sulfur-containing compound and composition

专利摘要:
sulfur-containing compound, composition, cured seal, opening sealed with a sealant and method for sealing an opening. sulfur-containing polymers comprising copolymerizable adhesion promoters and compositions including useful sealing compositions in aerospace applications are described which comprise sulfur-containing polymers containing copolymerizable adhesion promoters. in particular, polyethers and polysulfides incorporating copolymerizable adhesion promoters are described.
公开号:BR112014031821B1
申请号:R112014031821-2
申请日:2013-06-19
公开日:2021-02-23
发明作者:Raquel Keledjian；Bruce Virnelson；Renhe Lin
申请人:Prc-Desoto International, Inc；
IPC主号:

专利说明:

Technical field
[0001] The present invention relates to polymers in which the adhesion promoters are copolymerized in a sulfur-containing polymer backbone, and to compositions comprising the copolymerizable adhesion promoters which have improved surface adhesion. Sulfur-containing polymers incorporating copolymerizable adhesion promoters and compositions thereof are described. Background of the invention
[0002] Seals useful in aerospace and other applications must satisfy mechanical, chemical, and environmental requirements. Sealants can be applied to a variety of surfaces including metal surfaces, primary coatings, intermediate coatings, finish coatings, and aged coatings. Adhesion promoters are typically added to sealant formulations to improve the adhesion of various components to each other and to the surfaces to which the sealant is applied. Ways to provide improved adhesion while maintaining other advantageous properties of a seal are continually desired.
[0003] Sulfur-containing polymers such as polyethers and polysulfides are useful in aerospace applications. Examples of polyethers and polysulfides are described, for example, in North American publications Nos .: US 2005/0010003, US 2006/0270796, US 2007/0287810, US 2009/0326167, and US 2010/036063. Summary of the invention
[0004] Adhesion promoters copolymerizable directly in a main chain of sulfur-containing polymers ensure that the adhesion promoters are tightly coupled to the polymeric network, which form the structure of a cured seal. Sulfur-containing polymers comprising copolymerizable adhesion promoters and compositions comprising such polymers are also described.
[0005] In a first aspect, sulfur-containing compounds are provided having the structure of formula (1):
where: each R1 is independently selected from C2-6 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkiidyl, C5-8 heterocycloalkanediyl, and - [- (CHR3) sX-] q- (CHR3) r -; where: each R3 is independently selected from hydrogen and methyl; each X is independently selected from -O-, -S-, and -NR-, where r is selected from hydrogen and methyl; s is an integer from 2 to 6; q is an integer from 1 to 5; er is an integer from 2 to 10; each A 'independently represents a moiety formed by reacting a compound a with a thiol group, where compound A is a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion; B represents a nucleus of a valiant-z, a polyfunctional compound terminated in alkenyl B (-V) z, where: z is the sum of z1 and z2, and z is an integer from 3 to 6; z 'is an integer from 1 to 4; z2 is an integer from 2 to 5; and each -V is a portion comprising a terminal group that is reactive with a thiol group; and each -V'- represents a portion formed by reacting each -V with a thiol group.
[0006] In a second aspect, sulfur-containing compounds are provided comprising the reaction product of reagents comprising: (a) a polyfunctional compound having terminal groups that are reactive with the thiol groups; (b) a dithiol; and (c) a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion.
[0007] In a third aspect, compositions are provided comprising: (a) at least one sulfur-containing compound provided by the present description; (b) at least one thiol-terminated sulfur-containing polymer; and (c) at least one curing agent.
[0008] In a fourth aspect, the seals comprising at least one sulfur-containing compound provided by the present description are provided.
[0009] In a fifth aspect, openings sealed with a seal comprising at least one sulfur-containing compound provided by the present description are provided.
[0010] In a sixth aspect, the methods of sealing an opening are provided comprising: (a) applying a sealant comprising at least one sulfur-containing compound provided by the present invention to at least one surface defining an opening; (b) arranging the surfaces by defining the opening; and (c) curing the seal to provide a cured opening. Detailed description of the invention Definitions:
[0011] For the purposes of the description below, it should be understood that the embodiments provided by the present description may assume several alternative variations and sequences of steps, except where expressly specified to the contrary. In addition, in addition to the examples, or where otherwise indicated, all numbers expressing, for example, quantity of ingredients used in the specification and claims should be understood to be modified in all examples by the terms "about".
[0012] Consequently, unless otherwise indicated, the parameters represented in the following report and linked to the claims are approximations that may vary depending on the desired properties to be obtained. At least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of protection of claims, each numerical parameter must at least be constructed in light of the number of significant digits reported and through the ordinary application of routine techniques.
[0013] However, the numerical ranges and parameters representing the broad scope of protection of the embodiments provided by the present description are approximations, the numerical values representing the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains a certain error, necessarily resulting from the standard variation found in their respective test measures.
[0014] Furthermore, it should be understood that any numerical range mentioned here intends to include all the sub-ranges covered here. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the minimum quoted value of about 1 and the maximum quoted value of about 10, that is, having a minimum value of about 1 and the maximum value quoted of about 10, that is, having a minimum value equal to or greater than about 1 hey, maximum value equal to or less than about 10. Furthermore, in this order, the use of "or" means "and / or" unless otherwise specifically stated, also "and / or" may be explicitly used in certain examples.
[0015] A dash (“-“) that is not between two letters or symbols is used to indicate a point of attachment for a substituent or between two atoms. For example, CONH2 is attached to another chemical moiety through the carbon atom.
[0016] "Alcanodiila" refers to a di-radical of a saturated straight or branched chain acyclic hydrocarbon group, having, for example, from 1 to 18 carbon atoms (C1-6), from 1 to 4 atoms of carbon (C1-4) or 1-3 carbon atoms (C1-3). It can be appreciated that a branched alkanediyl has a minimum of three carbon atoms. In certain embodiments, the alkanediyl is C214 alkanediyl, C2-10 alkanediyl, C2-8 alkanediyl, C2-6 alkanediyl, C2-4 alkanediyl, and in certain embodiments, C2-3 alkanediyl. Examples of alkanediyl groups include methane-diyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl and iso-propane-1,2-diyl (for example, -CH2CH2CH2 - and - CH (CH3) CH2-), hexane-1,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane-1,7-diyl, octanum-1,8-diyl, nonane-1,9, decane-1, 10-diyl, dodecane-1,12-diyl, and the like.
[0017] "alkanocycloalkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanodiyl groups and one or more alkyl and / or alkanodiyl group, where cycloalkyl, cycloalkanodiyl, alkyl, and alkanodiyl are defined here. In certain embodiments, each cycloalkyl and / or cycloalkanodiyl group is C3-6, C5-6 and in certain embodiments, cyclohexyl or cyclohexanediyl. In certain embodiments, each alkyl and / or alkanodiyl group is C1-6, C1-4, C1-3, and in certain embodiments, methyl, methanodiyl, ethyl, or ethane-1,2-diyl. In certain embodiments, the C4-18 alkanocycloalkane, C4-16 alkanocycloalkane, C6-10 alkanocycloalkane group, and in certain embodiments, C6-9 alkanocycloalkane. Examples of alkanocycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.
[0018] "Alcanocycloalkanodiyl" refers to a di-radical of an alkanocycloalkane group. In certain embodiments, the alkanocycloalkanediyl group is alkanocycloalkanodiyl C4-18, alkanocycloalkanodiyl C4-16, alkanocycloalkanodiyl C4-8, alkanocycloalkodiyl C6-12, alkanocycloalkanodiyl in C6-10 and. Examples of alkanocycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.
[0019] The group "alkenyl" refers to a group (R) 2C = C (R) 2 or -RC = C (R) 2 where the alkenyl group is a germinal group and is attached to a large molecule. In such embodiments, each R can be selected from, for example, hydrogen and C1-3 alkyl. In certain embodiments, each R is hydrogen and an alkyl group having the structure CH = CH2.
[0020] "Alkoxy" refers to an -OR group where R is an alkyl as defined here. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. In certain embodiments, the alkoxy group is C1-8 alkoxy, C1-6 alkoxy, C1-4 alkoxy, and in certain embodiments, C1-3 alkoxy.
[0021] "Alkyl" refers to a mono-radical of a saturated straight or branched chain acyclic hydrocarbon group having, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 atoms carbon, from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms. In certain embodiments, the alkyl group is C2-6 alkyl, C2-4 alkyl, and in certain embodiments, C2-3 alkyl. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like. In certain embodiments, 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.
[0022] "Cycloalkanediyl" refers to a saturated diradical polycyclic or monocyclic hydrocarbon group. In certain embodiments, the cycloalkanodiyl group is C3-12 cycloalkanodiyl, C3-8 cycloalkanodiyl, C3-6 cycloalkanodiyl, and in certain embodiments, C5-6 cycloalkanodiyl. Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.
[0023] "Cycloalkyl" refers to a mono-radical group of saturated polycyclic or monocyclic hydrocarbons. In certain embodiments, the cycloalkyl group is C3-12 cycloalkyl, C3-8 cycloalkyl, C3-6 cycloalkyl, and in certain embodiments, C5-6 cycloalkyl.
[0024] "Heteroalkanediyl" refers to an alkanodiyl 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 heteroalkanodiyl, the heteroatom is selected from N and O.
[0025] A "Michael acceptor" refers to an activated alkene, such as an alkenyl group proximal to an electron removing 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 removing group. In certain embodiments, a Michael acceptor group is selected from a vinyl ketone, a vinyl sulfone, a quinone, an enamine, a satin, an aldimine, an oxazolidine, and an acrylate. Other examples of Michael acceptors are described in Mather et al., “Prog. Polym. Sci. ”, 2006, 31, 487-531, and include acrylate esters, acrylonitrile, acrylamide, maleimide, alkyl methacrylates, cyanoacrylates. Other Michael acceptors include vinyl ketones, aldehydes, α, β-unsaturated vinyl phosphonates, acrylonitrile, vinyl pyridines, certain azo compounds, β-keto acetylenes and acetylene esters. In certain embodiments, a Michael acceptor group is derived from a vinyl ketone and has the structure of the formula -S (O) 2-C (R) 2 = CH2, where each R is independently selected from hydrogen, fluorine, and C1-3 alkyl. In certain embodiments, each R is hydrogen. In certain embodiments, a Michael acceptor or Michael acceptor group does not cover acrylates. A "Michael acceptor compound" refers to a compound comprising at least one Michael acceptor. In certain embodiments, a Michael acceptor compound is divinyl sulfone, and a Michael acceptor group is vinylsulfonyl, for example, -S (O) 2-CH2 = CH2.
[0026] As used here, "polymer" refers to oligomers, homopolymers, and copolymers. Unless otherwise indicated, molecular weights are the average number of molecular weight for the polymeric materials indicated as "Mn" as determined, for example, through gel permeation chromatography using a polystyrene standard in a manner recognized in the art. .
[0027] "Substituted" refers to a group in which one or more hydrogen atoms are each independently replaced with the same or a different substituent. In certain embodiments, the substituent is selected from halogen, -S (O) 2OH, -S (O) 2, -SH, -SR where R is C1-6 alkyl, -COOH, -NO2, -NR2 where each R is independently selected from hydrogen and C1-3 alkyl, -CN, = O, C1-6 alkyl, -CF3, -OH, phenyl, C2-6 heteroalkyl, C5-6 heteroaryl, C1-6 alkoxy, and -COR where R is C1-6 alkyl. In certain embodiments, the substituent is chosen from -OH, -NH2, and C1-3 alkyl.
[0028] Reference is now made to certain embodiments of sulfur-containing compounds, adhesion promoters, polymers, compositions, and methods. The described embodiments are not intended to be limiting to the claims. On the contrary, the claims are intended to cover all alternatives, modifications, and equivalents. Adhesion promoters containing sulfur:
[0029] Adherence promoters by copolymerization directly to the main chain of the sulfur-containing polymer can improve the adhesion of a composition such as a sealing composition. It will be appreciated that the general concept can be applied to any adhesion promoter and to any polymer.
[0030] In certain embodiments, the adhesion promoters provided by the present description are copolymerized to the main chain of the sulfur-containing polymer such as a thiol-terminated sulfur-containing polymer, including, for example, thiol-terminated polyethers and thiol-terminated polysulfides.
[0031] In certain embodiments, an adhesion promoter is copolymerized in a thiol-terminated polythioether polymer. Examples of polythio functional thiol are described, for example, in U.S. Patent No. US 6,172,179. In certain embodiments, the functional polythio thiol comprises Permapol® P3.1E, available from PRC- DeSoto International Inc., Sylmar, CA.
[0032] In certain embodiments, an adhesion promoter is copolymerized in a polysulfide polymer. In certain embodiments, a polysulfide polymer can be any of the polymers described, for example, in U.S. Patent No. US 4,623,711.
[0033] In certain embodiments, an adhesion promoter useful for copolymerization in a polymeric backbone comprises a sulfur-containing compound having the structure of formula (1):
where: each R1 is independently selected from C2-6 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkiidyl, C5-8 heterocycloalkanediyl, and - [- (CHR3) sX-] q- (CHR3) r -; where: each R3 is independently selected from hydrogen and methyl; each X is independently selected from -O-, -S-, and -NR-, where r is selected from hydrogen and methyl; s is an integer from 2 to 6; q is an integer from 1 to 5; er is an integer from 2 to 10; each A 'independently represents a moiety formed by reacting a compound a with a thiol group, where compound A is a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion; B represents a nucleus of a valiant-z, a polyfunctional compound terminated in alkenyl B (-V) z, where: z is the sum of z1 and z2, and z is an integer from 3 to 6; z 'is an integer from 1 to 4; z2 is an integer from 2 to 5; and each -V is a portion comprising a terminal group that is reactive with a thiol group; and each -V'- represents a portion formed by reacting each -V with a thiol group.
The compounds of formula (1) comprise at least a portion of the terminal adhesion promoter and at least two terminal thiol groups. At least a portion of the adhesion promoter provides adhesion to the surface and / or other constituents of a formulation of which it is a part, and the terminal thiol groups react with a curing agent to form a polymeric network. Thus, in the compounds of formula (1), z2 is at least 2, and in certain embodiments, z2 is 2, 3, 4 and in certain embodiments z2 is 5. In certain embodiments, z1 is 4. In certain embodiments, a compound of formula (1) is trivalent, so that z is 3, in certain embodiments, a compound of formula (1) is tetravalent, so that z is 4, and in certain embodiments, z is 5, and in certain embodiments, z is 6.
[0035] In certain embodiments, R1 is selected from C2-6 alkanediyl and - [- (CHR3) s-X-] q- (CHR3) r-.
[0036] In certain embodiments, R1 is - [- (CHR3) s-X-] q- (CHR3) r-, and in certain embodiments, X is -O- and in certain embodiments, X is-S-.
[0037] In certain embodiments where R1 is - [- (CHR3) s- X-] q- (CHR3) r-, p is 2, r is 2, q is 1, and X is -S-; in certain embodiments, p is 2, q is 2, and X is -O-; and in certain embodiments, p is 2, 4 is 2, q is 2, and X is -O-.
[0038] In certain embodiments, where R1 is - [- (CHR3) s-X-] q- (CHR3) r-, each R3 is hydrogen, and in certain embodiments, at least one R3 is methyl.
[0039] In certain embodiments of a compound of formula (1), 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, and a Michael acceptor group . In certain embodiments of a compound of formula (1), the terminal group that is reactive with a thiol group in compound A is an alkenyl group, an isocyanate group, an epoxy group, and in certain embodiments, a Michael acceptor group.
[0040] In certain embodiments of a compound of formula (1), a terminal group that promotes adhesion is selected from a silane, a phosphonate, an amine, a carboxylic acid, and a phosphonic acid. In certain embodiments of a compound of formula (1), a terminal group that promotes adhesion is a silane group, a phosphonate group, an amine group, a carboxylic acid group, and in certain embodiments, a phosphonic acid group.
[0041] -V- is a moiety comprising a terminal group that is reactive with a thiol group. For example, in certain embodiments, -V is -R10-CH = CH2, where R10 is selected from C1-6 alkanediyl, substituted C1-6 alkanediyl, C1-6 heteroalkanediyl, and substituted C1-6 heteroalkanediyl. However, the structure of -V is not limited. In certain embodiments, each -V can be the same, and in certain embodiments, at least one -V can be different.
[0042] Each A 'independently represents a moiety formed by reacting a compound A with a thiol group, where compound A is a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion. As indicated above, groups that are reactive with thiol groups include alkenyl groups, isocyanate groups, epoxy groups, and Michael acceptor groups. Groups that promote adherence are well known in the art. Examples of groups that promote adhesion include silane groups, phosphonate groups, amine groups, including primary and secondary amines, carboxylic acid groups, and phosphonic acid groups.
[0043] In compounds of the formula (1), each A 'may be the same or, in certain embodiments, at least one A' may be different. For example, in certain embodiments, each A 'may comprise the same adhesion-promoting group, and in certain embodiments, at least one of the adhesion-promoting groups may be different.
[0044] In certain embodiments, the adhesion-promoting group may be a silane group, which may have the structure - Si (R4) y1 (OR5) y2 where y1 is selected from 0, 1, and 2; y2 is selected from 1, 2 and 3; and the sum of y1 and y2 is 3; each R4 is independently selected from C1-4 alkyl; and R5 is independently selected from C1-4 alkyl.
[0045] In certain embodiments, the adhesion-promoting group may be a phosphonate group, which may have the structure -P (= O) (OR6) 2 where each R6 is independently selected from C1-4 alkyl. In certain embodiments, an adhesion-promoting group may be a phosphonic acid group, which has the structure -P (= O) (OR6) 2 where each R6 is hydrogen.
[0046] In certain embodiments, an adhesion-promoting group can be a primary amine, and in certain embodiments, a secondary amine.
[0047] In certain embodiments, an adhesion-promoting group may be a carboxylic acid group.
[0048] In certain embodiments of A in which a terminal group that is reactive with a thiol group is an alkenyl group, A is selected from: (a) a compound of formula (2):
where: y1 is selected from 0, 1, and 2; y2 is selected from 1, 2, and 3; and the sum of y1 and y2 is 3; R4 is selected from a Covalent and C1-6 alkanodiyl bond; Each R5 is independently selected from C1-4 alkyl; and each R6 is independently selected from C1-4 alkyl; (b) a compound of the formula (3):
where: R7 is selected from a C1-6 alkanodiyl and covalent bond; and Each R8 is independently selected from C1-4 alkyl; (c) a compound of the formula (4):
where R9 is selected from C1-10 alkanediyl, substituted C1-10 alkanediyl, C1-10 heteroalkanediyl, and substituted C1-10 heteroalkanediyl; and (d) a compound of the formula (5):
where R10 is C1-6-alkanediyl
[0049] In certain embodiments, a group that is reactive with a thiol group is a Michael acceptor group. In certain embodiments, a Michael acceptor group comprises a portion in which an electron-removing group such as a ketone or a sulfone is proximal to a terminal alkenyl group. Examples of Michael acceptor groups include vinyl ketones, vinyl sulfones, quinones, enamines, aldimines, satinines, and acrylates. Other examples of electron removing groups include a hindered secondary amine group, a tertiary amine group, an aziridinyl group, an urea group, a carbamate group, a carbodiimide group, and a halogen group. Consequently, in said embodiment, compound A comprises a Michael acceptor group and a group that promotes adhesion.
[0050] In certain embodiments of a compound of formula (1), each -A 'is the same and is selected from formula (2a), formula (3a), formula (4a), and formula (5a):

[0051] Where each R4, R5, R6, R7, R8, R9 and R10 are comodefined for formulas (2) - (5).
[0052] In certain embodiments of a compound of formula (1), each -A 'is the same and is a portion of formula (2a), a portion of formula (3a), a portion of formula (4a), and in certain embodiments, a portion of the formula (5a).
[0053] In certain embodiments in which compound A comprises a Michael acceptor group, compound A comprises the reaction products of (a) a compound of the formula HS-R10-SD, where R10 is selected from C1-10 alkanediyl , substituted C1-10 alkanediyl, C1-10 heteroalkanediyl, and C1-10 heteroalkanediyl; and D comprises a terminal group that promotes adhesion; and (b) a compound having the terminal Michael acceptor group and a terminal group and a terminal group that is reactive with a thiol group. In certain embodiments, a terminal Michael acceptor group is a vinyl sulfone and a terminal group that is reactive with a thiol group selected from an alkenyl group and an epoxy group. In certain embodiments, compound A is divinyl sulfone.
[0054] In certain embodiments, a compound having a terminal Michael acceptor group and a terminal group that promotes adhesion has the formula CH2 = S (O) 2-CH2-S-R10-S-D. said compounds can be reacted with a polythiol, such as a trityl, a tetrathiol, a pentathiol, a hexathiol, or a combination of any of the above. The polythiols may have the structure B (-V) z where each -V is a moiety having a terminal thiol group and z is an integer from 3 to 6. Examples of suitable polythiols are described in publication No. US No. 2011/0319559 .
[0055] In certain embodiments of a compound of Formula (1), each -A 'is the same and is selected from formula (2b), formula (3b), formula (4b), and formula (5b):

[0056] Where each R4, R5, R6, R7, R8, R9 and R10 are co-defined for formulas (2) - (5).
[0057] In certain embodiments of a compound of formula (1), each -A 'is the same and is a portion of formula (2b), a portion of formula (3b), a portion of formula (4b), and in certain embodiments, a portion of the formula (5b). [0058] B represents a nucleus 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 compound is trialyl cyanide (TAC) where B has the structure;

[0059] And each -V has the structure -O-CH2-CH = CH2.
[0060] In certain embodiments, the 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. The polyfunctional compound B (-V) z in which z is at least 3 can be any of the polyfunctionalizing agents useful in polymer chemistry. Polyfunctionalizing agents having mixed functionality, that is, agents that include portions (typically separate portions), which react with both groups, thiol and vinyl, can also be employed. Other useful polyfunctionalizing agents include trivinyl trimethylolpropane ether, and the polythiols described in U.S. Pat. US 4,366,307, US 4,609,762, and US 5,225,472, each of which is incorporated by reference in its entirety. Combinations of polyfunctionalizing agents having the same terminal group as the thiol groups or allyl groups can also be used.
[0061] 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, or a Michael acceptor group. In certain embodiments, each -V is the same, and in certain embodiments, at least one -V is different. In certain embodiments, -V is selected from C3-8-1-yl alkene and C3-8-1-yl heteroalkene, and V 'is selected from C3-8 alkanediyl and C3-8 heteroalkanediyl. Reaction product:
[0062] In certain embodiments, a sulfur-containing adhesion promoter comprises the reagent reaction product comprising: (a) a polyfunctional sulfur-containing compound having terminal groups that are reactive with the thiol groups: (b) a dithiol; and (c) a compound having a terminal group that is reactive with a thiol group and a second terminal group that promotes adhesion. In certain embodiments of the reaction, the reaction product comprises one or more compounds of the formula (1).
[0063] In certain embodiments, 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 here.
[0064] In certain embodiments, of B (-V) z, each -V comprises a terminal alkenyl group.
[0065] In certain embodiments, a dithiol has the structure of formula (6):

[0066] Where:
[0067] R1 is selected from C2-6 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl, and - [- (CHR3) s-X-] q- (CHR3) r-; Where:
[0068] Each R3 is independently selected from hydrogen and methyl;
[0069] Each X is independently selected from - O-, -S-, and -NR-, where R is selected from hydrogen and methyl;
[0070] s is an integer from 2 to 6;
[0071] q is an integer from 1 to 5; and
[0072] r is an integer from 2 to 10.
[0073] In certain embodiments, R1 is - {- (CHR3) s-X-] q- (CHR3) r-.
[0074] In certain embodiments of a compound of formula (6), X is selected from -O-, and -S-, and thus - {- (CHR3) sX-] q- (CHR3) r- na formula (6) is - [(- CH2-] pO-] q-CH2) r- or - [(- CH2-] pS-] q-CH2) r-. In certain embodiments, p and r are the same, such as when p and r are both two.
[0075] In certain embodiments, R1 is selected from C2-6 alkanediyl and - [- (CHR3) s-X-] q- (CHR3) r-.
[0076] In certain embodiments R1 is - [- (CHR3) s-X-] q- (CHR3) r-, and in certain embodiments X is -O-, and in certain embodiments, X is -S-.
[0077] In certain embodiments, where R1 is - [- (CHR3) s- X-] q- (CHR3) 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 -O-, and in certain embodiments, p is 2, r is 2, q is 1, and X is -O-.
[0078] In certain embodiments, where R1 is - [- (CHR3) s- X-] q- (CHR3) r-, each R3 is hydrogen, and in certain embodiments, at least one R3 is methyl.
[0079] In certain embodiments of a compound of formula (1), each R1 is the same, and in certain embodiments, at least one R1 is different.
Examples of suitable dithols 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, 1,3-dimercapto-3-metibutane, dipentanedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl-substituted diethylsulfide, dimercaptodiethyl 1-dimethoxydene sulfide substituted with dimethoxyane, dimethylapetane substituted with dimethoxy , 5-dimercapto-3-oxapentane, and a combination of any of the above. A polythiol can have one or more pendant groups selected from a lower alkyl group (for example, C1-6), a lower alkoxy group, and a hydroxyl group. Suitable pendant alkyl groups include, for example, linear C1-6 alkyl, a branched C3-6 alkyl group, cyclopentyl, and cyclohexyl.
[0081] Other examples of suitable dithiols include dimercaptodiethylsulfide (DMDS) (in formula (6), R1 is - [- (CHR3) sX-] q- (CHR3) r-, where p is 2, r is 2, q is 1, and is -S-); dimercaptodioxaoctane (DMDO) (in formula (6) R1 is - [- (CH2-) p- X-] q- (CH2) r—, where p is 2, q is 2, r is 2, and X is -O -); and 1,5-dimercapto-3-oxapentane (in formula (6), R1 is - [- (CH2-) pX-] q- (CH2) r-, where p is 2, r is 2, q is 2, and is -O-). It is also possible to use dithiols that include both hetero atoms in the main carbon chain and pendant alkyl groups, such as methyl groups. Said compounds include, for example, methyl substituted DMDS, such as HS-CH2CH (CH3) -S-CH2CH2-SH, HS-CH (CH3) CH2-S-CH2CH2-SH and dimethyl substituted DMDS, such as HS- CH (CH3) -S-CHCH3CH2-SH and HS-CH (CH3) CH2-S-CH2CH (CH3) -SH.
[0082] In certain embodiments of a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion, the terminal group that is reactive with the thiol group is selected from an alkenyl group, a group isocyanate, an epoxy group, and a Michael acceptor group, and the terminal group that promotes adhesion is selected from a silane, a phosphonate, an amine, a carboxylic acid, and a phosphonic acid.
[0083] In certain embodiments, a compound having a first group that is reactive with a thiol group and a second group that promotes adhesion is a vinyl silane. In certain embodiments, a vinyl-silane group has the structure of formula (2):
where: y1 is selected from 0, 1, and 2; y2 is selected from 1, 2, and 3; and the sum of y1 and y2 is 3; R4 is selected from a Covalent and C1-6 alkanodiyl bond; Each R5 is independently selected from C1-4 alkyl; and each R6 is independently selected from C1-4 alkyl.
[0084] In certain embodiments, a vinyl silane is selected from trimethoxy (vinyl) silane, ethoxydimethoxy (vinyl) silane, dietoxy (methoxy) (vinyl) silane, triethoxy (vinyl) silane, and a combination of any of the above mentioned.
[0085] In certain embodiments, a compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion is a vinyl phosphonate. In certain embodiments, a vinyl phosphonate has the structure of formula (3)
where: R7 is selected from a C1-6 alkanodiyl and covalent bond; and Each R8 is independently selected from C1-4 alkyl
[0086] In certain embodiments, a vinyl-phosphonate is selected from vinylphosphonic acid, dimethyl-vinylphosphonate, ethyl-methylvinylphosphonate, diethyl-vinylphosphonate, and a combination of any of the above.
[0087] In certain embodiments, the compound that promotes adhesion having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion is a vinyl-amine. In certain embodiments, a vinyl amine has the structure of formula (4):
where R9 is selected from C1-10 alkanediyl, substituted C1-10 alkanediyl, C1-10 heteroalkanediyl, and substituted C1-10 heteroalkanediyl.
[0088] In certain embodiments, a vinyl amine comprises the reaction product of reagents comprising an epoxy vinyl and a diamine. In certain embodiments, epoxy vinyl has the structure of formula (7):

[0089] Where R11 is C1-6 alkanediyl. In certain embodiments, an epoxy vinyl is allyl-glycidyl ether. In certain embodiments, the diamine has the structure of formula (8):
Where R12 is C1-6 alkanediyl. In certain embodiments, a diamine is selected from N- (aminomethyl) methanediamine, N1- (2-aminoethyl) ethane-1,2-diamine, and a combination thereof.
[0090] In certain embodiments, the compound having a terminal group that is reactive with a thiol group and a terminal group that promotes adhesion is a vinyl carboxylic acid and has the structure of the formula (5):
Where R10 is C1-6-alkanediyl. In certain embodiments, a vinyl carboxylic acid is selected from but-3-enoic acid, pent-4-enoic acid, and hex-5-enoic acid.
[0091] In certain embodiments, the terminal group that is reactive with a thiol group is a Micheel acceptor group, and the terminal group that promotes adhesion is selected from a silane, a phosphonate, an amine, a carboxylic acid, and a phosphonic acid. In certain embodiments, the compound can be prepared by the reaction and (a) a thiol-terminated compound of the formula HS-RSD, where R is selected from C1-10 alkanediyl, substituted C1-10 alkanediyl, C1-10 heteroalkanediyl, and substituted heteroalkanediyl C1-10, and D comprises a group that promotes adhesion: with (b) a compound comprising a group that is reactive with a thiol group and a Michael acceptor group. In certain embodiments, a compound comprising a group that is reactive with a thiol group and a Michael acceptor group is a vinyl sulfone. In certain embodiments, a compound comprises a group that is reactive with a thiol group and a Michael acceptor group is divinyl sulfone.
[0092] In certain embodiments of a reaction to form a sulfur-containing compound, the polyfunctionalizing agent and dithiol can be reacted to form a thiol-terminated intermediate. As such, the molar proportions of the reagents are appropriately selected. For example, 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 can 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 can be selected to provide a polyfunctional compound having a desired average adhesion promoter functionality. For example, to obtain an average adhesion promoter functionality of about one, about one mole of the 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 is reactive with a thiol group. promotes adherence.
[0093] In sulfur-containing compounds comprising the adhesion-promoting groups provided by the present invention, the compounds are intended to comprise at least one terminal group that promotes the adhesion of at least two terminal thiol groups capable of reacting with a curing agent and thus be incorporated into the main chain of the polymeric network, for example, copolymerized. In certain embodiments, the sulfur-containing compound comprises, on average, one adhesion-promoting group, per molecule, and in certain embodiments, an average of two adhesion-promoting groups per molecule.
[0094] In certain embodiments, the sulfur-containing adhesion promoter comprises the reaction product of the reagents comprising TAC, DMDO, and a vinyl silane selected from trimethoxy (vinyl) silane, ethoxydimethoxy (vinyl) silane, dietoxy (methoxy) (vinyl) silane, and trietoxy (vinyl) silane.
[0095] In certain embodiments, a sulfur-containing adhesion promoter comprises the reaction product of reagents comprising TAC, DMDO, and a diamine selected from N- (aminomethyl) methanediamine and N1- (2-aminoethyl) ethane-1, 2-diamine. Compositions:
[0096] The sulfur-containing adhesion promoters provided by the present description can be used in compositions, such as compositions formulated as sealants, useful in the aerospace industry.
[0097] In certain embodiments, compositions such as sealants provided by the present description comprise (a) at least one sulfur-containing compound provided by the present description; (b) at least one thiol-terminated sulfur-containing polymer; and (c) at least one curing agent.
[0098] In certain embodiments, a thiol-containing sulfur-containing polymer is selected from a thiol-terminated polythioether, a thiol-terminated polysulfide, and a combination thereof.
[0099] In certain embodiments, a thiol-terminated sulfur-containing polymer comprises a thiol-terminated polythioether. A thiol-terminated polythioether may comprise a mixture of different polyethers and the polythioethers may have the same or a different functionality than thiol groups. In certain embodiments, thiol-terminated polythioether has an average functionality of 2 to 6, 2 to 4, 2 to 3, and in certain embodiments, 2.05 to 2.8. For example, a thiol-terminated polythioether can be selected from a polymer containing difunctional sulfur, a polymer containing trifunctional sulfur, and a combination thereof.
[0100] Examples of polythioethers with thiol functionality are described, for example, in U.S. Patent No. US 6,172,179. In certain embodiments, a polythioether with thiol functionality comprises Permapol® P3.1E available from PRC-DeSoto International Inc., Sylmar, Ca.
[0101] In certain embodiments, a thiol-functional polythioether comprises (a) a main chain comprising a structure having the formula (12):
where: (i) each R1 is independently selected from an alkanodiyl-n-C2-10 group, a branched C6-10 alkanodiyl group, a heterocyclic group, a - [(- CH2-) p-X0] q- ( CH2) r-, and a group - [(- CH2-) pX-] q- (CH2) r-, in which at least one -CH2- moiety is replaced with a methyl group; (ii) each R2 is independently selected from a C2-10 alkanediyl-n group, a C3-6 branched alkanodiyl group, a C6-8 cycloalkanodiyl group, a C6-14 alkanocycloalkanediyl group, a heterocyclic group, and a - [( -CH2-) pX -] - (CH2) r-; (iii) each X is independently selected from 0, S and a group -NR6-, in which R6 is selected from hydrogen and a methyl group; (iv) m ranges from 0 to 50; (v) n is an integer from 1 to 60; (vi) p is an integer from 2 to 6; (vii) q is an integer from 1 to 5; and (viii) r is an integer from 2 to 10.
[0102] In certain embodiments, a thiol-terminated polythioether is selected from a thiol-terminated polythioether of formula (13), a thiol-terminated polythioether of formula (13a), and combinations thereof:
where: each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkodiyl, C5-8 heterocycloalkanediyl, and - [(-CHR3-) sS-] q - (- CHR3 -) r-, 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 R3 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 R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl, and - [(- CHR3-) sX-] q - (- CHR3-) r-, where s, q, r, R3, 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; B represents a nucleus of a Z-valence, a polyfunctionalization agent terminated in vinyl B (-V) z, where: Z is an integer from 3 to 6; and -V is a portion comprising a group that is reactive with a thiol group; and Each -V'- represents a portion formed by reacting -V with a thiol group.
[0103] In certain embodiments, R1 in formula (13) and formula (13a) is - [(- CH2-) pX-] q- (CH2) r-, where p is 2, X is - O-, q is 2, R2 is ethanediyl, m is 2 and n is 9.
[0104] In certain embodiments of the formula (13) and the
formula (13a), R1 is selected from C2-6 alkanodiyl and - [- (CHR3) s — X—] q- (CHR3) r-.
[0105] In certain embodiments of formula (13) and formula (13a), R1 is - [- (CHR3) sX-] q- (CHR3) r-, and in certain embodiments, X is -O- and in certain embodiments embodiments, X is —S-.
[0106] In certain embodiments of formula (13) and formula (13a), where R1 is - [- (CHR3) sX-] q- (CHR3) 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 -O-; and in certain embodiments, p is 2, r is 2, q is 1, and X is -O-.
[0107] In certain embodiments of formula (13) and formula (13a), where R1 is - [- (CHR3) sX-] q- (CHR3) r-, each R3 is hydrogen, and in certain embodiments, at least least one R3 is methyl.
[0108] In certain embodiments of the compounds of formula (13) and formula (13a), each R1 is the same, and in certain embodiments, at least one R1 is different.
[0109] Various methods can be used to prepare such polyethers. Examples of suitable functional thiol polythioethers, and methods for their production, which are suitable for use in the compositions described herein, are described in U.S. Patent No. US 6,172,179, in column 2, line 29 to column 4, line 22; column 6, line 39 to column 10, line 50; and column 11, line 65 to column 12, line 22, the cited portions of this patent being incorporated herein by reference. Said polythioethers with thiol functionality can be difunctional, that is, linear polymers having two final thiol groups, or polyfunctional, i.e., branched polymers having three or more final thiol groups. Suitable polythioethers with functional thiol are commercially available, for example, as Permapol® P3.1E, from PRC-DeSoto International Inc., Sylmar, CA.
[0110] The appropriate polythioethers with thiol functionality can be produced by reacting a divinyl-ether or mixtures of divinyl-ethers with an excess of dithiol or a mixture of dithols. For example, dithols suitable for use in the preparation of such functional thiol polyethers include those having formula (6), other dithiols described herein, or combinations of any of the dithiols described herein.
[0111] Suitable divinyl ethers include, for example, divinyl ethers having the formula (14):

[0112] Where R2 in formula (14) is selected from a C2-6 alkanodiyl-n group, a C3-6 branched alkanodiyl group, a C6-8 cycloalkanodiyl group, a C6-10 alkanocycloalkany group, and - [( -CH2-) pO-] 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. In certain embodiments of a divinyl-ether of the formula (14), R2 is a C2-6 alkanodiyl-n group, a C3-6 branched alkanodiyl group, a C6-8 cycloalkanodiyl group, a C6-10 alkanocycloalkanediyl group, and in certain embodiments , - [(- CH2-) pO-] q - (- CH2-) r.
[0113] Suitable divinyl ethers include, for example, compounds having at least one oxyalkanediyl group, such as from 1 to 4 oxyalkanediyl groups, that is, compounds in which m in formula (24) is an integer ranging from 1 to 4. In certain embodiments, m in formula (14) is an integer ranging from 2 to 4. It is also possible to use mixtures of commercially available divinyl-ethers that are characterized by an unintegrated average value for the number of oxyalkanodiyl units per molecule. Thus, m in formula (14) can also be a rational numerical value 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.
[0114] Examples of suitable divinyl-ethers include, for example, divinyl-ether, ethylene glycol divinyl-ether (EG-DVE) (R2 in formula (14) is ethanediyl in is 1), butanodiyl divinyl-ether (BD -DVE) (R2 in formula (14) is butanediyl in is 1), hexanediol divinyl-ether (HD-DVE) (R2 in formula (14) is hexanediyl in is 1), diethylene glycol divinyl-ether (DEG- DVE) (R2 in formula (14) is ethanediyl in is 2), divinyl-ether in triethylene glycol (R2 in formula (14) is ethanediyl in is 3), divinyl-ether in tetraethylene glycol (R2 in formula (14) is ethanediyl in is 4), cyclohexanedimethanol divinyl-ether, polytetrahydrofuryl divinyl-ether, trivinyl ether monomers, such as trimethylolpropane trivinyl-ether, tetrafunctional ether monomers, such as tetravinyl ether or two more, and pentaeritrol ether or more as polyvinyl ether monomers. A polyvinyl ether can have one or more pendant groups selected from the alkyl group, hydroxyl groups, alkoxy groups, and amine groups.
[0115] In certain embodiments, the divinyl ethers in which R2 in formula (14) is branched alkanodiyl C3-6 can be prepared by reacting a polyhydroxy compound with acetylene. Examples of divinyl-ethers of this type include compounds in which R2 in formula (14) is an alkyl substituted methanodiyl group such as -CH (CH3) - (for example, a mixture of Pluriol® such as Pluriol®E-200-divinyl -ether (BASF corp., Parsippany, NJ), for which R2 in formula (14) (is ethanediyl and is 3.8) or an alkyl-substituted ethanediyl (for example, -CH2CH (CH3) - such as polymeric mixtures DPE including DPE-2 and DPE-3 (International Specialty Products, Wayen, NH)).
[0116] Other useful divinethers include compounds in which R2 in formula (14) is polytetrahydrofuryl (poly-THF) or polyoxyalkanediyl, such as those tending to average about 3 monomer units).
[0117] Two or more types of polyvinyl ether monomers of the formula (14) may be used. Thus, in certain embodiments, two dithiols of formula (6) and one polyvinyl ether monomer of formula (14), one dithiol of formula (6) and two polyvinyl ether monomers of formula (14), two dithiols of formula (6) and two divinyl ether monomers of the formula (14), and more than two compounds of one or both of the formulas, can be used to produce a variety of functional thiol polyethers.
[0118] In certain embodiments, a polyvinyl ether monomer comprises 20 to less than 50 mol percent of reagents used to prepare a functional polythio thiol and, in certain embodiments, from 30 to less than 50 mol percent.
[0119] In certain embodiments provided by the present description, the relative amounts of dithiols and divinyl-ether are selected to result in terminal thiol groups. In this way, a dithiol of formula (6) or a mixture of at least two different dithiols of formula (6), are reacted with one of a divinyl-ether of formula (14) or a mixture of at least two different divinyl-ethers of formula (14) 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.
[0120] The reaction between the compounds of dithiols and divinyl ethers can be catalyzed by a free radical catalyst. Suitable free radical catalysts include, for example, azo compounds, for example azobisnitrile 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 can be a free radical catalyst, an ionic catalyst, or an ultraviolet radiation. In certain embodiments, the catalyst does not comprise basic or acidic compounds, and does not produce acidic or basic compounds during decomposition. Examples of free radical catalysts include zo-type catalysts, 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). Examples of other free radical catalysts are alkyl peroxides, such as t-butyl peroxide. The reaction can also be carried out by irradiation with either ultraviolet light or without a portion of cationic photo-initiation.
[0121] The functional thiol polyethers provided by the present invention can be prepared by combining at least one compound of the formula (6) and at least one compound of the formula (14) followed by the addition of an appropriate catalyst, and carrying out the reaction in a temperature of 30 ° C to 120 ° C, such as 70 ° C to 90 ° C, for a period of 2 to 24 hours, such as 2 to 6 hours.
[0122] As discussed here, thiol-functional polythioethers may comprise a polyfunctional polythioether, that is, they may have an average functionality greater than 2.0. Polyfunctional thiol-terminated polythioethers include, for example, those having the structure of formula (15):

[0123] Where: (i) A comprises the structure of formula (15), (ii) B denotes a z-valent residue from a polyfunctionalizing agent; and (iii) z has an average value 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, it is an integer from 3 to 6.
[0124] Polyfunctionalizing agents suitable for use in the preparation of said polyfunctional thiol-functional polymers include trifunctionalizing agents, that is, compounds where z is 3. Suitable trifunctionalizing agents include, for example, trialyl cyanurate (TAC), 1,2,3-propanotritiol, tritols containing isocyanurate, and combinations thereof, as described in North American publication No. 2010/0010133, in paragraphs [0102] - [0105], the portion cited being incorporated herein by reference. Other useful polyfunctionalizing agents include trimethylolpropane trivinyl-ether, and the polythioles described in U.S. Pat. US 4,366,307; US 4,609,762; and US 5,225,472. Mixtures of polyfunctionalizing agents can also be used.
[0125] As a result, thiol-functional polyethers suitable for use in the embodiments provided by the present description can have a wide range of average functionality. For example, trifunctionalization agents can achieve an average functionality of 2.05 to 3.0, such as 2.1 to 2.6. The broadest ranges of medium functionality can be achieved through the use of tetrafunctional agents or polyfunctionalizing agents of greater functionality. Functionality can also be affected by factors such as stoichiometry, as should be understood by those skilled in the art.
[0126] Thiol-functional polythioethers having a functionality greater than 2.0 can be prepared in a similar manner to the difunctional thiol-functional polyethers described in North American publication No. US 2010/0010133. In certain embodiments, polyethers can be prepared by combining (i) one or more dithiols described herein, with (ii) one or more divinyl ethers described here, and (iiI) one or more polyfunctionalizing agents. The mixture can then be reacted, optionally in the presence of an appropriate catalyst, to achieve a thiol-functional polythioether having a functionality greater than 2.0.
[0127] Thus, in certain embodiments, a thiol-terminated polythether comprises the reaction product of reagents comprising: (a) a dithiol of formula (6): HS-R1-SH (6) where: R1 is selected from alkanodiyl C2-6, cycloalkanodiyl C6-8, alkanocycloalkanodiyl C6-10, heterocycloalkanodiyl C5-8, and - [- (CHR3) sX-] q- (CHR3) r-; where: Each R3 is independently selected from hydrogen and methyl; Each X is independently selected from -O-, -S-, -NH-, and - NR-, where R is selected from hydrogen and methyl; s is an integer from 2 to 6; q is an integer from 1 to 5; er is an integer from 2 to 10; and (b) a divinyl-ether of the formula (14):
where: Each R2 is independently selected from C1-10 alkanodiyl, C6-8 cycloalkanodiyl, C6-14 alkanocycloalkanodiyl, and - [(- CHR3-) sX-] q - (- CHR3) -) r-, where s, q, r, R3, and X are as defined above; m is an integer from 0 to 50; n is an integer from 1 to 60; ep is an integer from 2 to 6.
[0128] And, in certain embodiments, the reagents comprise (c) a polyfunctional compound such as a polyfunctional compound B (-V) z, where B, -V, and z are as defined herein.
[0129] The thiol-terminated polyethers provided by the present invention represent the thiol-terminated polyethers having a molecular weight distribution. In certain embodiments, the thiol-terminated polyethers useful in the compositions may have an average number of molecular weight ranging from 500 Daltons to 20,000 Daltons, in certain embodiments, from 2,000 Daltons to 5,000 Daltons and, in certain embodiments, from 3,000 Daltons to 4,000 Daltons . In certain embodiments, the thiol-terminated polyethers useful in the compositions provided by the present description have a polydispersity (Mw / Mn; average molecular weight / average number of molecular weight) ranging from 1 to 20, and in certain embodiments, from 1 to 5. The molecular weight distribution of the thiol-terminated polythioethers can be characterized by gel permeation chromatography.
[0130] In certain embodiments, a thiol-terminated sulfur-containing polymer comprises a thiol-terminated polysulfide.
[0131] As used here, the term "polysulfide" refers to a polymer that contains one or more disulfide bonds, that is, bonds - [SS] -, in the polymeric main chain and / or in the terminal or pendant positions on the chain polymeric. Often, a polysulfide polymer will have two or more sulfur-sulfur bonds. The appropriate polysulfides are commercially available from Akzo Nobel under the name Thioplast®. Thioplast® products are available in a wide range of molecular weight ranges, for example, less than 1. k100 to over 8,000, with the molecular weight being the average molecular weight in grams per mol. In certain embodiments, a polysulfide has an average molecular weight number of 1,000 to 4,000. The crosslink density of these products also varies, depending on the amount of crosslinking agent used. The -SH content, that is, mercaptan or thiol content, of these products may also vary. The content of mercaptan and the molecular weight of the polysulfide can affect the cure speed of the polymer, with the cure rate increasing with the molecular weight.
[0132] In certain embodiments, in addition to or in place of, a polysulfide as previously described, comprising a thiol-terminated polysulfide comprises a polymeric mixture containing: (a) from 90 mol percent to 25 mol percent of finished disulfide polymer in mercaptan of the formula HS (RSS) mR'SH; and (b) 10 mol percent to 75 mol percent polysulfide terminated in formal diethyl mercaptan of the formula HS (RSSS) nRSH, where R is -C2H4-O-CH2-O-C2H4-; R 'is a divalent member selected from alkyl of 2 to 12 carbon atoms; alkyl thioether of 4 to 20 carbon atoms, alkyl ether of 4 to 20 carbon atoms and one oxygen atom, alkyl ether of 4 to 20 carbon atoms and 2 to 4 oxygen atoms, each of which is separated the other through at least 2 carbon atoms; alicyclic from 6 to 12 carbon atoms, and lower aromatic alkyl; and the value of m and n is such that the polysulfide polymer terminated in formal diethyl mercaptan and the disulfide polymer terminated in mercaptan have an average molecular weight of 1,000 to 4,000, such as 1,000 to 2,500. Said polymeric mixtures are described in U.S. Patent No. US 4,523,711, in column 4, line 18, column 8, line 35, the cited portion of which is incorporated herein by reference. In some cases, R 'in the above formula is - CH2-CH2-; -C2H4-O-C2H4-; -C2H4-S-C2H4-; C2H4-O-C2H4-O-C2H4-; or - CH2-C6H4-CH2-.
[0133] In certain embodiments, a polysulfide comprises a thiol-terminated polysulfide such as that commercially available from Akzo Nobel under the name Thioplast® and from Toray under the name Thiokol®-LP.
[0134] A curing agent can be selected, which is reactive with the terminal groups of the sulfur-containing polymer and the sulfur-containing compound. In certain embodiments, a sulfur-containing polymer and a sulfur-containing compound provided by the present description comprise the same groups reactive with the curing agent. For example, in certain embodiments, both a sulfur-containing polymer and a sulfur-containing compound provided by the present description comprise reactive thiol groups, and the curing agent comprises reactive alkenyl groups, epoxy groups, isocyanate groups, or Michael acceptor groups.
[0135] In certain embodiments, a sulfur-containing compound provided by the present description may be present in an amount of 0.1% by weight to 15% by weight of a composition, such as 0.1 less than 5% by weight, 0.1 less than 2% by weight and in certain embodiments, 0.1 less than 1% by weight, based on the total dry weight of the composition.
[0136] In certain embodiments, the compounds provided by the present description comprise, in addition, to one or more sulfur-containing compounds provided by the present description, one or more additional adhesion promoters. One or more additional adhesion promoters can be present in an amount of 0.1% by weight to 15% by weight of a composition, such as 0.1 to less than 5% by weight, 0.1 to less than 2% by weight, and in certain embodiments, 0.1 to less than 1% by weight, based on the total dry weight of the composition. Examples of adhesion promoters include phenolics, such as phenolic Methylon® resin, and organosilanes, such as epoxy, mercapto or amino functional silanes, such as Silquest® A-187 and Silquest® A-1100. Other useful adhesion promoters are known in the art.
[0137] In certain embodiments, a composition provided by the present description 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 metallic substrate. As used herein, the term ethylenically unsaturated silane containing sulfur refers to a compound comprising, within the molecule, (i), at least one sulfur atom (S), (ii) at least one, in some cases at least two ethylenically unsaturated carbon-carbon bonds, such as a carbon-carbon double bond (C = C); and (iii) at least one silane group, -Si (-R) m (-OR) 3-m, where each R is independently selected from hydrogen, alkyl, cycloalkyl, aryl, and others, and is selected from from 0, 1 and 2. Examples of ethylenically unsaturated silanes are described in the North American publication NO. Us 2012/0040104, which is incorporated by reference.
[0138] In certain embodiments, an ethylenically unsaturated silane containing sulfur, which is suitable for use in a composition provided by the present description, comprises the reaction products of reagents comprising (i) a mercaptosilane, and (ii) a polyene. As used herein, the term mercaptosilane refers to a molecular compound that comprises, within the molecule, (i) at least one mercapto group (--SH), and (ii) at least one silane group. Suitable mercaptosilanes include, for example, those having an HS-R'-Si (-R) m (-OR) 3-m structure, where R and m are defined as by a silane group, and R 'is a divalent organic group .
[0139] Examples of mercaptosilanes, which are suitable for use in the preparation of ethylenically unsaturated sulfur-containing silanes include Y-mercaptopropyltrimethoxysilane, Y-mercaptopropyltriethoxysilane, Y-mercaptopropylmethydimethoxyethyl methanes, metaphysyl methanes, compounded, above.
[0140] In certain embodiments, a polyene used to prepare ethylenically unsaturated silanes containing sulfur comprises a trene, which refers to a compound containing three carbon-carbon double bonds, such as, for example, trialyl cyanide and trialyl isocyanurate.
[0141] In certain embodiments, a polyene comprises a triene, such as one or more of the trialyl compounds mentioned above, and a mercaptosilane and triene are reacted together in relative quantities so that the resulting reaction product theoretically comprises an average of at least two ethylenically unsaturated groups per molecule. In certain embodiments, an ethylenically unsaturated silane comprises the reaction product of Y-mercaptopropyltrimethoxysilane and trialyl-cyanutra.
[0142] In certain embodiments, compositions provided by the present description contain an essentially stoichiometric equivalent amount of thiol groups for the "eno" groups in order to obtain a cured seal having acceptable seal properties as described here during exposure of the composition to actinic radiation. As used here, "essentially stoichiometric equivalent" means that the number of thiol groups and "eno" groups present in the compositions differ by no more than 10% from each other, in some cases, by no more than 5% or, in in some cases, no more than 1% or no more than 0.1%. In some cases, the number of thiol groups and "eno" groups present in the composition are the same. In addition, as will be appreciated, the "eno" group source may include the ethylenically unsaturated silane itself (if used) as well as the other polyene included in the composition. In certain embodiments, an ethylenically unsaturated silane is present in an amount such that 0.1 to 30, such as 1 to 30, or in some cases, 10 to 25 percent of the total number of ethylenically unsaturated groups present in the composition are part of an ethylenically unsaturated silane molecule, based on the number of ethylenically unsaturated groups in the composition.
[0143] In certain embodiments, the methods provided by the present description comprise exposing an uncured seal composition to actinic radiation to provide a cured seal. In certain embodiments, particularly when the cured seal must be formed by exposing the previously described uncured seal compositions to UV radiation, the composition also comprises a photoinitiator. As will be appreciated by those skilled in the art, a photoinitiator absorbs ultraviolet radiation and transforms it into a radical that initiates polymerization. Photoinitiators are classified into two major groups based on a form of action, both one and both of which can be used in the compositions described here. Cleavage-type photoinitiators include aceotphenones, α-aminoalkylphenones, benzoyl ethers, benzoyloximes, acylphosphone oxides and bisacylphosphine oxides and mixtures thereof. Abstraction type photoinitiators include benzophenone, Michler's ketone, thioxanthone, anthraquinone, camforquinone, fluorine, ketocoumarin, and mixtures thereof.
[0144] Non-limiting examples of suitable photoinitiators include benzyl, benzoyl, beoin methyl ether, benzoyl isobutyl benzophenol ether, acetophenone, benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (N, N'-dimethylamino) benzophenone, diethoxyacetophenone, fluorenes, for example, the H-Nu series of initiators available from Spectra Group Ltd., 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylixanthone, α-aminoalkylphenone , for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, acylphosphine oxides, for example, 2,6-dimethylbenzyldiphenyl phosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzyldiphenylphosphine oxide, bisacylphosphine oxides, for example, bis (2,6-dimethioxybenzoyl oxide) - 2,4,4-trimethylpentylphosphine, bis (2,6-dimethylbenzoyl) oxide - 2,4,4-trimethylpentylphosphine, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine, and bis (2,6-dichlorobenzoyl) oxide -2,4,4-trimethylpentylphosphine, and combinations thereof.
[0145] In certain embodiments, a composition described here comprises 0.01 to 15 weight percent of photoinitiator or, in some embodiments, 0.01 to 10 weight percent or, in still other embodiments, 0.01 to 5 percent by weight of photoinitiator based on the total weight of the composition.
[0146] As described above, in certain embodiments, the methods comprise exposing an uncured seal composition to actinic radiation to provide a cured seal. In certain embodiments, a thiol-ene reaction, which forms the cured seal, can be carried out by irradiating an uncured composition comprising: (a) a thiol-terminated polythioether (such as any rum from those described above); (b) a sulfur-containing adhesion promoter, and (c) a polyene comprising a polyvinyl ether and / or a polyalkyl compound as described above, with actinic radiation. As used here, actinic radiation encompasses electron beam (EB) radiation, ultraviolet (UV) radiation, and visible light. In many cases, a thiol-ene radiation is effected by irradiating the composition with UV light and, in such cases, as mentioned above; the composition additionally and often comprises a photoinitiator, among other optional ingredients.
[0147] Ultraviolet radiation from any available source with emission of ultraviolet light having a wavelength ranging from, for example, 180 nm to 400 nm, can be used to initiate the thiol-ene reaction described above and thus form the cured sealant. Suitable sources of ultraviolet light are generally known and include, for example, mercury arcs, carbon arcs, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, plasma flow arcs swirl-flow and ultraviolet light emitting diodes. Certain embodiments of the compositions can exhibit an excellent degree of curing in air on exposure to relatively low energy in ultraviolet light.
[0148] In certain embodiments, the compositions provided by the present description can be cured using actinic radiation. Examples of compositions comprising polythioether curable compositions using actinic radiation are described in North American publication No. US 2012/0040104. Said compositions may include, in addition to a sulfur-containing compound (adhesion promoter) provided by the present description, and one or more sulfur-containing polymers such as a thiol-terminated sulfur-containing polymer, a polyene such as a polyvinyl ether including, for example, a polyvinyl ether of the formula (14).
[0149] Although the compositions provided by the present description are intended to be UV curable, it will be understood by those skilled in the art, other curing chemicals may also be employed with the use of one or more appropriate curing agents. The term curing agent refers to a compound that can be added to a composition provided by the present description to accelerate the curing or gelatinization of the composition. The curing or curing process can refer to the point at which the sealant achieves a curing hardness of 30 durometer when measured according to ASTM D2240. Any suitable curing agent can be used. In certain embodiments, a curing agent comprises an oxidizing agent that oxidizes the terminal mercaptan groups to form the disulfide bonds. Suitable oxidation curing agents include, for example, lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, dichromate and epoxy. Other suitable curing agents may contain reactive functional groups that are reactive with the functional groups in the sulfur-containing polymer described herein. Examples include polythiols such as polyethers; polyisocyanates such as isophorone, diisocyanate, and hexamethylene diisocyanate including mixtures thereof, and including isocyanurate derivatives thereof, and polyepoxides. Examples of polyepoxides include diepoxide hydantoin, bisphenol-A epoxides, bisphenol-F epoxides, Novolac type epoxides, aliphatic polyepoxides, and any of the epoxidized phenolic and unsaturated resins. The term polyepoxides refers to a compound having a 1,2-epoxy equivalent greater than one and includes monomers, oligomers and polymers.
[0150] In certain embodiments, the compositions provided by the present invention comprise one or more curing agents such as an iso-epoxy, an isocyanate, and a combination thereof.
[0151] The compositions provided by the present description can include one or more catalysts.
[0152] The compositions provided by the present description can comprise one or more different types of filler. The appropriate filler material includes those commonly known to those skilled in the art, including inorganic fillers, such as carbon black and calcium carbonate (CaCO3), silica, polymer powder, and lightweight filler material. Light weight cargo materials include, for example, those described in U.S. Patent No. US 6,525,168. In certain embodiments, a composition includes 5% by weight to 60% by weight of the filler or combination material and filler material, 10% by weight to 50% by weight, and in certain embodiments, from 20% by weight to 40% by weight, based on the total dry weight of the composition. The compositions provided by the present description can additionally include one or more dyes, thixotropic agents, accelerators, flame retardants, adhesion promoters, solvents, masking agents, or a combination of any of the above. As can be appreciated, the filler material and additives used in a composition can be selected to be compatible with each one, as well as the polymeric component, curing agent, and or catalyst.
[0153] In certain embodiments, the compositions provided by the present description include low density filler particles. As used here, 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. The appropriate light weight filler particles often fall into two categories - microspheres and amorphous particles. The specific gravity of microspheres can vary from 0.1 to 0.7 and include, for example, polystyrene foam, polyacrylate and polyolefin microspheres, and silica microspheres having particle size ranging from 5 to 100 microns and a specific gravity of 0.25 (Eccospheres®). Other examples include alumina / silica microspheres having a particle size in the range of 5 to 300 microns and a specific gravity of 0.7 (Fillite®), aluminum silicate microspheres having a specific gravity of about 0.45 to about 0.7 (Z-Light®), microspheres of polyvinylidene copolymer coated with calcium carbonate having a specific gravity of 0.13 (Dualite® 6001AE), and microspheres and acrylonitrile copolymer coated with calcium carbonate such as Dualite® E135 , having an average particle size of about 40 μm and a density of 0.135 g / cc (Henkel). The filler material suitable for decreasing the specific gravity of the composition includes, for example, hollow microspheres such as Expancel® microspheres (available from Akzo Nobel) or low density Dualite® polymer microspheres (available from Henkel). In certain embodiments, the compositions provided by the present description include light weight particles comprising an outer surface coated with a thin coating, such as those described in North American publication No. US 2010/0041839, in paragraphs [0016] to [0052) , the quoted portion of which is incorporated herein by reference.
[0154] In certain embodiments, a low density filler comprises less than 2% by weight of a composition, less than 1.5% by weight, less than 1.0% by weight, less than 0.8% by weight, less than 0.75% by weight, less than 0.7% by weight and in certain embodiments, less than 0.5% by weight of a composition, where the% by weight is based on the weight of the total dry solids of the composition.
[0155] In certain embodiments, the composition provided by the present description comprises at least one filler material that is effective in reducing the specific gravity of the composition. In certain embodiments, the specific gravity of a composition is 0.8 to 1.0.7 to 0.9, 0.75 to 0.85, and in certain embodiments, it is 0.8. In certain embodiments, 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.
[0156] In certain embodiments, a thiol-terminated sulfur-containing polymer including a thiol-terminated sulfur-containing polymer comprises from about 50% by weight to about 90% by weight of a composition, from about 60% by weight to about 90% by weight, from about 70% by weight to about 90% by weight, and in certain embodiments, from about 80% by weight to about 90% by weight of the composition, where% by weight is based on the total dry solids weight of the composition.
[0157] In certain embodiments, a thiol-terminated polythether including a combination of thiol-terminated polyethers comprises from about 50% by weight to about 90% by weight of a composition, from about 60% by weight to about 90% % by weight, from about 70% by weight to about 90% by weight, and in certain embodiments, from about 80% by weight to about 90% by weight of the composition, where% by weight is based on the weight of the total dry solids of the composition.
[0158] A composition can also include any number of additives as desired. Examples of suitable additives include plasticizers, pigments, surfactants, adhesion promoters, thixotropic agents, flame retardants, masking agents, and accelerators (such as amines, including 1,4-diaza-bicyclo [2,2,2] octane, DABCO®), and combinations of any of the above. When used, additives can be present in a composition in an amount ranging from, for example, from about 0% to 60 "by weight. In certain embodiments, additives can be present in a composition in an amount ranging from about 25% to 60% by weight. USES:
[0159] The compositions provided by the present description can be used, for example, in sealants, coatings, encapsulants, and potting compositions. A seal includes a composition capable of producing a film that has the ability to withstand operating conditions, such as humidity and temperature, and at least partially block the transmission of materials, such as water, fuel, and other liquids and gases. A composition and coating includes a coating that is applied to the surface of a substrate to, for example, improve the properties of the substrate such as appearance, adhesion, wettability, corrosion resistance, wear resistance, fuel resistance, and / or resistance abrasion. A pot composition includes a material useful in an electronic arrangement to provide resistance to shock and vibration and to exclude moisture and corrosive agents. In certain embodiments, the sealing compositions provided by the present description are useful, for example, as aerospace seals and as a coating for fuel tanks.
[0160] In certain embodiments, the compositions, such as seals, can be provided as multi-pack compositions, such as two-pack compositions, where a pack comprises one or more polythio-ethers terminated by the present description and a second pack comprises a or more epoxides containing polyfunctional sulfur provided by the present description. Additives and / or other materials can be added to the packaging when desired or necessary. The two packages can be combined and mixed before use. In certain embodiments, the service life of one or more thiol and epoxy-terminated polyethers is at least 30 minutes, at least 1 hour, at least 2 hours, and in certain embodiments, more than 2 hours, where the service life is refers to the length of time that the mixed composition remains suitable for use as a seal after mixing.
[0161] The compositions, including sealants, provided by the present description can be applied to any of a variety of substrates. Examples of substrates to which a composition can be applied include metals such as titanium, stainless steel, and aluminum, any of which can be anodized, primed, coated with organic or coated with chrome, epoxy, urethane, graphite, composite glass fiber , Kevlar®, acrylics, and polycarbonates. In certain embodiments, the compositions provided by the present description can be applied to a coating on a substrate, such as a polyurethane coating.
[0162] The compositions provided by the present description can be applied directly to the surface of a substrate or over an sublayer through any suitable coating process known to those skilled in the art.
[0163] The time to form a viable seal using curable compositions of the present description may depend on several factors as can be appreciated by those skilled in the art, and as defined by the requirements of applicable standards and specifications. In general, the curable compositions of the present description develop adhesion resistance within 24 hours to 30 hours, and 90% of the total adhesion resistance is developed from 2 days to 3 days, after mixing and application to a surface. In general, the total adhesion resistance as well as other properties of cured compositions of the present description becomes fully developed within 7 days after mixing and applying a curable composition to the surface.
[0164] Cured compositions such as cured sealants have acceptable properties for use in aerospace applications. In general, it is desirable that seals used in aviation and aerospace applications have the following properties: peel strength greater than 20 pounds per linear inch (pli) on substrates with the Aerospace Material Specification (AMS) 3265B determined under conditions dried, after immersion in JRF for 7 days, and after immersion in a 3% NaCl solution according to the specifications of the AMS 3265B test; 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 durometers A. These and other properties of the cured sealant suitable for application in aviation and aerospace applications are described in AMS 3265B, all of which are incorporated herein by reference. It is also desirable that when cured, the curable compositions of the present description used in aviation and aerospace applications have an optimum percentage volume not greater than 25% after immersion for one week at 60 ° C (140 ° F) and ambient pressure in JRF type 1. Other properties, ranges, and / or limits may be appropriate for other sealing applications.
[0165] In certain embodiments, the compositions provided by the present description are so resistant to fuel. As used here, the term “fuel resistant” means that a composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, which has an optimum percentage volume not greater than 40% in some cases not greater than 25%, in some cases, not greater than 20%, yet in other cases not greater than 10%, after immersion for one week at 140 ° F (60 ° C) and ambient pressure in Rapid Reference Fluid (JRF ) type I according to methods similar to those described in ASTM D792 (American Society for Testing and Materials) or AMS 3269 (Aerospae Material Specification). "Jet Reference Fluid JRF Type I", (Rapid Reference Fluid Type I), as an employee for determining 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 2, 1980; § 3.1.1, available from SAE (Society of Automotive Engineers)).
[0166] In certain embodiments, the compositions provide a cured product, such as a sealant, showing an elongation of at least 100% and a tensile strength of at least 400 psi when measured according to the procedure described in AMS 3279, § 3.3.17.1, test procedure AS5127 / 1, § 7.7.
[0167] In certain embodiments, the compositions provide a cured product, such as a sealant, that has a shear strength of coverage greater than 200 psi in some cases at least 400 psi when measured according to the procedure described in SAE AS5127 / 1, paragraph 7.8.
[0168] In certain embodiments, the compositions provided by the present invention provide a cured seal, having a shear strength of> 200 psi, such as at least 220 psi, or in certain embodiments, at least 250 psi, when measured accordingly. with paragraph 7.8 of As 5127/1.
[0169] In certain embodiments, a cured seal comprising a composition provided by the present description meets or exceeds the requirements for aerospace seals as shown in AMS 3277.
[0170] The curable compositions of the present description can have a Tg when cured of -55 ° C or less, in certain embodiments, -60 ° C or less, and in certain embodiments -65 ° C or less. The glass transition temperature, Tg can be measured using differential scanning calorimetry.
[0171] In addition, methods are provided for sealing an opening using a composition provided by the present description. These methods comprise, for example, applying a composition provided by the present description such as a sealant for a surface to seal an opening, and to cure the composition. In certain embodiments, a method of sealing an opening comprises (a) applying a sealing composition provided by the present description to one or more surfaces defining an opening, (b) arranging the surfaces defining the opening, and (c) curing the seal, to provide a sealed opening.
[0172] In certain embodiments, a composition can be cured under ambient conditions, when ambient conditions refer to a temperature of 20 ° C to 25 ° C. In certain embodiments, a composition can be cured under conditions ranging from 0 ° C to 100 ° C. In certain embodiments, a composition can 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 can be cured at room temperature, for example, 25 ° C. In certain embodiments, a composition can be cured during exposure to actinic radiation such as ultraviolet radiation. As will be appreciated, the methods can be used to seal openings in aerospace vehicles including aircraft and space vehicles.
[0173] Openings, including openings for space vehicles, sealed with compositions provided by the present description are also described. EXAMPLES
[0174] Embodiments provided by the present description are further illustrated by reference in the following examples, which describe the synthesis, properties, and uses of certain sulfur-containing compounds and compositions comprising the sulfur-containing compounds. It will be apparent to those skilled in the art that many modifications, both materials, and methods, can be practiced without departing from the scope of protection of the invention.

[0175] In a 300 mL round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 98 g (0.394 mol) of trialilcianuarto (TAC) and 215 g of 1 , 8-dimercapto-3,6-dioxaoctane (DMDO) were loaded, and the mixture stirred at room temperature for 20 minutes. The mixture was then heated to 70 ° C, and 100 mg of Vazo®-67 (Dupont) was added. The reaction mixture was maintained at 70 ° C for 8 hours to provide the thiol-terminated intermediate. The progress of the reaction was monitored by determining mercaptan equivalent weight (MEW). The final MEW was 297, and the material had a viscosity of 20 poise at 25 ° C, spindle # 6 at 50 rpm, measured using a CAP2000 viscometer.
[0176] In a 300 mL round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 99 g (0.374 mol) of thiol A-terminated intermediate was added. Then, 18 g of (0.123 mol) vinyltrimethoxysilane (Silquest® A-171, Momentive Performance Materials) was slowly added to the flask. The reaction was stirred until the temperature stabilized. After the temperature was stabilized, the reaction temperature was adjusted to 70 ° C and 100 mg of Vazo®-67 (Dupont) was added. The progress of the reaction was monitored using MEW determination. The reaction was completed in 12 hours to provide the sulfur-containing compound 1 with a final MEW of 431. Example 2:

[0177] In a 300 mL round-bottom flask, with 3-necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 58 g (0.218 mol) of thiol A-terminated intermediate from Examples 1 and 7 , 8 g of vinyl phosphonic acid (VPA) was added at 18 ° C. After addition, there was a small exotherm at 21 ° C. The reaction temperature was adjusted to 65 ° C and 75 mg of Vazo®-67 (Dupont) was added. The reaction was stirred for 6 hours. The reaction was restarted again after adjustment for 17 hours at room temperature and 70 mg of Vazo®-67 was added. After stirring for an additional 4 hours at elevated temperature, the reaction was completed. The final MEW of the sulfur-containing compound was 436. Example 3:

[0178] In a 300 mL round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen input (N2), 36 g (0.127 mol) of thiol A-terminated intermediate from Example 1 and 5.7 g of phosphonic vinyl methyl ester (VPA) were added at 18 ° C. After addition, there was a small exotherm at 21 ° C. The reaction temperature was adjusted to 100 ° C and 171 mg of Vazo®-67 was added. The reaction was stirred for 14 hours. The final MEW of the sulfur-containing compound 3 was 456. Example 4:

[0179] In a 300 ml round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 49 g (0.476 mol) of diethylenetriamine, 54 g (0.475 mol) of allylglycidol ether, and 43 g (0.714 mol) of isopropyl alcohol (IPA) were added at room temperature and stirred for 10 minutes. The reaction temperature was then adjusted to 64 ° C and after 10 minutes it increased to 120 ° C. The reaction was removed from the heat source while stirring. The reaction was monitored by determining the weight of epoxide equivalent (EEW). When the EEW reached 5412, 94% of the epoxide was consumed and the reaction was stopped to provide 1- (allyloxy) -3- (2- (2-aminoethylamino) ethylamino) propane-2-ol. The IPA was removed by rotary evaporation.
[0180] In a 300 mL round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 5 g (0.026 mol) of 1- (allyloxy) -3- ( 2- (2-aminoethylamino) ethylamino) propane-2-ol and 22.48 g (0.026 mol0 of thiol-terminated intermediate A of Example 1, and 100 mg of Vazo®-67 were added. The reaction temperature was adjusted to 80 ° C and the reaction was monitored by MEW, after 2 hours, the reaction was completed and the final MEW of the sulfur-containing compound 4 was 549. Example 5:

[0181] In a 300 mL round-bottom flask, with 3 necks fitted with a thermal probe, mechanical stirrer, and nitrogen (N2) inlet, 6.3 g (0.062 mol) of aminopropylvinyleter and 53.5 g ( 0.069 mol) of the thiol-terminated intermediate a of Example 1 were added. The reaction temperature was adjusted to 80 ° C and 50 mg of Vazo®-67 was added. The reaction was monitored by MEW. After two hours of reaction MEW it was 445, indicating that about one third of the mercaptan groups were reacted and the reaction was considered complete. Viscosity was 350 poise with # 6 spindle, 50 rpm, measured using a CAP2000 viscometer. Example 6: Comparative Composition 1
[0182] The components of comparative composition 1 are shown in table 1. Table 1Comparative composition 1
Silane is 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane; **% by weight based on the total solids weight of the composition. § thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0183] The mixture was carried out in a 60 gram plastic container with a lid. The thiol-terminated polythioether, divinyl-ether triethylene glycol (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil), and 3- (N-styrylmethyl-2-aminoethylamino ) propyltrimethoxysilane (Gelest, Morrisville, PA) was added to the 60 gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The container was opened, Irgacure® 2022 (BASF) was added, and the container was placed in a mixed speed and the composition mixed for 1 minute at 2,300 rpm. Example 7: Composition 2
[0184] The components of composition 2 are shown in table 2. Table 2Composition 2
* Silane is 3- (N-styrylmethyl-2-aminoethylamino) propyl-trimethoxysilane; **% by weight based on the total solids weight of the composition. § thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0185] The mixture was carried out in a 60 gram plastic container with a lid. The thiol-terminated polythioether, the sulfur-containing adhesion promoter 1 of Example 1, triethylene glycol divinyl ether (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil ), and 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane (Gelest, Morrisville, PA) were added to the 60 gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The vessel was opened, Irgacure® 2022 (BASF) added, and the composition mixed for 1 minute at 2,300 rpm. Example 8 - Composition 3:
[0186] The components of composition 3 are illustrated in Table 3. Table 3 Composition 3
* Silane is 3- (N-styrylmethyl-2-aminoethylamino) propyl-trimethoxysilane; **% by weight based on the total solids weight of the composition. § thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0187] The mixture was carried out in a 60-gram plastic container with a lid. The thiol-terminated polythioether, the sulfur-containing adhesion promoter 2 of Example 2, triethylene glycol divinyl ether (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil ), and 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane (Gelest, Morrisville, PA) were added to the 60 gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The vessel was opened, Irgacure® 2022 (BASF) added, and the composition mixed for 1 minute at 2,300 rpm. Example 9 - Composition 4:
[0188] The components of composition 4 are shown in table 4. Table 4 Composition 4
1 Silane is 3- (N-styrylmethyl-2-aminoethylamino) propyl-trimethoxysilane; 2 *% by weight based on the total solids weight of the composition. § thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0189] The mixing was carried out in a 60-gram plastic container with a lid. The thiol-terminated polythioether, the sulfur-containing adhesion promoter 3 of Example 3, triethylene glycol divinyl ether (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil ), and 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane (Gelest, Morrisville, PA), Silquest A-1120, and silica were added to the 60-gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The vessel was opened, Irgacure® 2022 (BASF) added, and the composition mixed for 1 minute at 2,300 rpm. Example 10 - Composition 5
[0190] The components of composition 5 are shown in Table 5.Table 5Composition 5
§ thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0191] The mixture was carried out in a 60-gram plastic container with a lid. The thiol-terminated polythioether, the sulfur-containing adhesion promoter 4 of Example 4, triethylene glycol divinyl ether (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil ), were added to the 60 gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The vessel was opened, Irgacure® 2022 (BASF) added, and the composition mixed for 1 minute at 2,300 rpm. Example 11 - Composition 6
[0192] The components of composition 6 are illustrated in Table 6. Table 6Composition 6
§ thiol-terminated polyethers of the type described in U.S. Patent No. US 6,172,179, average thiol functionality: 2.05-2.95, commercially available from PRC-DeSoto International, Inc., Sylmar, CA.
[0193] The mixture was carried out in a 60 gram plastic container with a lid. The thiol-terminated polythioether, the sulfur-containing adhesion promoter 5 of Example 5, triethylene glycol divinyl ether (TEG-DVE), the adduct described in Example 12 of North American publication No. US 2012/0040104 (TAC-Sil ), were added to the 60 gram container. The container was placed in a high speed mixer (DAC 600 FVZ) and mixed for 30 seconds at 2,300 rpm. The vessel was opened, Irgacure® 2022 (BASF) added, and the composition mixed for 1 minute at 2,300 rpm. Example 12 - Measure of adherence
[0194] The mixed compositions of Examples 6-8, and 11 were individually poured over an anodized aluminum pan (Mil-227725), and placed under UV light for 90 seconds, after which time the compositions were cured to an sticky-free solid. The compositions were cured using a Phoseon Firelfly curing unit, available from Phoseon Technology, Hillsboro, Oregon.
[0195] The cured pans were kept in ambient conditions for a predetermined number of days, after this time, adherence was measured as a percentage of cohesive failure. The adhesion scale was varied from 0 to 5 was marked in each test, with a value of 5 being 100% of cohesive failure and a value of 0 being 100% of adhesive failure. (Note that the adhesion test method is not a standard test).
[0196] The adhesion of the cured composition is illustrated in table 7.Table 7Adhesion of compositions for anodized aluminum pots

[0197] The results demonstrated that compositions comprising the adhesion promoters containing copolymerizable sulfur provided by the present invention show improved adhesion to anodized aluminum substrates compared to similar compositions without a copolymerizable sulfur containing adhesion promoter.
[0198] Finally, it should be noted that there are alternative ways of implementing the embodiments described here. Consequently, the present embodiment should be considered as illustrative and not restrictive. In addition, the claims are not limited to the details given here, and are entitled to their full and equivalent scope of protection.

权利要求:
Claims (11)
[0001]
1. Sulfur-containing compound, characterized by the fact that it has the structure of formula (1):
[0002]
Sulfur-containing compound according to claim 1, characterized in that the group that is reactive with a thiol group in compound A is selected from an alkenyl group, an isocyanate group, and an epoxy group.
[0003]
3. Sulfur-containing compound according to claim 1, characterized in that A is selected from: (a) a compound of formula (2):
[0004]
4. Sulfur-containing compound according to claim 1, characterized in that A is a compound comprising a Michael acceptor and a group that promotes adhesion.
[0005]
5. Composition, characterized by the fact that it comprises: at least one sulfur-containing compound as defined in claim 1; at least one thiol-terminated sulfur-containing polymer; and at least one curing agent.
[0006]
6. Composition according to claim 5, characterized in that at least one thiol-terminated sulfur-containing polymer is selected from a thiol-terminated polythioether and a thiol-terminated polysulfide.
[0007]
7. Composition according to claim 5, characterized in that at least one thiol-terminated sulfur-containing polymer is selected from the thiol-terminated polythioether of formula (13), a thiol-terminated polythioether of formula (13a), and a combination thereof:
[0008]
8. Composition according to claim 5, characterized in that at least one curing agent is selected from an iso-epoxy and an isocyanate, or the curing agent comprises reactive alkenyl groups, epoxy groups, isocyanate groups, or accepting groups of Michael.
[0009]
Composition according to claim 5, characterized in that the composition is curable by actinic radiation and comprises a polyene, preferably a polyvinylether.
[0010]
10. Composition according to claim 5, characterized by the fact that it comprises at least a second adhesion compound.
[0011]
11. Composition according to claim 5, characterized by the fact that it is formulated as a sealant.

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US20130344287A1|2013-12-26|

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JP2018090614A|2018-06-14|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2021-01-12| B09A| Decision: intention to grant|

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2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/529,183|2012-06-21|

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US13/529,183|US8513339B1|2012-06-21|2012-06-21|Copolymerizable sulfur-containing adhesion promoters and compositions thereof|

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PCT/US2013/046471|WO2013192266A2|2012-06-21|2013-06-19|Copolymerizable sulfur-containing adhesion promoters and compositions thereof|

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