type I according to methods similar to those described in ASTM D792 (American Society for Testing and Materials) or AMS 3269 (Aerospace Material Specification).
  • JRF Jet Reference Fluid
  • Jet Reference Fluid JRF Type I as employed for determination of fuel resistance, has the following composition: toluene: 28% ⁇ 1% by volume; cyclohexane (technical): 34% ⁇ 1% by volume; isooctane: 38% ⁇ 1% by volume; and tertiary dibutyl disulfide: 1% ⁇ 0.005% by volume (see AMS 2629, issued July 1, 1989, ⁇ 3.1.1 etc., available from SAE (Society of Automotive Engineers)).
  • compositions provided herein provide a cured product, such as a sealant, exhibiting a tensile elongation of at least 100% and a tensile strength of at least 400 psi when measured in accordance with the procedure described in AMS 3279, ⁇ 3.3.17.1, test procedure AS5127/1, ⁇ 7.7.
  • compositions provide a cured product, such as a sealant, that exhibits a lap shear strength of greater than 200 psi, such as at least 220 psi, at least 250 psi, and, in some cases, at least 400 psi, when measured according to the procedure described in SAE AS5127/1 paragraph 7.8.
  • a cured sealant comprising a composition provided by the present disclosure meets or exceeds the requirements for aerospace sealants as set forth in AMS 3277.
  • Apertures, including apertures of aerospace vehicles, sealed with compositions provided by the present disclosure are also disclosed.
  • a cured sealant provided by the present disclosure exhibits the following properties when cured for 2 days at room temperature, 1 day at 140 °F, and 1 day at 200 °F: a dry hardness of 49, a tensile strength of 428 psi, and an elongation of 266%; and after 7 days in JRF Type I, a hardness of 36, a tensile strength of 312 psi, and an elongation of 247%.
  • compositions provided by the present disclosure exhibit a Shore A hardness (following 7-day cure) greater than 10, greater than 20, greater than 30, and in certain embodiments, greater than 40; a tensile strength greater than 10 psi, greater than 100 psi, greater than 200 psi, and in certain embodiments, greater than 500 psi; an elongation greater than 100%), greater than 200%, greater than 500%, and in certain embodiments, greater than 1 ,000%>; and a swell following exposure to JRF Type I (7 days) less than 20%.
  • Embodiments provided by the present disclosure are further illustrated by reference to the following examples, which describe the synthesis, properties, and uses of certain adhesion promoting adducts and compositions comprising adhesion promoting adducts. It will be apparent to those skilled in the art that many modifications, both to materials, and methods, may be practiced without departing from the scope of the disclosure.
  • Permapol® P3.1E is a thiol-terminated polymer and the accelerator S-5304 is an epoxy compound, both commercially available from PRC-DeSoto, International, Inc., Sylmar, CA.
  • DABCO® 33-LV is an amine catalyst, commercially available from Air Products and Chemicals, Inc.
  • a sealant (Sealant 1) was prepared having the composition of Table 1. Table 1.
  • Permapol® P3.1E and the aminosilane adhesion promoting adduct were weighed in a mixing cup and mixed in Hauschild mixer for 30 seconds. CaC03 was added and mixed for 30 sec. The contents were hand-mixed and then mixed again in the Hauschild mixer for 30 seconds. Accelerator S-5304 was added, hand-mixed and mixed again with the Hauschild mixer for 30 seconds. Catalyst DABCO® 33-LV was added (3 drops from a plastic pipette) and the contents mixed. The cured sealant (24 hours at 140 °F) had a hardness of 35 (Shore A), and the percent cohesive failure for the tested surfaces is shown in Table 2.
  • a first sealant (Sealant 1) was prepared having the composition of Table
  • Permapol® 3 IE prepolymer and the amino-hydroquinone adhesion promoting adduct (1.46 g of -14% solution) were weighed in a mixing cup and mixed in Hauschild mixer for 30 seconds. CaC03 was added and mixed by hand and in the Hauschild mixer. Accelerator S-5304 was added and mixed. Catalyst DABCO® 33-LV was added (3 drops from a plastic pipette) and mixed.
  • a second sealant (Sealant 2) was prepared having the composition of
  • a sealant was prepared having the composition of Table 6. Table 6.
  • Adhesion specimens were cured for 5 days at room temperature followed by curing from 27 hours at 140 °F.
  • the percent cohesive failure of the cured sealant samples are shown in Table 7.
  • Permapol® P3.1E polymer (10 g, a thiol-terminated polymer, commercially available from PRC-DeSoto International, Sylmar, California ) and calcium carbonate (5.0 g) were mixed in Hauschild mixer for 30 seconds at 2300 rpm.
  • An accelerator S-5304 (2.6 g, an epoxy paste, commercially available from PRC-DeSoto International, Sylmar, California), and the catalyst triethylenediamine (0.08 g) were sequentially added and mixed. Samples were applied on various substrates and cured at room temperature for 24 hours followed by curing for 48 hours at 140 °F. The percent cohesive failure was measured by peeling the sample from the substrates. The results are shown in Table 8.
  • Titanium (per AMS-4911 spec) 0
  • HOPO interacts with AI4O6 as a bi-dentate ligand: i.e., carbonyl oxygen (in HOPO) binds to aluminum (in AI4O6) and the hydroxyl group (in HOPO) is hydrogen bonded with oxygen (in AI4O6).
  • a tri-dentate binding mode for BSP with AI4O6 was identified: two sulfonyl groups (in BSP) bind to two aluminum atoms (in AI4O6) in addition to the hydrogen bond between hydroxyl group (in BSP) and oxygen atom (in AI4O6).
  • BSP is not very electron donating (as shown by the low HOMO energy in Table 9), strong binding with AI4O6 with three coordination sites is nevertheless observed.
  • BSP functional group was shown to bind to aluminum oxide through tri-dentate mode, resulting in very strong interaction (adhesion). Unlike other strong binding ligands such as HOPO, BSP is difficult to oxidize and is expected to have good stability. Structures with binding motifs similar to that of BSP can also lead to strong binding toward aluminum oxide.
  • Similar methods may be used to identify other metal ligands appropriate for enhancing adhesion to a particular metal surface and that may be incorporated into the backbone of a prepolymer and/or provided as a terminal group of a prepolymer as described in the present disclosure.

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