JP6436988B2 - Metal-ligand-containing prepolymer, synthesis method thereof, and composition thereof - Google Patents

Description

  This application is a continuation-in-part of U.S. Patent Application No. 13 / 923,903, filed on June 21, 2013, and U.S. Patent Application No. 13 / 923,941 filed on June 21, 2013. And a continuation-in-part of US patent application Ser. No. 13 / 833,827 filed Mar. 13, 2013, each of which is incorporated by reference.

TECHNICAL FIELD The present disclosure relates to metal ligand-containing prepolymers, compositions containing metal ligand-containing prepolymers, methods for synthesizing metal ligand-containing prepolymers, and the use of metal ligand-containing prepolymers in aerospace sealant applications. Metal ligand-containing prepolymers include metal ligands such as bis (sulfonyl) alkanol, acetylacetonate, or hydroxypyridinone groups that are incorporated into a prepolymer backbone such as, for example, a polythioether prepolymer or a polysulfide prepolymer.

  Sealants useful for aerospace and other applications must meet stringent mechanical, chemical, and environmental requirements. For example, aerospace sealants desirably function over a temperature range of about −67 ° F. to about 360 ° F. and exhibit fuel oil resistance. Bis (sulfonyl) alkanol groups incorporated into the main chain and / or present as terminal groups, as disclosed in US patent application 13 / 923,903 and US patent application 13 / 923,941 Sealants formed using polythioether prepolymers having an improved adhesion to metal surfaces and meet other performance requirements for aerospace sealants.

  Aerospace vehicles often include lightweight surfaces made of aluminum and titanium alloys. Previous work by the inventors has shown that by using prepolymers with bis (sulfonyl) alkanol moieties incorporated into the prepolymer backbone, compositions with improved adhesion to these surfaces can be realized. . This work will be expanded to include other metal ligands, providing additional opportunities to enhance surface adhesion to aerospace and other surfaces.

  Sulfur-containing prepolymers with improved adhesion to metal surfaces and meeting other performance requirements for use in aerospace and other applications are desired.

  In a first aspect, a metal ligand-containing prepolymer is provided that includes a metal ligand incorporated into the prepolymer backbone.

In a second embodiment, a thiol-terminated metal ligand-containing polythioether comprising:
(A) The thiol-terminated polythioether of formula (18a), the thiol-terminated polythioether of formula (18b), or a combination thereof HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) ^{_{m - (CH 2) 2 -S}} -R 1 -] n -SH (18a)
{HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SV′—} _z B (18b )
(Where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s —. X—] _q — (— CHR ³ —) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a terminal thiol group,
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated polythioether comprising:
(B) a reaction product of a reactant comprising a metal chelator R ⁹ -LR ⁹ , wherein each R ⁹ independently contains a terminal group that reacts with a thiol and -L- contains a metal ligand. A thiol-terminated metal ligand-containing polythioether is provided.

In a third embodiment, a thiol-terminated metal ligand-containing polythioether prepolymer comprising:
(A) A thiol-terminated metal ligand-containing polythioether of formula (29a), a thiol-terminated metal ligand-containing polythioether of formula (29b), or a combination thereof HA-[-R ^{9 '} -LR ^9' -A -] _N -H (29a)
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently a formula (12)
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the core of the z-valent alkenyl-terminated polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6;
Each V is a group containing a terminal alkenyl group;
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated metal ligand-containing polythioether comprising:
(B) A thiol-terminated metal ligand-containing polythioether prepolymer comprising a reaction product of a reactant comprising a polyalkenyl compound is provided.

In a fourth embodiment, a process for preparing a thiol-terminated metal ligand-containing polythioether of formula (29a), wherein the thiol-terminated polythioether (N + 1) mole of formula (18a) is converted to a metal chelator R ⁹ -LR ⁹ A method is provided comprising the step of reacting with (N) moles:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently a formula (12)
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ includes hydrogen or methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6).

In a fifth embodiment, a process for preparing a thiol-terminated metal ligand-containing polythioether of formula (29b), wherein thiol-terminated metal ligand-containing polythioether of formula (29a) is converted to 1 mol of polyfunctionalizing agent. A method is provided that comprises reacting with B {V} _z :
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently a formula (12)
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —;
Where R ⁵ includes hydrogen or methyl,
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a terminal thiol group,
Each -V'- is a group derived from the reaction of -V and a thiol).

  In a sixth aspect, a composition comprising a metal ligand-containing prepolymer is provided.

  In a seventh aspect, a cured sealant is provided that includes a composition comprising a metal ligand-containing prepolymer.

It is a table | surface which shows the calculated value of the interaction energy of a ligand and aluminum (III) surface as described in Example 4. FIG.

  Several embodiments of the composition and method are described below. The disclosed embodiments are not intended to limit the scope of the claims. On the other hand, the claims are intended to cover all alternatives, modifications, and equivalents.

DETAILED DESCRIPTION Definitions For purposes of detailed description of the invention that follows, the embodiments provided by this disclosure are subject to various alternative variations and process sequences, unless otherwise specified. It should be understood that assumptions can be made. Further, except where stated in the examples or elsewhere, all numbers used in the specification and claims, for example, representing component amounts, are all modified with the word “about” in all cases. Should be understood. Accordingly, unless stated otherwise, the numerical parameters set forth in the following specification and appended claims are approximate values that vary depending on the desired characteristics to be obtained. At least not as an attempt to limit the application of the doctrine of equivalents to the claims, but each numerical parameter is interpreted by applying the usual rounding method, taking into account at least the number of significant figures reported Should.

  Although numerical ranges and parameters that broadly describe the scope of the invention are approximate, the numerical values set forth in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

  It should also be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, the range “1 to 10” is all between the minimum value of about 1 and the maximum value of about 10 (and includes a minimum value of about 1 and a maximum value of about 10). Is intended to include sub-ranges, i.e. having a minimum value equal to or greater than about 1 and a maximum value equal to or less than about 10. In addition, the expression “and / or” may be used explicitly in certain examples, but in this application, the use of “or” means “and / or” unless stated otherwise. To do.

A dash symbol ("-") used other than between two letters or symbols indicates a covalent bond point between a substituent or two atoms. For example, the chemical group —CONH ₂ is covalently bonded to other chemical moieties through the carbon atom.

The “acetylacetonate group” has the formula (1)

Means a group having the structure:
In certain embodiments, acetylacetonate refers to a metal chelator comprising an acetylacetonate ligand and one or more reactive functional groups. In certain embodiments, the one or more reactive functional groups are epoxy groups, alkenyl groups, Michael acceptor groups, or, for example, —Cl, —Br, —, which can react with a thiol group. I, -OSO ₂ CH _{3 (mesylate),} - such as _{OSO 2 -C 6 H 4 -CH 3} ( tosylate) is a group such as a group containing a saturated carbon with well suited leaving nucleophilic substitution.

“Alkanearene” means a hydrocarbon group having one or more aryl and / or arenediyl groups and one or more alkyl and / or alkanediyl groups, where aryl, arenediyl, alkyl, and Alkanediyl is defined herein. In certain embodiments, each of the aryl and / or arenediyl group (s) is C _6-12 , C _6-10 , and in certain embodiments, phenyl or benzenediyl. In certain embodiments, each alkyl and / or alkanediyl group (s) is C _1-6 , C _1-4 , C _1-3 , and in certain embodiments, methyl, methanediyl, ethyl Or ethane-1,2-diyl. In certain embodiments, the alkane arene _{groups, C 4 to 18} alkanes _{arene, C 4 to 16} alkanes _{arene, C 4 to 12} alkanes _{arene, C 4 to 8} alkanes _{arene, C 6 to 12} alkanes _{arene, C. 6 to 10} alkanearenes, and in certain embodiments, C _6-9 alkanearenes. An example of an alkanearene group is diphenylmethane.

“Alkanearenediyl” means a diradical of an alkanearene group. In certain embodiments, the alkanearene diyl group is C _4-18 alkanearene diyl, C _4-16 alkanearene diyl, C _4-12 alkanearene diyl, C _4-8 alkanearene diyl, C _6-12 alkane. arenediyl _{a C 6 to 10} alkane arene diyl, in certain _embodiments, it is a _{C 6 to 9} alkane arene diyl. An example of an alkanearenediyl group is diphenylmethane-4,4′-diyl.

“Alkanediyl” is a saturated, branched or straight chain, eg 1 to 18 carbon atoms (C _1-18 ), 1 to 14 carbon atoms (C _1-14 ), 1 to 6 carbons. Means an acyclic hydrocarbon radical diradical having an atom ( _C1-6 ), 1 to 4 carbon atoms ( _C1-4 ), or 1 to 3 carbon atoms ( _C1-3 ) To do. It will be appreciated that branched alkanediyl has a minimum of 3 carbon atoms. In certain embodiments, the alkanediyl is C _2-14 alkanediyl, C _2-10 alkanediyl, C _2-8 alkanediyl, C _2-6 alkanediyl, C _2-4 alkanediyl, certain in the _embodiment, it is _{C 2 to 3} alkanediyl. Examples of alkanediyl groups include methane-diyl (—CH ₂ —), ethane-1,2-diyl (—CH ₂ CH ₂ —), propane-1,3-diyl and iso-propane-1,2-diyl. (e.g. _-CH 2 _CH 2 CH ₂ - and _{-CH (CH 3) CH 2 -} ), butane-1,4-diyl _{(-CH 2 CH 2 CH 2 CH} 2 -), pentane-1,5-diyl ( _{-CH 2 CH 2 CH 2 CH 2} CH 2 -), hexane-1,6-diyl _{(-CH 2 CH 2 CH 2 CH} 2 CH 2 CH 2 -), heptane-1,7-diyl, octane-1, Examples include 8-diyl, nonane-1,9-diyl, decane-1,10-diyl, and dodecane-1,12-diyl.

“Alkanecycloalkane” means a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanediyl groups and one or more alkyl and / or alkanediyl groups, where cycloalkyl , Cycloalkanediyl, alkyl, and alkanediyl are defined herein. In certain embodiments, each cycloalkyl and / or cycloalkanediyl group (s) is C _3-6 , C _5-6 , and in certain embodiments, cyclohexyl or cyclohexanediyl. In certain embodiments, each alkyl and / or alkanediyl group (s) is C _1-6 , C _1-4 , C _1-3 , and in certain embodiments, methyl, methanediyl, Ethyl or ethane-1,2-diyl. In certain embodiments, the _{alkanecycloalkane} group is C _{4-18 alkanecycloalkane} , C _{4-16 alkanecycloalkane} , C _{4-12 alkanecycloalkane} , C _{4-8 alkanecycloalkane} , C _6-12 alkane. A cycloalkane, a _C6-10 alkanecycloalkane, and in certain embodiments, a _{C6-9 alkanecycloalkane} . Examples of alkanecycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

“Alkanecycloalkanediyl” means a diradical of an alkanecycloalkane group. In certain embodiments, the alkanecycloalkanediyl group is C _4-18 alkanecycloalkanediyl, C _4-16 alkanecycloalkanediyl, C _4-12 alkanecycloalkanediyl, C _4-8 alkanecycloalkanediyl, C _6-12 alkanecycloalkanediyl, C _6-10 alkanecycloalkanediyl, and in certain embodiments, C _6-9 alkanecycloalkanediyl. Examples of alkanecycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4′-diyl.

An “alkenyl” group refers to a group having the structure —CR═CR ₂ where the alkenyl group is a terminal group and is attached to a larger molecule. In such embodiments, each R may be selected from, for example, hydrogen and C _1-3 alkyl. In certain embodiments, each R is hydrogen and the alkenyl group has a —CH═CH ₂ structure.

“Alkoxy” means an —OR group, where R is alkyl, as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. In certain embodiments, the alkoxy group is C _1-8 alkoxy, C _1-6 alkoxy, C _1-4 alkoxy, and in certain embodiments, C _1-3 alkoxy.

“Alkyl” is a saturated, branched or straight chain, eg, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to It means a monoradical of an acyclic hydrocarbon group having 3 carbon atoms. It will be appreciated that a branched alkyl has a minimum of 3 carbon atoms. In certain embodiments, the alkyl group is C _1-6 alkyl, C _1-4 alkyl, and in certain embodiments, C _1-3 alkyl. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl, and tetradecyl. In certain embodiments, the alkyl group is C _1-6 alkyl, C _1-4 alkyl, and in certain embodiments, C _1-3 alkyl. It will be understood that a branched alkyl has at least 3 carbon atoms.

The “bis (sulfonyl) alkanol group” has the general formula:
—S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ — (2)
(Wherein each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH)
Means a group having In certain embodiments, the bis (sulfonyl) alkanol group is —CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH ₂ —CH. _2- has a structure.

In certain embodiments, a “bis (sulfonyl) alkanol group” can be a monovalent bis (sulfonyl) alkanol group or a divalent bis (sulfonyl) alkanol group. In certain embodiments, the monovalent bis (sulfonyl) alkanol group may be a terminal bis (sulfonyl) alkanol group such as “1- (ethylenesulfonyl) -n- (vinylsulfonyl) alkanol group”. A terminal bis (sulfonyl) alkanol group can be derived from the reaction of a bis (sulfonyl) alkanol and has the general structure —R ^{8 ′} —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S ( _O) can have a distal portion with 2 -R ^8. Here, R ^{8 ′} is a moiety derived from the reaction between R ⁸ and a moiety that reacts with R ⁸ , and each R ¹⁰ is independently C _1-3 alkanediyl and substituted C _1-3 alkane. Selected from diyl, wherein the one or more substituents are —OH. In certain embodiments, each R ⁸ includes a reactive functional group, and in certain embodiments, —CH═CH ₂ . In certain embodiments, the terminal bis (sulfonyl) alkanol group is 1- (ethylenesulfonyl) -3- (vinylsulfonyl) propan-2-ol, ie, —CH ₂ —CH ₂ —S (O) ₂ —CH. such _{2 -CH (-OH) -CH 2 -S} (O) 2 -CH = CH 2, 1- (ethylene sulfonyl)-n-(vinylsulfonyl) alkanol group. In certain embodiments, the terminal bis (sulfonyl) alkanol group is —CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH═CH. Has _two structures.

In certain embodiments, a bis (sulfonyl) alkanol group may be divalent when, for example, a bis (sulfonyl) alkanol group is incorporated into the main chain of a prepolymer such as the polythioether disclosed herein. . In certain embodiments, the divalent bis (sulfonyl) alkanol group has the general structure —R ^{8 ′} —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —R. ^{8 '-} and in certain ^{_{embodiments, -CH 2 -CH 2 -S (O}} ) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH 2 -CH 2 - and In certain embodiments, —R ^{8 ′} —S (O) ₂ —CH ₂ —CH (—OH) —CH ₂ —S (O) ₂ —R ^{8 ′} — _{-CH 2 -CH 2 -S (O)} 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH 2 -CH 2 - can have, where R ^{8 'and} R ¹⁰ is defined herein. In certain embodiments of the bis (sulfonyl) alkanol, each R ⁸ is an alkenyl group, each R ^{8 ′} is an ethane-diyl group, and / or each R ¹⁰ is methane-diyl.

“Bis (sulfonyl) alkanol” means a compound of the general formula R ⁸ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —R ⁸ , wherein each R ⁸ is a moiety having a reactive functional group, each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, one or more substituents here -OH is there. In certain embodiments, each R ⁸ is, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or, for example, —Cl, —Br, —I, —OSO ₂ CH ₃ (mesylate), —OSO ₂ —C. _It contains a terminal group that reacts with a thiol group, such as a group containing a saturated carbon with a leaving group well suited for nucleophilic substitution such as ₆ H ₄ —CH ₃ (tosylate). In certain embodiments, the bis (sulfonyl) alkanol can be a bis (vinylsulfonyl) alkanol containing a terminal alkenyl group. In certain embodiments, the bis (sulfonyl) alkanol has the formula CH ₂ ═CH—S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH═CH ₂ . The compound can be a bis (vinylsulfonyl) alkanol in which R ⁸ contains a terminal alkenyl group, such as a compound. In certain embodiments, the bis (vinylsulfonyl) alkanol is 1,3-bis (vinylsulfonyl) -2-propanol. In certain embodiments, a compound containing a bis (sulfonyl) alkanol is a compound having a reactive end functional group and a terminal group that reacts with a terminal alkenyl group of a bis (vinylsulfonyl) alkanol such as a thiol group or an epoxy group. Can be prepared by reacting a bis (vinylsulfonyl) alkanol. In such embodiments, the bis (sulfonyl) alkanol is R ^{8 ′} —CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH _2. It may have a —CH ₂ —R ^{8 ′} structure, where each R ^{8 ′} is a moiety derived from the reaction of the above compound with a terminal alkenyl group of a bis (vinylsulfonyl) alkanol.

  A “bis (sulfonyl) alkanol-containing” polymer, prepolymer, or adduct is a polymer in which one or more divalent bis (sulfonyl) alkanol groups are incorporated into the main chain of the polymer, prepolymer, or adduct, Represents a prepolymer or an adduct.

A divalent bis (sulfonyl) alkanol group can be converted to a prepolymer by reacting, for example, a polythiol monomer or prepolymer of formula (3a) with a bis (sulfonyl) alkanol of formula (4a) in an appropriate ratio. Can be incorporated:
R (-SH) _w (3a)
^{_{R 8 -S (O) 2 -R}} 10 -CH (-OH) -R 10 -S (O) 2 -R 8 (4a)
(Wherein R is an organic moiety, w is an integer of 2 or more, and each R ⁸ is, for example, an alkenyl group and an epoxy group, a Michael acceptor group, or, for example, —Cl, —Br, —I, — End groups that react with thiol groups, such as groups containing saturated carbons with leaving groups well suited for nucleophilic substitution such as OSO ₂ CH ₃ (mesylate), —OSO ₂ —C ₆ H ₄ —CH ₃ (tosylate), etc. Including). In certain embodiments, the bis (sulfonyl) alkanol of formula (4a) is of formula (4b):
^{_{CH 2 = CH-S (O}} ) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH = CH 2 (4b)
(Wherein each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH)
It may be a bis (vinylsulfonyl) alkanol having the structure: In certain embodiments, the bis (sulfonyl) alkanol can be 1,3-bis (vinylsulfonyl) -2-propanol. Alternatively, bis (sulfonyl) alkanol groups are incorporated into the prepolymer backbone by reacting the thiol-terminated bis (sulfonyl) alkanol of formula (4c) with the reactant of formula (3b) in the appropriate ratio. Can:
HS—R ^{8 ′} —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —R ^{8 ′} —SH (4c)
R (−R ⁷ ) _w (3b)
(Wherein, R is an organic moiety, w is an integer of 2 or more, R 8 ^'is a R ^8, a moiety derived from reaction with the portion that reacts with R ^8, each R ¹⁰ Are defined herein, and each R ⁷ is, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or, for example, —Cl, —Br, —I, —OSO ₂ CH ₃ (mesylate), —OSO _2. -C 6 _H 4 _-CH 3 such group consisting of saturated carbon having a leaving group well known in the nucleophilic substitution such _(tosylate) or the like, comprises a terminal group that reacts with thiol groups).

  By selecting an appropriate ratio of the reactant groups of formula (3a) and formula (4a) or formula (4c) and formula (3b), one or more bis (sulfonyl) alkanol groups as chain segments Or can be incorporated into the prepolymer as part of a terminal end having a reactive group, or both. For example, bis (vinylsulfonyl) alkanol is used to introduce one or more 1, n bis (ethylenesulfonyl) alkanol groups into the main chain of the prepolymer, or one or more terminal 1- (ethylenesulfonyl)- It can be used to introduce n- (vinylsulfonyl) alkanol groups, or both.

  In certain embodiments, bis (vinylsulfonyl) -2-propanol reacts with a thiol-terminated monomer / polymer to incorporate 1,3-bis (ethylenesulfonyl) -2-propanol groups in the prepolymer backbone. Can do.

  In certain embodiments, bis (vinylsulfonyl) -2-propanol is reacted with a thiol-terminated monomer / polymer to provide 1- (ethylenesulfonyl) -3- (vinylsulfonyl) -2-propanol end groups. Where the terminal alkenyl group is a well-recognized Michael acceptor group.

A moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group means a reaction product of a thiol group and a moiety containing a terminal group that reacts with the thiol group. Examples of terminal groups that react with thiol groups include epoxy groups, ethylene groups, and Michael acceptor groups. In certain embodiments, the moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group is —CH ₂ —CH ₂ —R—, —CH (—OH) —CH ₂ —R—, —CH ₂ —. It has a CH (—OH) —R— or —CH ₂ —CH ₂ —SO ₂ —R— structure, wherein R represents a covalent bond or an organic moiety bound to a sulfonyl group.

The part derived from the reaction of the bis (sulfonyl) alkanol and the thiol group also means the part of R ^{8 ′} derived from the reaction of the R ⁸ group and the thiol group, where R ⁸ includes a terminal group that reacts with the thiol group. .

In certain embodiments, R ^{8 ′} is a group derived from the reaction of a bis (sulfonyl) alkanol with a compound having a terminal group that reacts with a thiol group and a group that reacts with a bis (sulfonyl) alkanol. In certain embodiments, R ^{8 ′} is a group derived from the reaction of a compound having a terminal group that reacts with a thiol group and a group that reacts with an ethylene group with a bis (ethylenesulfonyl) alkanol. In such embodiments, R ^{8 ′} is —CH ₂ —CH ₂ —R′—CH ₂ —CH ₂ —, —CH (—OH) —CH ₂ —R′—CH ₂ —CH ₂ —, — _{CH 2 -CH (-OH) -R'-} CH 2 -CH 2 -, or _{-CH 2 -CH 2 -SO 2 -R'-} CH 2 -CH 2 - may have a structure, wherein R ' bis a compound used to cap (ethylene sulfonyl) alkanol, an ethylene group, an epoxy group, Michael acceptor groups, or, for example _{-Cl, -Br, -I, -OSO 2} CH 3 ( mesylate), Organic moieties derived from reaction with functional groups such as groups containing saturated carbons with leaving groups well suited for nucleophilic substitution such as —OSO ₂ —C ₆ H ₄ —CH ₃ (tosylate).

In certain embodiments, R ^{8 ′} is C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted C _2-10 heteroalkanediyl, C _{4-14 alkanecyclo. Alkanediyl} , substituted _{C4-14 alkanecycloalkanediyl} , _C4-14 heteroalkanecycloalkanediyl, substituted _C4-14 heteroalkanecycloalkanediyl, _{C4-14 alkanearenediyl} , substituted _{C4-14 alkanearenediyl} , C _4-14 heteroalkane _arenediyl , and substituted C _4-14 heteroalkane arene diyl. In certain embodiments, R ^{8 ′} is ethane-diyl.

In certain embodiments, R ⁸ is C _2-10 alkyl, substituted C _2-10 alkyl, C _2-10 heteroalkyl, substituted C _2-10 heteroalkyl, C _{4-14 alkanecycloalkyl} , substituted C _{4. -14} alkane _{cycloalkyl, C 4 to 14} heteroalkanes cycloalkyl, substituted _{C 4 to 14} heteroalkanes _{cycloalkyl, C 4 to 14} alkanes aryl, substituted _{C 4 to 14} alkane _{aryl, C 4 to 14} heteroalkanes aryl, and substituted Selected from _C4-14 heteroalkanearyl. In certain embodiments, R ⁸ is ethylene, ie, —CH═CH ₂ .

“Cycloalkanediyl” means a diradical of a saturated monocyclic or polycyclic hydrocarbon group. In certain embodiments, the cycloalkanediyl group is C _3-12 cycloalkanediyl, C _3-8 cycloalkanediyl, C _3-6 cycloalkanediyl, and in certain embodiments, C _5-6 Cycloalkanediyl. Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

“Cycloalkyl” means a monoradical group of saturated, monocyclic or polycyclic hydrocarbons. In certain embodiments, the cycloalkyl group is C _3-12 cycloalkyl, C _3-8 cycloalkyl, C _3-6 cycloalkyl, and in certain embodiments, C _5-6 cycloalkyl. .

  “Heteroalkanediyl” means an alkanediyl group in which one or more carbon atoms have been replaced by a heteroatom such as N, O, S, or P. In certain embodiments of heteroalkanediyl, the heteroatom is selected from N and O.

  “Heteroalkanearenediyl” means an alkanearenediyl group in which one or more carbon atoms have been replaced with a heteroatom such as N, O, S, or P. In certain embodiments of heteroalkanearenediyl, the heteroatom is selected from N and O.

  “Heterocycloalkanediyl” means a cycloalkanediyl group in which one or more carbon atoms have been replaced by a heteroatom such as N, O, S, or P. In certain embodiments of heterocycloalkanediyl, the heteroatom is selected from N and O.

“Michael acceptor” has at least one alkene / alkyne group in which carbonyl (—CO), nitro (—NO ₂ ), nitrile (—CN), alkoxycarbonyl (—COOR), phosphonate (—PO (OR) ₂ ), Trifluoromethyl (—CF ₃ ), sulfonyl (—SO ₂ —), trifluoroomethanesulfonyl (—SO ₂ CF ₃ ), p-toluenesulfonyl (—SO ₂ —C ₆ H ₄ —CH ₃ ), etc. A substituted alkene / alkyne compound that is directly bonded to one or more of the electron withdrawing groups. The types of compounds that function as Michael acceptors are vinyl ketone, quinone, nitroalkene, acrylonitrile, acrylate, methacrylate, cyanoacrylate, acrylamide, maleimide, dialkyl vinyl phosphonate, and vinyl sulfone. Other examples of Michael acceptors are Mother et al., Prog. Polym. Sci. 2006, Vol. 31, pages 487-531. Michael acceptor compounds having a plurality of Michael acceptor groups are also well known. Examples include diacrylates such as ethylene glycol diacrylate and diethylene glycol diacrylate, dimethacrylates such as ethylene glycol methacrylate and diethylene glycol methacrylate, bismaleimides such as N, N ′-(1,3-phenylene) dimaleimide and 1, Examples include 1 ′-(methylenedi-4,1-phenylene) bismaleimide, and vinyl sulfones such as divinyl sulfone and 1,3-bis (vinylsulfonyl) -2-propanol. In certain embodiments, the Michael acceptor group has a structure of formula (7a) or formula (7b):
—CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH═CH ₂ (7a)
_{-CH 2 -CH 2 -S (O)} 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH = CH 2 (7b)
(Wherein each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH).

“Michael acceptor compound” means a compound comprising at least one terminal Michael acceptor group. In certain embodiments, the Michael acceptor compound is divinyl sulfone and the Michael acceptor group is vinylsulfonyl, ie, —S (O) ₂ —CH═CH ₂ . In certain embodiments, the Michael acceptor compound is a bis (vinylsulfonyl) alkanol and the Michael acceptor group is 1- (ethylenesulfonyl) -n- (vinylsulfonyl) alkanol (—CH ₂ —CH ₂ —S ( _O) is ^{2 -R 10 -CH (-OH) -R} 10 -S (O) 2 -CH = CH 2), in certain embodiments, 1 - (ethylene) -3- (vinylsulfonyl) propane-2-ol _{(-CH 2 -CH 2 -S (O} ) 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH = CH 2).

Hydroxypyridinones include 3-hydroxy-4-pyridinone and 3-hydroxy-2-pyridinone having the structure of formula (8a) or formula (8b), respectively:

(Wherein R is an organic group such as an alkyl group). The metal chelating agent derived from hydroxypyridinone contains one or more reactive functional groups such as a hydroxypyridinone group and a terminal thiol group.

  “Metal ligand” means an ion or molecule that binds to a metal atom and potentially other atoms to form a coordination complex. Bonds between metals and / or atoms generally involve donation of one or more electron pairs to the metal, and the nature of the bond can be covalent or ionic. The metal ligands provided by the present disclosure can form coordination complexes on aerospace surfaces that can be oxidized, such as aluminum and titanium surfaces. In the case of an oxidized surface, the metal ligand can form a coordination complex with a metal such as Al (III) and an oxygen atom. Coordination complexes can improve adhesion to metal or oxidized metal surfaces.

  As this disclosure provides, metal ligands can be incorporated into the backbone of the prepolymer. For incorporation into the prepolymer backbone, the metal ligand may contain or be derivatized to contain at least two groups that react with the subunit groups of the prepolymer in addition to the moieties that can form coordination complexes. . Such reactive metal ligands may be obtained commercially or may be derivatized to include appropriate reactive substituents using methods known to those skilled in the art.

The “polyalkoxysilyl group” has the formula —Si (—R ⁴ ) _P (—OR ⁴ ) _3-P (9)
Wherein p is selected from 0, 1, and 2 and each R ⁴ is independently selected from C _1-4 alkyl.
Means a group having In certain embodiments of the polyalkoxysilyl group, p is 0, p is 1, and in certain embodiments, p is 2. In certain embodiments of the polyalkoxysilyl group, each R ⁴ is independently selected from ethyl and methyl. In certain embodiments of the polyalkoxysilyl group, each R ⁴ is ethyl, and in certain embodiments, each R ⁴ is methyl. In certain embodiments of the polyalkoxysilyl group, the group is —Si (—OCH ₂ CH ₃ ) ₃ , —Si (—OCH ₃ ) ₃ , —Si (—CH ₃ ) (— OCH ₃ ) ₂ , _{-Si (-CH 3) 2 (-OCH} 3), - Si (-CH 3) (- OCH 2 CH 3) 2, -Si (-CH 3) 2 (-OCH 2 CH 3), - Si (- _{CH 2 CH 3) (- OCH} 3), and is selected from _{-Si (-CH 2 CH 3) 2} (-OCH 3).

“Substituted” means a group in which one or more hydrogen atoms are independently replaced with the same or different substituent (s). In certain embodiments, the substituent group is halogen, —S (O) ₂ OH, —S (O) ₂ , —SH, where R is C _1-6 alkyl, —SR, —COOH, —NO ₂ , _-NR 2 where each R is independently selected from hydrogen and _{C 1 to 3 alkyl, -CN, -C = O, C} 1~6 _alkyl, -CF 3, -OH, _{phenyl, C 2 to 6} heteroalkyl, C _{5 to 6 heteroaryl, C 1 to 6} alkoxy, and R is selected from -COR a _{C 1 to 6} alkyl. In certain embodiments, the substituent is selected from —OH, —NH ₂ , and C _1-3 alkyl.

As used herein, “polymer” means oligomers, homopolymers, and copolymers. Unless otherwise stated, the molecular weight is determined by art-recognized techniques, eg, gel permeation chromatography using standard polystyrene, and the number average molecular weight of the polymeric material represented by “M _n ” It is.

  Hereinafter, several embodiments of metal ligand-containing prepolymers such as metal ligand-containing polythioether, compositions thereof, and synthesis methods will be described. The disclosed embodiments are not intended to limit the scope of the claims. On the other hand, the claims are intended to cover all alternatives, modifications, and equivalents.

  Metal ligands such as bis (sulfonyl) alkanols are incorporated into the backbone of sulfur-containing prepolymers to improve tensile strength and adhesion of cured aerospace sealants to surfaces such as bare or anodized metal surfaces. . The metal ligand-containing prepolymer, such as a bis (sulfonyl) alkanol-containing sulfur-containing prepolymer, can be adapted to any suitable curing chemistry. For example, thiol-terminated metal ligand-containing polythioether prepolymers and polyepoxy curing agents provide useful sealants for aerospace applications.

Bis (sulfonyl) alkanol-containing polythioether The bis (sulfonyl) alkanol-containing polythioether provided by the present disclosure is characterized by having one or a plurality of bis (sulfonyl) alkanol groups incorporated into the main chain of the polythioether.

  Polythioethers useful for aerospace sealant applications are disclosed, for example, in US Pat. No. 6,172,179. The polythioether means a compound containing at least two thioethers and —C—S—C— bonds. Polythioethers can be prepared, for example, by reacting dithiol with divinyl ether. In general, bis (sulfonyl) alkanol-containing polythioethers can be prepared by reacting monomeric bis (sulfonyl) alkanols having terminal groups that react with the ends of the polythioether.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether has the formula (10):
—S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ — (10)
(Wherein each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH)
Including the part.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether has the formula (11):
—AR ^{8 ′} —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —R ^{8 ′} —A— (11)
(Where
Each R ^{8 ′} is a moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group,
Each ^{R 10} is _{independently} selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6)
Including the structure.

In certain embodiments of formula (11) and formula (12), each R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, wherein each X is Independently selected from -O- and -S-. In certain embodiments wherein R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, each X is —O—, and in certain embodiments, each X is -S-. In certain embodiments, each R ³ is hydrogen.

In certain embodiments of formula (11) and formula (12), each R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r —, wherein each X is Independently selected from -O- and -S-. In certain embodiments where R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r —, each X is —O—, and in certain embodiments, each X is -S-.

In certain embodiments of formula (11) and formula (12), each R ¹ is — [(— CH ₂ —) _s —X—] _q — (CH ₂ ) _r —, wherein s is 2, X is O, q is 2, r is 2, R ² is ethanediyl, m is 2, and n is 9.

In certain embodiments of Formula (11) and Formula (12), each R ¹ is a group derived from dimercaptodioxaoctane (DMDO), and in certain embodiments, each R ¹ is dimercapto. This is a group derived from diethyl sulfide (DMDS).

  In certain embodiments of Formula (11) and Formula (12), each m is independently an integer from 1 to 3. In certain embodiments, each m is the same, 1 or 2, and in certain embodiments is 3.

  In certain embodiments of Formula (11) and Formula (12), n is an integer from 1 to 30, an integer from 1 to 20, and an integer from 1 to 10, and in certain embodiments, from 1 to It is an integer of 5. In a specific embodiment, n may be any integer from 1 to 60.

  In certain embodiments of Formula (11) and Formula (12), each p is independently selected from 2, 3, 4, 5, and 6. In certain embodiments, each p is the same and is 2, 3, 4, 5, or 6.

In the formula (11), each R ^{8 ′} is a group derived from a reaction between a thiol group and a group that reacts with a thiol group such as a terminal alkenyl group, a terminal epoxy group, or a terminal Michael acceptor group. In certain embodiments of formula (11) and formula (12), each R ^{8 ′} is independently C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted _{C 4 to 10 heteroalkanediyl, C 4 to 14} alkane cycloalkanediyl, substituted _{C 4 to 14} alkane _{cycloalkanediyl, C 4 to 14} heteroalkanes cycloalkanediyl, substituted _{C 4 to 14} heteroalkanes cycloalkanediyl, C _{Selected from 2-14 alkanearene} diyl, substituted _{C4-14 alkanearene} diyl, _C4-14 heteroalkanearene diyl, and substituted _C4-14 heteroalkanearene diyl. In certain embodiments, each R ^{8 ′} is the same. In certain embodiments, each R ^{8 ′} is ethane-diyl, ie, —CH ₂ —CH ₂ —.

In certain embodiments of formula (11), each R ¹⁰ is independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In certain embodiments, each R ¹⁰ is methane-diyl, in certain embodiments, ethane-diyl, and in certain embodiments, 1,3-propane-diyl.

In certain embodiments of formula (11), each R ^{8 ′} is ethane-diyl and each R ¹⁰ is methane-diyl.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether is a bis (sulfonyl) alkanol-containing polythioether of formula (13a), a bis (sulfonyl) alkanol-containing polythioether of formula (13b), and combinations thereof Selected:
^{R 6 -A - [- R 8} '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -R 6 (13a)
^{{R 6 -A - [- R} 8 '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -V'-} z B (13b)
(Where
N is an integer from 1 to 10,
Each R ^{8 ′} is a moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group,
Each ^{R 10} is _{independently} selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _r- ,
s is an integer from 2 to 6,
q is an integer from 1 to 5;
r is an integer from 2 to 10,
Each R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V with a thiol;
Each R ⁶ is independently selected from hydrogen and a moiety having a terminal reactive group).

  In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), N is 1, 2, 3, 4, 5, 6, 7, 8, 9. In certain embodiments, N is 10. In certain embodiments of the bis (sulfonyl) alkanol-containing polymer of formula (13a) and formula (13b), the molecular weight is from 400 daltons to 20,000 daltons. In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether of formula (13a) comprises a combination of bis (sulfonyl) alkanol-containing polythioethers of formula (13a) with different values of N. In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether of formula (13b) comprises a combination of bis (sulfonyl) alkanol-containing polythioethers of formula (13b) with different values of N. In certain embodiments of the bis (sulfonyl) alkanol containing polythioether of formula (13a) and formula (13b), N is 1.

In certain embodiments of formula (13a) and formula (13b), each R ^{8 ′} is a thiol group and a group that reacts with a thiol group, such as a terminal alkenyl group, a terminal epoxy group, or a terminal Michael acceptor group. It is a group derived from the reaction of In certain embodiments of formula (13a) and formula (13b), each R ^{8 ′} is independently C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted _{C 2 to 10 heteroalkanediyl, C 4 to 14} alkane cycloalkanediyl, substituted _{C 4 to 14} alkane _{cycloalkanediyl, C 4 to 14} heteroalkanes cycloalkanediyl, substituted _{C 4 to 14} heteroalkanes cycloalkanediyl, C _{Selected from 4-14} alkane arene diyl, substituted C _4-14 alkane arene diyl, C _4-14 heteroalkane arene diyl, and substituted C _4-14 heteroalkane arene diyl. In certain embodiments, each R ^{8 ′} is the same. In certain embodiments, each R ^{8 ′} is ethane-diyl, ie, —CH ₂ —CH ₂ —.

In certain embodiments of formula (13a) and formula (13b), each R ¹⁰ is independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In certain embodiments, each R ¹⁰ is methane-diyl, in certain embodiments, ethane-diyl, and in certain embodiments, 1,3-propane-diyl.

In certain embodiments of formula (13a) and formula (13b), each R ^{8 ′} is ethane-diyl and each R ¹⁰ is methane-diyl.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of Formula (13a) and Formula (13b), each R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r -Where each X is independently selected from -O- and -S-. In certain embodiments wherein R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, each X is —O—, and in certain embodiments, each X is -S-. In certain embodiments, each R ³ is hydrogen.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r. -Where each X is independently selected from -O- and -S-. In certain embodiments where R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r —, each X is —O—, and in certain embodiments, each X is -S-.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ¹ is — [(— CH ₂ —) _s —X—] _q — (CH ₂ ). _r— , where s is 2, X is O, q is 2, r is 2, R ² is ethanediyl, m is 2, and n is 9.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioethers of formula (13a) and formula (13b), each R ¹ is a group derived from DMDO, and in certain embodiments, each R ¹ is It is a group derived from DMDS.

  In certain embodiments, each m is independently an integer from 1 to 3. In certain embodiments, each m is the same, 1 or 2, and in certain embodiments is 3.

  In certain embodiments of the bis (sulfonyl) alkanol containing polythioether of formula (13a) and formula (13b), n is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, In certain embodiments, an integer from 1 to 5. Also, in certain embodiments, n may be an integer from 1 to 60.

  In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each p is independently selected from 2, 3, 4, 5, and 6. In certain embodiments, each p is the same and is 2, 3, 4, 5, or 6.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ¹ is — [(— CH ₂ —) _s —X—] _q — (CH ₂ ). _r— , where s is 2, X is —O—, q is 2, r is 2, R ² is ethanediyl, m is 2, and n is 9.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ¹ is C _2-6 alkanediyl, and — [— (CHR ³ ) _s —X -] _Q- (CHR ³ ) _r- .

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of Formula (13a) and Formula (13b), each R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, In certain embodiments, X is —O—, and in certain embodiments, X is —S—.

Certain implementations of bis (sulfonyl) alkanol-containing polythioethers of formula (13a) and formula (13b), wherein R ¹ is-[-(CHR ³ ) _s -X-] _q- (CHR ³ ) _r- In embodiments, s is 2, r is 2, q is 1, and X is -S-. In certain embodiments, s is 2, q is 2, r is 2, and X is -O-. In certain embodiments, s is 2, r is 2, q is 1, and X is -O-.

Certain implementations of bis (sulfonyl) alkanol-containing polythioethers of formula (13a) and formula (13b), wherein R ¹ is-[-(CHR ³ ) _s -X-] _q- (CHR ³ ) _r- In a form, each R ³ is hydrogen, and in certain embodiments, at least one R ³ is methyl.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ¹ is the same, and in certain embodiments, at least one R ¹ is different.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ⁶ is the same and the terminal reactive group is —SH, —CH═CH ₂ , — Selected from NH ₂ , —OH, epoxy group, polyalkoxysilyl group, and Michael acceptor group.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether of formula (13a) is of formula (14):
_{^{R 11 -R 8 '-S (O}} ) 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -R 8' -R 11 (14)
Wherein each R ^{8 ′} is as defined herein and each R ¹¹ is H — [— S — (— R ¹² —O—) ₂ —R ¹² —S — (— R ¹² —O—) ₃ —R ¹² —] ₂ —S — (— R ¹² —O—) ₂ —R ¹² —S—, wherein each R ¹² is —CH ₂ —CH ₂ —.
It has the structure of.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether of formula (13a) is of formula (15):
^{_{R 11 -CH 2 CH 2 -S (}} O) 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH 2 CH 2 -R 11 (15)
Wherein each R ¹¹ is H-[— S — (— R ¹² —O—) ₂ —R ¹² —S — (— R ¹² —O—) ₃ —R ¹² —] ₂ —S — (— R ¹² _-O-) is 2 ^-R 12 -S-, where each ^{R 12} is _-CH 2 -CH ₂ - and is)
It has the structure of.

In certain embodiments of the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b), each R ⁶ is hydrogen, the bis (sulfonyl) alkanol-containing polythioether is terminated with a thiol, It has the structure of formula (16a), formula (16b), formula (16c), or formula (16d):
^{H-A - [- R 8} '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -H (16a)
{H-A - [- R 8 '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -V'-} z B (16b)
H—A — [— CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH ₂ —CH ₂ —A—] _N— H (16c )
^{_{{H-A - [- CH}} 2 -CH 2 -S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH 2 -CH 2 -A-] N -V ' −} _Z B (16d)
(Wherein A, N, R ^{8 ′} , R ¹⁰ , V ′, z, and B are defined herein).

B (-V) _z represents a polyfunctional agent. The polyfunctionalizing agent may be a single type of polyfunctionalizing agent or a combination of different polyfunctionalizing agents that may have the same or different functionality. In certain embodiments, z is 3, 4, 5, or 6. Suitable polyfunctionalizing agents include trifunctionalizing agents where z is a compound of 3. Suitable trifunctionalizing agents such as, for example, triallyl cyanurate (TAC) as disclosed in paragraphs [0102] to [0105] of US Patent Application Publication No. 2010/0010133, the citation of which is incorporated by reference. , Modified 1,2,3-propanetrithiol, modified isocyanurate-containing trithiol, 1,2,4-trivinylcyclohexane, and any combination of the foregoing. Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether. Mixtures of polyfunctionalizing agents may be used. Suitable isocyanurate-containing functionalizing agents are disclosed, for example, in US Patent Application Publication No. 2011/0319559.

R ⁶ represents a moiety having a terminal reactive group. The terminal reactive group can be selected as suitable for a particular curing chemistry. For example, in certain embodiments, each R ⁶ is the same and the reactive group is —SH, —CH═CH ₂ , —NH ₂ , —OH, an epoxy group, a polyalkoxysilyl group, and a Michael acceptor group. Selected from. The use of a particular cure chemistry may be selected to achieve, for example, the desired cure time, application method, surface affinity, shelf life, pot life, and / or cure sealant composition properties of the composition. it can. For example, in certain embodiments, the bis (sulfonyl) alkanol containing polythioether of formula (13a) and / or formula (13b) is terminated with a thiol and R ⁶ is a hydrogen or a moiety terminated with a thiol group. is there. In certain embodiments, B (-V) _z is an alkenyl-terminated polyfunctionalizing agent, wherein each -V includes a terminal alkenyl group, thus each -V'- is an alkenyl group, and an alkenyl group. Represents a moiety formed by the reaction of a group that reacts with.

In certain embodiments, the polyfunctionalizing agent can include one or more bis (sulfonyl) alkanol groups. For example, in certain embodiments, the polyfunctionalizing agent can react with a bis (sulfonyl) alkanol having a terminal group that reacts with a terminal group of the multifunctionalizing agent and a terminal group that reacts with a thiol group. Accordingly, in certain embodiments, the bis (sulfonyl) alkanol containing polyfunctionalizing agent of formula (17) is a polyfunctionalizing having the bis (sulfonyl) alkanol of formula (4a) and the formula B (-V) _z . Can be formed by reacting with an agent:
{R ⁸ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —R ^{8 ′} —V′—} _z B (17)
(Wherein R ⁸ , R ^{8 ′} , R ¹⁰ , B, and V ′ are defined herein).

In certain embodiments of the bis (sulfonyl) alkanol containing polythioether of formula (13a) and formula (13b), R ⁶ is hydrogen and the bis (sulfonyl) alkanol containing formula (13a) and formula (13b) Polythioethers are terminated with thiols.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether of formula (13a) and formula (13b) is an uncapped bis (sulfonyl) alkanol, for example, each R ⁶ is hydrogen, terminated with a thiol. It can be called polythioether containing. In certain embodiments, the polythioether containing uncapped bis (sulfonyl) alkanol is liquid at room temperature. Further, in certain embodiments, the polythioether containing an uncapped bis (sulfonyl) alkanol is determined according to ASTM D-2849 § 79-90, and has a Brookfield CAP2000 viscosity at a temperature of about 25 ° C. and a pressure of about 760 mmHg. It has a viscosity of less than 500 poise, such as 100 poise to 300 poise, or even 100 poise to 200 poise at 100% solids, as measured using a meter. Any endpoint within the aforementioned range can also be used. In certain embodiments, the polythioether containing uncapped bis (sulfonyl) alkanol has a number average molecular weight of 400 grams per mole, such as from 1,000 grams per mole to 8,000 grams per mole. To 10,000 grams per mole. The molecular weight is determined, for example, by gel permeation chromatography using standard polystyrene. Any endpoint within the aforementioned range can also be used. In certain embodiments, the Tg of the polythioether containing uncapped bis (sulfonyl) alkanol is −55 ° C. or lower, such as −60 ° C. or lower.

  In certain embodiments, to adapt the bis (sulfonyl) alkanol-containing polythioether for use in different curing chemistries, the bis (sulfonyl) alkanol-containing polythioether may be capped with a specific reactive group, Or it may be terminated.

The bis (sulfonyl) alkanol-containing polythioethers of formula (13a) and formula (13b) in which R ⁶ is a moiety having a terminal reactive group are represented by the corresponding formulas (13a) and (13b) in which each R ⁶ is hydrogen. A thiol-terminated bis (sulfonyl) alkanol-containing polythioether can be prepared by capping with a moiety having a terminal reactive group and a group that reacts with a thiol group. Capped polythioether analogs and methods of preparing capped polythioether analogs useful for aerospace sealant applications are described, for example, in US Pat. No. 6,172,179 and US This is disclosed in Japanese Patent Application Publication No. 2011/0319559. In certain embodiments, R ⁶ comprises a terminal alkenyl group, a terminal epoxy group, a terminal polyalkoxysilyl group, a terminal amine group, or a terminal Michael acceptor group. The molecular weight of the cap group R ⁶ may be less than 500 daltons.

  The terminally modified bis (sulfonyl) alkanol containing polythioethers provided by this disclosure can be prepared by a number of methods known to those skilled in the art. For example, to obtain a terminally modified bis (sulfonyl) alkanol containing polythioether of formula (13a) and formula (13b), as disclosed herein, a thiol terminated bis of formula (16a) or formula (16b) The (sulfonyl) alkanol-containing polythioether can react with a compound having a terminal functional group and a terminal group that reacts with a thiol group.

For example, to obtain an alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a), the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) is composed of a terminal alkenyl group and TMI, methacrylic acid 2- It can react with a compound containing an isocyanate group, such as a group derived from isocyanatoethyl or allyl isocyanate, in the presence of a dibutyltin dilaurate catalyst. As a further example, a bis (sulfonyl) alkanol-containing polythioether of formula (13a) is an Amberlyst ™ 15 in an alkene-ol such as 3-buten-1-ol and an aldehyde such as formaldehyde and an organic solvent such as toluene. Can be reacted in the presence of a sulfonic acid such as 4.7 meq / gH ⁺ to provide an alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a). In certain embodiments, an alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) is reacted with a polyalkenyl compound, such as a dialkenyl compound, with a thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a). Can be prepared.

  The polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) is, for example, a thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) and 3-isocyanatopropyltrimethoxysilane, or 3- It can be prepared by reacting with a polyalkoxysilane such as isocyanatopropyltriethoxysilane in the presence of dibutyltin dilaurate to provide the corresponding polyalkoxysilyl terminated bis (sulfonyl) alkanol containing polythioether of formula (13a) . In certain embodiments, the polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) can be prepared by reacting a vinylalkoxysilane with a thiol-terminated bis (sulfonyl) alkanol-containing polythioether.

  The epoxy-terminated bis (sulfonyl) alkanol-containing polythioether of the formula (13a) is, for example, a thiol-terminated bis (sulfonyl) alkanol-containing polythioether of the formula (16a) and a monoepoxide such as epichlorohydrin or an alkenyl such as allyl glycidyl ether. It can be prepared by reacting with a glycidyl compound to provide the corresponding epoxy-terminated bis (sulfonyl) alkanol containing polythioether of formula (13a).

The amine-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) may be, for example, an activated alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) or Michael acceptor-terminated bis ( A sulfonyl) alkanol-containing polythioether and an diamine, an amino-substituted aniline such as 4- (aminomethyl) aniline, or an alkylamine such as n-butylamine, optionally in an organic solvent, 1,8-diazabicyclo [5.4.0]. It can be prepared by reacting in the presence of a catalyst such as undec-7-ene (DBU) to provide the corresponding amine-terminated bis (sulfonyl) alkanol containing polythioether of formula (13a). Alternatively, the amine-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) is reacted with an isocyanate-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) and a diamine such as 4- (aminomethyl) aniline. The corresponding amine-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) is provided. The amine-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) is obtained by combining a hydroxyl-terminated bis (sulfonyl) alkanol-containing polythioether of formula (13a) with an amino-substituted benzoate such as ethyl-4-aminobenzoate. It can also be obtained by reacting at elevated temperature in the presence of ₂ SnO or NaOMe to provide the corresponding amine-terminated bis (sulfonyl) alkanol containing polythioether of formula (13a).

Isocyanate-terminated bis (sulfonyl) alkanol-containing polythioethers of formula (13a) include, for example, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers of formula (16a) and TDI, Isonate ™ 143L (polycarbodiimide-modified diphenylmethanedi Isocyanato), Desmodur® N3400 (1,3-bis (6-isocyanatohexyl) -1,3-diazetidine-2,4-dione), IPDI (isophorone diisocyanate), or Desmodur® ) Prepared by reacting a diisocyanate such as W (H ₁₂ MDI), optionally in the presence of a catalyst such as dibutyltin dilaurate. Isocyanate-terminated sulfur-containing polymers can be used as intermediates in the synthesis of other end-modified sulfur-containing polymers, such as certain amine-terminated and thiol-terminated bis (sulfonyl) alkanol-containing polythioethers provided by this disclosure. .

  Similar reactions may be used to prepare capped bis (sulfonyl) alkanol-containing prepolymers of formula (13b).

In certain embodiments, the thiol-terminated bis (sulfonyl) alkanol-containing polythioether is
(A) the thiol-terminated polythioether of formula (18a), the thiol-terminated polythioether of formula (18b), and combinations thereof:
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
{HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SV′—} _z B (18b )
(Where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s —. X—] _q — (— CHR ³ —) _r —, wherein s is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10,
Each R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated polythioether selected from
(B) Formula (19):
_{^{R 8 -S (O) 2 -R}} 10 -CH (-OH) -R 10 -S (O) 2 -R 8 (19)
(Where
Each R ⁸ is independently selected from moieties containing terminal groups that react with terminal thiol groups;
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH)
The reaction product of a reaction product comprising a bis (sulfonyl) alkanol.

In certain embodiments of the thiol-terminated polythioether of formula (18a) and formula (18b), each R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, Here, each X is independently selected from -O- and -S-. In certain embodiments wherein R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, each X is —O—, and in certain embodiments, each X is -S-. In certain embodiments, each R ³ is hydrogen.

In certain embodiments of the thiol-terminated polythioether of formula (18a) and formula (18b), each R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r —, Here, each X is independently selected from -O- and -S-. In certain embodiments where R ¹ is — [— (CH ₂ ) _s —X—] _q — (CH ₂ ) _r —, each X is —O—, and in certain embodiments, each X is -S-.

In certain embodiments of the thiol-terminated polythioether of formula (18a) and formula (18b), each R ¹ is — [— (CH ₂ ) _p —X—] _q — (CH ₂ ) _r —, Here, s is 2, X is O, q is 2, r is 2, R ² is ethanediyl, m is 2, and n is 9.

In certain embodiments of the thiol-terminated polythioethers of formula (18a) and formula (18b), each R ¹ is a group derived from DMDO, and in certain embodiments, each R ¹ is derived from DMDS. It is a group.

  In certain embodiments of the thiol-terminated polythioether of formula (18a) and formula (18b), each m is independently an integer from 1 to 3. In certain embodiments, each m is the same, 1 or 2, and in certain embodiments is 3.

  In certain embodiments of the thiol-terminated polythioethers of formula (18a) and formula (18b), n is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, and certain implementations In form, it is an integer from 1 to 5. In a specific embodiment, n may be any integer from 1 to 60.

  In certain embodiments of the thiol-terminated polythioether of formula (18a) and formula (18b), each p is independently selected from 2, 3, 4, 5, and 6. In certain embodiments, each p is the same and is 2, 3, 4, 5, or 6.

In certain embodiments of the thiol-terminated polythioethers of formula (18a) and formula (18b), R ¹ is a group derived from DMDO, R ² is a group derived from divinyl ether, and a multifunctional agent Is TAC.

In certain embodiments, the polythioether prepolymer of formula (18a) is of formula (20):
_{H - [- S - (-} CH 2 CH 2 -O-) 2 -CH 2 CH 2 -S - (- CH 2 CH 2 -O-) 3 -CH 2 CH 2 -] N -S - (- CH _{2 CH 2 -O-) 2 -CH 2} CH 2 -SH (20)
It has the structure of.

In certain embodiments of formula (19), each R ¹⁰ is independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In certain embodiments, each R ¹⁰ is methane-diyl, in certain embodiments, ethane-diyl, and in certain embodiments, 1,3-propane-diyl.

In certain embodiments of formula (19), R ⁸ comprises a group that reacts with a thiol group selected from alkenyl groups, epoxy groups, and Michael acceptor groups. In certain embodiments, each R ⁸ is terminated with an alkenyl group. In certain embodiments, R ⁸ is C _2-10 alkyl, substituted C _2-10 alkyl, C _2-10 heteroalkyl, substituted C _2-10 heteroalkyl, C _{4-14 alkanecycloalkyl} , substituted C _{4. -14} alkane _{cycloalkyl, C 4 to 14} heteroalkanes cycloalkyl, substituted _{C 4 to 14} heteroalkanes _{cycloalkyl, C 4 to 14} alkanes aryl, substituted _{C 4 to 14} alkane _{aryl, C 4 to 14} heteroalkanes aryl, and substituted Selected from _C4-14 heteroalkanearyl. In certain embodiments, R ⁸ is ethylene, ie, —CH═CH ₂ .

In certain embodiments, the bis (sulfonyl) alkanol of formula (19) comprises a bis (vinylsulfonyl) alkanol. In certain embodiments, the bis (vinylsulfonyl) alkanol has the formula (21):
^{_{CH 2 = CH-S (O}} ) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH = CH 2 (21)
Wherein R ¹⁰ is defined herein.
It has the structure of.

In certain embodiments, the bis (vinylsulfonyl) alkanol of formula (19) comprises 1,3-bis (vinylsulfonyl) -2-propanol and has the formula (22):
_{CH 2 = CH-S (O} ) 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH = CH 2 (22)
It has the structure of.

  The thiol-terminated polythioethers of formula (18a) and formula (18b) and the bis (vinylsulfonyl) alkanol of formula (19) can be reacted in the presence of a base catalyst such as an amine catalyst. Examples of suitable amine catalysts include, for example, triethylenediamine (1,4-diazabicyclo [2.2.2] octane, DABCO), dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA), bis- (2-dimethyl Aminoethyl) ether, N-ethylmorpholine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), pentamethyldiethylenetriamine (PMDETA), benzyldimethylamine (BDMA), N, N , N′-trimethyl-N′-hydroxyethyl-bis (aminoethyl) ether, and N ′-(3- (dimethylamino) propyl) -N, N-dimethyl-1,3-propanediamine.

  In certain embodiments, the bis (sulfonyl) alkanol-containing polythioethers provided by the present disclosure are characterized by a mercaptan equivalent weight (MEW) of about 400 to about 4,000.

  Various methods can be used to prepare the thiol-terminated polythioethers of formula (18a) and formula (18b). Examples of suitable thiol-terminated polythioethers and methods for their preparation are described in US Pat. No. 6,172,179, column 2, line 29 to column 4, line 22, 6 It is described in column 39 line to 10th column 50 line, and eleventh column 65 line to twelfth column 22 line. Such thiol-terminated polythioethers may be difunctional, i.e. linear polymers having two terminal thiol groups, or multifunctional, i.e. branched polymers having three or more terminal thiol groups. There may be. Suitable thiol-terminated polythioethers are described, for example, by PRC-DeSoto International Inc. (Commercially available from Schermer, Calif.), Such as Permapol® P3.1E.

  In certain embodiments, preparing the thiol-terminated polythioether by selecting the amount of each reactant used to prepare the polythioether to produce a terminal thiol group and reacting the polythiol and a diene such as divinyl ether. Can do. Thus, optionally (n, or> n, such as n + 1) moles of polythiol (such as dithiol, or a mixture of at least two different dithiols), and from about 0.05 mole to 1 mole, such as from 0.1 mole. A thiol-terminated polyfunctionalizing agent, such as 0.8 mole, can be reacted with (n) moles of a diene (eg, divinyl ether or a mixture of at least two different dienes such as divinyl ether). In certain embodiments, the thiol-terminated polyfunctionalizing agent reacts in an amount sufficient to provide a thiol-terminated polythioether having an average functionality of 2.05 to 3, such as 2.1 to 2.8. Present in the mixture.

  The reaction used to make the thiol-terminated polythioether can be catalyzed by a free radical catalyst. Suitable free radical catalysts include azo compounds such as azobisnitrile compounds such as azo (bis) isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and t-butyl peroxide; and inorganics such as hydrogen peroxide A peroxide is mentioned. The reaction can proceed either with or without a radical initiator / photosensitizer and upon irradiation with ultraviolet light. For example, an ion catalyst method using either an organic base such as triethylamine or an inorganic base may be used.

  Suitable thiol-terminated polythioethers can be made by reacting divinyl ether or a mixture of divinyl ethers with excess dithiol or a mixture of dithiols.

Thus, in certain embodiments, the thiol-terminated polythioether is
(A) Formula (23):
HS-R ¹ -SH (23)
Wherein R ¹ is C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [— (CHR ³ ) _{s ^{-X-] q - (CHR 3)}} r - is selected from wherein each ^{R 3} is independently selected from hydrogen and methyl,
Each X is independently selected from -O-, -S-, -NH-, and -NR-, wherein R is selected from hydrogen and methyl;
s is an integer from 2 to 6,
q is an integer from 1 to 5;
r is an integer from 2 to 10)
Dithiol,
(B) Formula (24):
_{^{CH 2 = CH-O - [}} - R 2 -O-] m -CH = CH 2 (24)
(Where
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined above,
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6)
The reaction product of a reaction product comprising a divinyl ether.
In certain embodiments, the reactant may also include a multifunctional compound such as (c) multifunctional compound B (-V) _z , where B, -V, and z are as defined herein. Defined by

In certain embodiments, suitable dithiols for use in preparing thiol-terminated polythioethers are those having formula (23), other dithiols disclosed herein, or disclosed herein. Any combination of dithiols can be mentioned. In certain embodiments, the dithiol has the formula (23):
HS-R ¹ -SH (23)
(Where
R ¹ is C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [— (CHR ³ ) _s —X—] _q- (CHR ³ ) _r-
here,
Each R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
s is an integer from 2 to 6,
q is an integer from 1 to 5;
r is an integer from 2 to 10)
It has the structure of.

In certain embodiments of the dithiol of formula (23), R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —.

In certain embodiments of the compound of formula (23), X is selected from —O— and —S—, and thus — [— (CHR ³ ) _s —X—] _q — ( CHR ³⁾ _r - _{^{is, - [(- CHR 3 -}} ) s -O-] q - (CHR 3) r -, or _{^{- [(- CHR 3 2 -}} ) s -S-] q - (CHR 3) _r- . In certain embodiments, p and r are equal, eg, p and r are both 2.

In certain embodiments of the dithiol of formula (23), R ¹ is selected from C _2-6 alkanediyl, and — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —. The

In certain embodiments of the dithiol of formula (23), R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, and in certain embodiments, X is —O—, and in certain embodiments, X is —S—.

In certain embodiments wherein R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, s is 2, r is 2, q is 1, and X is —S. In certain embodiments, s is 2, q is 2, r is 2, and X is —O—, and in certain embodiments, s is 2, r is 2, and q is 1. , And X are —O—.

In certain embodiments, wherein R ¹ is — [— (CHR ³ ) _s —X—] _q — (CHR ³ ) _r —, each R ³ is hydrogen, and in certain embodiments, at least 1 One R ³ is methyl.

Examples of suitable dithiols include, for example, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,3-dimercapto-3-methylbutane, dipentene dimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl substitution Examples include dimercaptodiethyl sulfide, dimethyl substituted dimercaptodiethyl sulfide, dimercaptodioxaoctane, 1,5-dimercapto-3-oxapentane, and any combination of the foregoing. The polythiol may have one or more pendant groups selected from lower (eg C _1-6 ) alkyl groups, lower alkoxy groups, and hydroxyl groups. Suitable alkyl pendant groups include, for example, C _1-6 straight chain alkyl, C _3-6 branched alkyl, cyclopentyl, and cyclohexyl.

Other examples of suitable dithiols include dimercaptodiethylsulfide (DMDS) (wherein R ¹ is — [(— CH ₂ —) _s —X—] _q — (CH ₂ ) _r —, where s is 2, r is 2, q is 1, and X is -S-), dimercaptodioxaoctane (DMDO) (in formula (23), R ¹ is-[(-CH _2- ) _s -X- _{] q - (CH 2) r} -, where s is in 2, q is 2, r is 2, and X is -O-), and 1,5-dimercapto-3-oxa-pentane (formula (23), R ¹ is — [(— CH ₂ —) _s —X—] _q — (CH ₂ ) _r —, where s is 2, r is 2, q is 1, and X is —O—. It is also possible to use dithiols containing both heteroatoms in the carbon backbone and pendant alkyl groups such as methyl groups. Such compounds, for _{example, HS-CH 2 CH (CH} 3) -S-CH 2 CH 2 -SH, HS-CH (CH 3) CH 2 -S-CH 2 CH 2 methyl such -SH substituted DMDS, as well as _{HS-CH 2 CH (CH 3} ) -S-CHCH 3 CH 2 -SH, and _{HS-CH (CH 3) CH} 2 -S-CH 2 CH (CH 3) dimethyl-substituted DMDS such as -SH.

Suitable divinyl ethers for preparing polythioethers include, for example, formula (24):
^{_{CH 2 = CH-O - (}} - R 2 -O-) m -CH = CH 2 (24)
Of divinyl ether and the like, wherein ^{R 2} in the formula _{(24), C 2 to 6} n-alkanediyl _{group, C 3 to 6} branched alkanediyl _{group, C 6-8} cycloalkane diyl _{group, C. 6 to 10} alkanecycloalkanediyl groups, and — [(— CH ₂ —) _s —O—] _q — (— CH ₂ —) _r —, where s is an integer in the range of 2 to 6, q is An integer from 1 to 5, and r is an integer from 2 to 10. In certain embodiments of the divinyl ether of formula (24), R ² is a C _2-6 n-alkanediyl group, a C _3-6 branched alkanediyl group, a C _6-8 cycloalkanediyl group, C _{6. To 10} alkanecycloalkanediyl groups, and in certain embodiments, — [(— CH ₂ —) _s —O—] _q — (— CH ₂ —) _r —.

  Suitable divinyl ethers include, for example, at least one oxyalkanediyl group such as a compound having 1 to 4 oxaalkanediyl groups (ie, a compound in which m is an integer ranging from 1 to 4 in formula (24)). And the like. In certain embodiments, m in formula (24) is an integer ranging from 2 to 4. It is also possible to employ commercially available divinyl ether mixtures, characterized in that the number of oxyalkanediyl units per molecule is a non-integer average value. Therefore, m in equation (24) is a rational number in the range from 0 to 10.0, for example, from 1.0 to 10.0, from 1.0 to 4.0, or from 2.0 to 4.0. The value of can also be taken.

Examples of suitable vinyl ethers include divinyl ether, ethylene glycol divinyl ether (EG-DVE) (R ² in formula (24) is ethanediyl, and m is 1), butanediol divinyl ether (BD-DVE) (formula (24) R ² in the formula is butanediyl, and m is 1), hexanediol divinyl ether (HD-DVE) (R ² in formula (24) is hexanediyl, and m is 1), diethylene glycol divinyl ether (DEG-DVE) (formula ( 24) R ² is ethanediyl, and m is 2), triethylene glycol divinyl ether (R ² in formula (24) is ethanediyl, and m is 3), tetraethylene glycol divinyl ether (R ² in formula (24) is Ethanediyl, and m is 4), cyclohex Nji divinyl ether, polytetrahydrofuryl divinyl ether, trivinyl ether monomers such as trimethylolpropane trivinyl ether, tetrafunctional ether monomers such pentaerythritol ether, and combinations of two or more such polyvinyl ether monomers like. The polyvinyl ether may have one or more pendant groups selected from alkyl groups, hydroxyl groups, alkoxy groups, and amine groups.

In certain embodiments, divinyl ethers where R ² in formula (24) is a C _3-6 branched alkanediyl can be prepared by reacting a polyhydroxy compound with acetylene. As an example of this type of divinyl ether, R ² in formula (24) is an alkyl-substituted methanediyl group, for example —CH (—CH ₃ ) — (wherein R ² in formula (24) is ethanediyl, and m is 3.8 ) Or an alkyl substituted ethanediyl.

Other useful divinyl ethers include compounds in which R ² in formula (24) is polytetrahydrofuryl (poly-THF) or polyoxyalkanediyl, and has, for example, an average of about 3 monomer units. .

  Two or more types of polyvinyl ether monomers of the formula (24) may be used. Thus, in certain embodiments, two dithiols of formula (23) and one polyvinyl ether monomer of formula (24), one dithiol of formula (23) and two polyvinyl ether monomers of formula (24), formula Using two or more dithiols of (23) and two divinyl ether monomers of formula (24) and one or both compounds of formula (23) and formula (24) Polythioethers can be produced.

  In certain embodiments, the polyvinyl ether monomer comprises the reactants used to prepare the thiol-terminated polythioether in a molar percentage of 20 to less than 50, and in certain embodiments, in a molar percentage of less than 30 to 50. Including.

  In certain embodiments provided by the present disclosure, the relative amounts of dithiol and divinyl ether are selected to produce a polythioether having terminal thiol groups. Thus, a dithiol of formula (23), or a mixture of at least two different dithiols of formula (23), with a divinyl ether of formula (24) or a mixture of at least two different divinyl ethers of formula (24); The reaction is carried out in a relative amount such that the molar ratio of thiol group to vinyl group is more than 1: 1, for example, 1.1 to 2.0: 1.0.

  The reaction between dithiol and divinyl ether and / or the reaction between polythiol and polyvinyl ether can be catalyzed by a free radical catalyst. Suitable free radical catalysts include, for example, azo compounds such as azobisnitriles such as azo (bis) isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and t-butyl peroxide; and hydrogen peroxide. An inorganic peroxide is mentioned. The catalyst may be a free radical catalyst, an ionic catalyst, or ultraviolet irradiation. In certain embodiments, the catalyst does not contain acidic or basic compounds and does not produce acidic or basic compounds upon decomposition. Examples of free radical catalysts include Vazo (R) -57 (Du Pont), Vazo (R) -64 (Du Pont), Vazo (R) -67 (Du Pont), V-70 (R) (Wako Specialty Chemicals) and V-65B (registered trademark) (Wako Specialty Chemicals). Examples of other free radical catalysts are alkyl peroxides such as t-butyl peroxide. The reaction can proceed with or without cationic photoinitiating moieties or by irradiation with ultraviolet light.

  The thiol-terminated polythioether provided by the present disclosure combines at least one compound of formula (23) and at least one compound of formula (24), followed by addition of a suitable catalyst and a temperature of 30 ° C. to 120 ° C. For example, 70 to 90 ° C., for 2 to 24 hours, for example 2 to 6 hours, and the like.

As disclosed herein, the thiol-terminated polythioether can comprise a multifunctional polythioether. That is, the thiol-terminated polythioether can have an average functionality greater than 2.0. Suitable multifunctional thiol-terminated polythioethers include, for example, formula (28a):
_{^{{HS-R 1 - [-}} S- (CH 2) p -O- (R 2 -O) m - (CH 2) 2 -S-R 1 -] n -S-V'-} z B (18a )
Wherein 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 is an integer from 3 to 6)
The thing which has the following structure is mentioned.

  Suitable polyfunctionalizing agents for use in preparing such multifunctional thiol-terminated polymers include trifunctionalizing agents, i.e. compounds with z = 3. Suitable trifunctionalizing agents include, for example, triallyl cyanate (TAC), as disclosed in paragraphs [0102] to [0105] of US Publication No. 2010/0010133, which is incorporated by reference. 1,2,3-propanetrithiol, isocyanurate-containing trithiols, and mixtures thereof, and isocyanurates, for example, as disclosed in US Patent Application Publication No. 2011/0319559, incorporated by reference. . Other useful polyfunctionalizing agents include trimethylolpropane trivinyl ether, and US Pat. Nos. 4,366,307, 4,609,762, and 5,225,472, each incorporated by reference. And the described polythiols. Mixtures of multifunctional agents can also be used. As a result, the bis (sulfonyl) alkanol-containing polythioethers provided by the present disclosure can have a wide range of average functionality. For example, a trifunctional agent can provide an average functionality of 2.05 to 3.0, such as 2.1 to 2.6. A wider range of average functionality can be achieved by using polyfunctionalizing agents that are tetrafunctional or higher. Functionality can also be determined by factors such as stoichiometry, as will be appreciated by those skilled in the art.

  Thiol-terminated polythioethers and bis (sulfonyl) alkanol-containing polythioethers having a functionality greater than 2.0 are each incorporated by reference, US Patent Application Publication No. 2010/0010133, US Patent Application Publication No. 2011/0319559, And can be prepared by methods similar to the bifunctional thiol-terminated polythioethers described in US Pat. No. 6,172,179. In certain embodiments, the polythioether comprises (i) one or more dithiols described herein, (ii) one or more divinyl ethers described herein, and (Iii) may be prepared by combining with one or more multifunctional agents. The mixture can then be reacted, optionally in the presence of a suitable catalyst, to provide a thiol-terminated polythioether or bis (sulfonyl) alkanol containing polythioether having a functionality greater than 2.0.

In certain embodiments, polythioethers, including thiol-terminated polythioethers, bis (sulfonyl) alkanol-containing polythioethers, and any capped analogs of the foregoing, correspond to polythioethers having a molecular weight distribution. In certain embodiments, useful polythioethers are from 500 daltons to 20,000 daltons, in certain embodiments, 2,000 daltons to 5,000 daltons, and in certain embodiments, 3,000 daltons. A number average molecular weight in the range of 1 to 4,000 daltons. In certain embodiments, useful polythioethers exhibit polydispersities (M _w / M _n : weight average molecular weight / number average molecular weight) in the range of 1 to 20, and in certain embodiments, from 1 to The range is 5. The molecular weight distribution of the polythioether can be characterized, for example, by gel permeation chromatography.

Metal Ligand-Containing Prepolymer Bis (sulfonyl) alkanol represents one type of metal ligand that can be incorporated into the main chain of a polymer, such as a sulfur-containing prepolymer, and improves surface adhesion. Other metal ligands can also be incorporated into the polymer backbone to enhance surface adhesion. In certain embodiments, such as for aerospace sealant applications, the metal ligand is disposed on the surface of aluminum, aluminum oxide, Al (III), anodized aluminum, titanium, titanium oxide, and / or Alodine®. The ligand can be selected. Metal ligands can form bidentate, tridentate, or more multidentate coordination complexes to surface atoms. Thus, metal ligand-containing prepolymers include any bis (sulfonyl) alkanol-containing prepolymer disclosed herein in which the bis (sulfonyl) alkanol group is replaced with another metal ligand. Similarly, as a method of synthesizing metal ligand-containing prepolymers, derivatives thereof, and capped analogs thereof, suitable for any method for preparing bis (sulfonyl) alkanol-containing prepolymers described herein. The thing which employ | adopted the metal chelating agent is mentioned. In addition to the portion -L- containing metal ligands, metal chelators R ⁹ -L-R ⁹ includes groups R ⁹ containing terminal groups that react with the precursor of sulfur-containing polymer. In certain embodiments, each R ⁹ includes a terminal group that reacts with a thiol group, such as an alkenyl, epoxy, or Michael acceptor group.

Strong as metal ligands, especially aluminum (III) metal ligands, such as —OH, —PO ₄ , —SO ₄ , —COOH, —C═O, and —NH ₂ groups, which can donate electrons to the metal's empty orbitals. Lewis base. Basic donor groups effective for the formation of multidentate complexes with aluminum (III) include aliphatic monohydroxy acid anions, catecholates, aromatic hydroxy acid anions, 3-hydroxy-4-pyridinone, hydroxamate, and 3-hydroxy-2-pyridinone is mentioned. Stable aluminum (III) complexes include multidentate ligands with negative oxygen electron donors. Metal ligands can form multidentate complexes with metals, such as bidentate or tridentate complexes.

  In certain embodiments, the functional group of the metal ligand is a group derived from a metal chelator selected from bis (sulfonyl) alkanols, hydroxypyridinones, and acetylacetonates.

  Examples of chelating agents for aluminum, aluminum oxide and Al (III) include 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy-2-pyridinone, 2- 2'-dihydroxyazobenzene, 8-hydroxyquinoline, oxylate, malonate, citrate, iminodiacetic acid, picolinic acid, maltol, kojic acid, N, N'-diacetic acid (EDTA), N- (2-hydroxy) ethylenediaminetriacetic acid (HEDTA), ethylenediamine-N, N′-bis (2-hydroxyphenylacetic acid (EDDHA), and N, N′-bis (hydroxybenzyl) ethylenediamine-N, N′-diacetic acid (HBED), acetoacetate, acetylacetate Nates, catecholates, hydroxamates, and Other aluminum chelators and aluminum oxide chelators are described in, for example, Yokel, “Coordination Chemistry Reviews 2002,” 228, 97-113, and Martell et al., “Complexes. Chemical Review 1996 (Coordination Chemistry Reviews 1996), 149, 311 to 328.

Examples of titanium metal ligands or titanium oxide metal ligands include H ₂ O ₂ , acetoacetonate (CH ₂ (COCH ₃ ) ₂ ), EDTA, trans-1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid ( GEDTA, (CH ₂ OCH ₂ CH ₂ N (CH ₂ COOH) ₂ ) ₂ ), diethylenetriaminepentaacetic acid (DTPA, HOOCH ₂ N (CH ₂ CH ₂ N (CH ₂ COOH) ₂ ) ₂ )), nitrile triacetic acid ( NTA, N (CH ₂ COOH) ₃ ), salicylic acid, lactic acid, acetoacetonate, triethanolamine, and any combination of the foregoing.

In certain embodiments, the metal ligand comprises at least two heteroatom groups (heteroatom-containing groups) that can coordinate to the aluminum (III) surface. In certain embodiments, the metal ligand is —OH, —PO ₄ , —P (O) ₂ —, —SO ₄ , —S (O) ₂ —, —COOH, —C═O, —NH ₂ , At least two heteroatom groups selected from —NH— and any combination of the foregoing.

In certain embodiments, the functional group of the metal ligand is represented by formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and any combination of the foregoing:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
Wherein -X- is independently selected from -C (O)-or -S (O) _2- , each n is independently selected from 1, 2, and 3, and R ⁵ is C _1-3 Alkanediyl)
The part selected from is included. In certain embodiments, each X is —C (O) —, and each n is 1. In certain embodiments, each X is —S (O) ₂ —, and each n is 1. .

With respect to bis (sulfonyl) alkanol-containing polythioethers, other metal ligands may be incorporated into the main chain of the prepolymer, such as a sulfur-containing prepolymer containing polythioether. Thus, in certain embodiments, the metal ligand-containing prepolymer has the formula (26):
^{-A-R 9 '-L-R} 9' -A- (26)
(Where
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6)
Including the part.

The metal chelator R ⁹ -LR ⁹ includes, for example, a group R ⁹ that reacts with a thiol group and a metal ligand -L-. The metal ligand -L- can include, for example, moieties of formulas (25a) to (25e). In certain embodiments, the metal chelator is selected from bis (sulfonyl) alkanols, hydroxypyridinones, acetylacetonates, and any combination of the foregoing.

In certain embodiments, the metal ligand-containing prepolymer comprises a metal ligand-containing polythioether of formula (28a), a metal ligand-containing polythioether of formula (28b), or combinations thereof:
^{R 6 -A - [- R 9} '-L-R 9' -A-] N -R 6 (28a)
^{{R 6 -A - [- R} 9 '-L-R 9' -A-] N -V'-} z B (28b)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a terminal thiol group,
Each -V'- is a group derived from the reaction of -V and thiol,
Each R ⁶ independently includes hydrogen or a moiety having a terminal reactive group)
including.

In certain embodiments of prepolymers of formula (28a) and formula (28b), each R ⁶ is hydrogen.

In certain embodiments of the prepolymers of formula (28a) and formula (28b), each R ⁶ is the same and the terminal reactive groups are —SH, —CH═CH ₂ , —NH ₂ , —OH, It is selected from epoxy groups, polyalkoxysilyl groups, isocyanate groups, and Michael acceptor groups.

In certain embodiments, the thiol-terminated metal ligand-containing polythioether is
(A) the thiol-terminated polythioether of formula (18a), the thiol-terminated polythioether of formula (18b), or combinations thereof:
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
{HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SV′—} _z B (18b )
(Where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s —. X—] _q — (— CHR ³ —) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a terminal thiol group,
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated polythioether comprising:
(B) a metal chelating agent R ⁹ -LR ⁹ (wherein each R ⁹ is a moiety containing a terminal group independently reacting with a thiol group, and -L- is a moiety containing a metal ligand). Including the reaction product of the containing reactant.

In certain embodiments of formula (18a) and formula (18b), the metal ligand is selected from formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and Any combination of things:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(Where
-X- is independently selected from -C (O)-or -S (O) _2-
Each n is independently selected from 1, 2, and 3;
R ⁵ is C _1-3 alkanediyl)
A portion selected from:

  In certain embodiments of formula (18a) and formula (18b), the metal ligand comprises a bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or any combination of the foregoing.

  In certain embodiments, the polythioether of formula (18a) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether.

  In certain embodiments, the polythioether of formula (18b) comprises a reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether, and triallyl cyanurate.

In certain embodiments, the thiol-terminated metal ligand-containing polythioether prepolymer is
(A) A thiol-terminated metal ligand-containing polythioether of formula (29a), a thiol-terminated metal ligand-containing polythioether of formula (29b), or a combination thereof:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the core of the z-valent alkenyl-terminated polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6;
Each V is a group containing a terminal alkenyl group;
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated metal ligand-containing polythioether comprising:
(B) a reaction product of a reaction product containing a polyalkenyl compound.

In certain embodiments of the polythioether of formula (29a) and formula (29b), the metal ligand is of formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), And any combination of the foregoing:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(Where
-X- is independently selected from -C (O)-or -S (O) _2-
Each n is independently selected from 1, 2, and 3;
R ⁵ is C _1-3 alkanediyl)
The part selected from is included.

  In certain embodiments of the thiol-terminated metal ligand-containing polythioether of formula (29a) and formula (29b), the polyalkenyl compound comprises diethylene glycol divinyl ether, triallyl cyanurate, or combinations thereof.

In certain embodiments, the method for preparing a thiol-terminated metal ligand-containing polythioether of formula (29a) comprises: Reacting with a metal chelator (N) mole comprising:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ includes hydrogen or methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6).

In certain embodiments of the method, the metal ligand is Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and any combination of the foregoing:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(Where
-X- is independently selected from -C (O)-or -S (O) _2-
Each n is independently selected from 1, 2, and 3;
R ⁵ is C _1-3 alkanediyl)
The part selected from is included.

  In certain embodiments of the method, the metal chelator comprises a bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or any combination of the foregoing.

In certain embodiments, the method for preparing a thiol-terminated metal ligand-containing polythioether of formula (29b) comprises converting a thiol-terminated metal ligand-containing polythioether of formula (29a) (z) moles to 1 mole of multifunctional agent B. Comprising reacting with {V} _z :
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ includes hydrogen or methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - wherein, where s, q, r, ^{R 3,} and X are as defined in ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a terminal thiol group,
Each -V'- is a group derived from the reaction of -V and a thiol).

In certain embodiments of the method, the metal ligand is Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and any combination of the foregoing:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(Where
-X- is independently selected from -C (O)-or -S (O) _2-
Each n is independently selected from 1, 2, and 3;
R ⁵ is C _1-3 alkanediyl)
The part selected from is included.

  In certain embodiments of the method, the metal chelator is selected from bis (sulfonyl) alkanols, hydroxypyridinones, acetylacetonates, or any combination of the foregoing.

Metal Ligand-Containing Sulfur-Containing Prepolymers In addition to polythioether prepolymers, metal ligands may be incorporated into the backbone of other polymers such as other sulfur-containing polymers to improve adhesion. The sulfur-containing polymer can be any polymer having at least one sulfur atom in the repeating unit, including, for example, polymeric thiols, polythiols, thioethers, polythioethers, sulfur-containing polyformals, and polysulfides. It is not limited. As used herein, “thiol” refers to a compound that contains a thiol or mercaptan group, ie, an “SH” group, as the only functional group, or other such as a hydroxyl group, such as a thioglycerol, eg, thioglycerol. Means a compound containing a combination of Polythiol means a compound that has multiple SH groups, such as dithiol or higher functionality thiols. Such groups are generally terminal and / or pendant groups that have active hydrogens that react with other functional groups. The polythiol can contain both terminal and / or pendant sulfur (—SH) and non-reactive sulfur atoms (—S— or —S—S—). Thus, the term polythiol generally includes polythioethers and polysulfides.

  The term polysulfide means a polymer containing one or more sulfide bonds, ie -Sx-bonds, where x is 2 to 4, in the polymer backbone and / or pendant positions on the polymer chain. To do. In certain embodiments, the polysulfide polymer will have more than one sulfur-sulfur bond. Suitable polysulfides are commercially available, for example, from Akzo Nobel and Toray Fine Chemicals under the product names Thioplast® and Thiocol-LP. Thioplast® products are available in a wide range of molecular weights, for example ranging from less than 1,100 to more than 8,000 (molecular weight is the average molecular weight in grams per mole). The polysulfide may have a number average molecular weight of 1,000 to 4,000 daltons.

  Sulfur-containing polyformal prepolymers useful for aerospace sealant applications are disclosed, for example, in US Patent Application Publication No. 2012/0234205 and US Patent Application Publication No. 2012/0238707.

Bis (sulfonyl) alkanol-containing polythioether synthesis method Generally, a thiol-terminated bis (sulfonyl) alkanol-containing polythioether is a thiol-terminated polythioether, or a mixture of thiol-terminated polythioethers, and a bis (sulfonyl) alkanol. ) Can be prepared by reacting with an alkanol. In certain embodiments, the thiol-terminated bis (sulfonyl) alkanol-containing polythioether is a bifunctional thiol-terminated polythioether or a mixture of difunctional thiol-terminated polythioethers having a bis ( It can be prepared by reacting with a bis (sulfonyl) alkanol, such as a sulfonyl) alkanol or bis (vinylsulfonyl) alkanol.

In certain embodiments, the process for preparing a thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) comprises thiol-terminated polythioether (N + 1) moles of formula (18a) and bis (sulfonyl) of formula (4a). ) Reacting with an alkanol (N) mole:
^{H-A - [- R 8} '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -H (16a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
_{^{R 8 -S (O) 2 -R}} 10 -CH (-OH) -R 10 -S (O) 2 -R 8 (4a)
(Where
N is an integer from 1 to 10,
Each R ⁸ is independently selected from moieties containing end groups that react with terminal thiol groups;
Each R ^{8 ′} is a moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group,
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6).

  In certain embodiments of the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a), N is 1, 2, 3, 4, 5, 6, 7, 8, 9, In the embodiment, N is 10. In certain embodiments of the bis (sulfonyl) alkanol containing polymer of formula (16a), the molecular weight is from 200 daltons to 20,000 daltons. In certain embodiments, the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) comprises a combination of bis (sulfonyl) alkanol-containing polythioethers of formula (16a) with different values of N. In certain embodiments of the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a), N is 1. Thus, in practice, when preparing the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a), the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) has different values of N The molar ratio of thiol-terminated polythioether to bis (sulfonyl) alkanol need not be an integer, such as corresponding to a mixture of bis (sulfonyl) alkanol-containing polythioethers.

In certain embodiments, the process for preparing the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16b) comprises 1 mole of the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a) _Comprising reacting with a polyfunctionalizing agent B {V} _z of:
{H-A - [- R 8 '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -V'-} z B (16b)
^{H-A - [- R 8} '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -H (16a)
(Where
Each R ^{8 'is} a moiety derived from the reaction of bis (sulfonyl) alkanol and a thiol group, each R ¹⁰ is selected from C _{1 to 3} alkanediyl and substituted C _{1 to 3} alkanediyl independently, wherein one The one or more substituents are —OH;
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V and a thiol).

  In certain embodiments, the reaction between a thiol-terminated bis (sulfonyl) alkanol-containing polythioether and a bis (sulfonyl) alkanol, such as bis (vinylsulfonyl) alkanol, can be, for example, any amine disclosed herein. It is carried out in the presence of a catalyst such as an amine catalyst containing the catalyst.

Thiol-terminated metal ligand-containing prepolymer synthesis method In certain embodiments, a thiol-terminated metal ligand-containing prepolymer, such as a thiol-terminated metal ligand-containing polythioether, is a bifunctional thiol-terminated prepolymer, or a bifunctional thiol-terminated prepolymer. Reacting the mixture with a metal chelator having at least two groups that react with thiol groups, such as bis (sulfonyl) alkanols, hydroxypyridinones, or acetylacetonates, which have at least two end groups that react with thiol groups. Can be prepared.

In certain embodiments, the method for preparing a thiol-terminated metal ligand-containing prepolymer of formula (29a) comprises converting (N + 1) moles of thiol-terminated polythioether of formula (18a) to (N) moles of metal chelator R ⁹ −. Comprising reacting with LR ⁹ :
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH (18a)
(Where
N is an integer from 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently a formula (12)
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6).

  In certain embodiments of the thiol-terminated metal ligand-containing polythioether of formula (29a), N is 1, 2, 3, 4, 5, 6, 7, 8, 9, and in certain embodiments , N is 10. In certain embodiments of the metal ligand-containing prepolymer of formula (29a), the molecular weight is from 200 daltons to 20,000 daltons. In certain embodiments, the thiol-terminated metal ligand-containing prepolymer of formula (6) comprises a combination of metal ligand-containing prepolymers of formula (29a) with different values of N. In certain embodiments of the thiol-terminated metal ligand-containing prepolymer of formula (29a), N is 1. Thus, in practice, when preparing the thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (29a), the thiol-terminated metal ligand-containing prepolymer of formula (29a) contains thiol-terminated metal ligands having different values of N The molar ratio of thiol-terminated polythioether to metal chelator need not be an integer, such as corresponding to a mixture of prepolymers.

In certain embodiments, the method for preparing a thiol-terminated metal ligand-containing prepolymer of formula (29b) comprises converting 1 mole of polyfunctionalizing agent B to a thiol-terminated metal ligand-containing prepolymer of formula (29a) (z). Comprising reacting with {V} _z :
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
(Where
Each R ^{9 'is} independently a moiety derived from the reaction of R ⁹ and thiol groups of the metal chelating agent R ⁹ -L-R ^9, wherein each of R ⁹ includes a terminal group which reacts with a thiol, L includes a metal ligand;
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V and a thiol).

  In certain embodiments, the reaction between the thiol-terminated metal ligand-containing polythioether and the metal chelator is performed in the presence of a catalyst, for example, an amine catalyst including any amine catalyst disclosed herein. .

Alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether prepolymers The thiol-terminated bis (sulfonyl) alkanol-containing polythioethers provided by the present disclosure can be reacted with polyalkenyls such as dialkenyl ethers and / or alkenyl-terminated polyfunctionalizing agents. An alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether prepolymer is provided. The alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether prepolymer may be combined with a curing agent to provide a curable composition such as a sealant composition.

For example, in certain embodiments, the alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether prepolymer is
(A) Thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16a), thiol-terminated bis (sulfonyl) alkanol-containing polythioether of formula (16b), and combinations thereof:
^{H-A - [- R 8} '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -H (16a)
{H-A - [- R 8 '-S (O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -R 8' -A-] N -V'-} z B (16b)
(Where
N is an integer from 1 to 10,
Each R ^{8 ′} is a moiety derived from the reaction of a bis (sulfonyl) alkanol and a thiol group,
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated bis (sulfonyl) alkanol-containing polythioether selected from
(B) a reaction product of a reaction product containing a polyalkenyl compound.

  In certain embodiments, the polyalkenyl compound is selected from divinyl ethers or mixtures of divinyl ethers including any divinyl ether disclosed herein, alkenyl-terminated polyfunctionalizing agents, and combinations thereof.

  In certain embodiments of the above reaction, (a) is a polythioether of formula (16a) and (b) is a polyvinyl ether selected from divinyl ethers, alkenyl terminated polyfunctionalizing agents, and combinations thereof. is there.

  In certain embodiments of the above reaction, (a) is a polythioether of formula (16a) and (b) is a polyalkenyl selected from diethylene glycol divinyl ether (DEG-DVE), TAC, and combinations thereof Ether.

Alkenyl-terminated metal ligand-containing polythioether prepolymers The thiol-terminated metal ligand-containing prepolymers provided by the present disclosure can react with polyalkenyls such as dialkenyl ethers and / or alkenyl-terminated polyfunctionalizing agents, and contain alkenyl-terminated metal ligands A prepolymer is provided. The alkenyl-terminated metal ligand-containing prepolymer may be combined with a curing agent to provide a curable composition such as a sealant composition.

For example, in certain embodiments, the alkenyl-terminated metal ligand-containing prepolymer is
(A) Thiol-terminated metal ligand-containing polythioether of formula (29a), metal ligand-containing polythioether of formula (29b), and combinations thereof:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (19a)
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
(Where
N is an integer from 1 to 10,
Each R ^{9 ′} is a moiety derived from the reaction of a metal chelating agent R ⁹ -LR ⁹ with a thiol group, where -L- contains a metal group and each R ⁹ represents a group that reacts with a thiol group. Including
Each ^{R 10} is independently selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH,
Each A is independently formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12)
And where
Each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, and — [(— CHR ³ —) _s -X-] _q -(-CHR ^3- ) _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 R ³ is independently selected from hydrogen and methyl;
Each X is independently selected from —O—, —S—, and —NR ⁵ —;
Wherein R ⁵ is selected from hydrogen and methyl;
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, and — [(— CHR ³ —) _s —X—] _q — (— CHR ³ _{-) r} - is selected from wherein s, q, r, ^{R 3,} and X are as defined for ^{R 1,}
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 the z-valent polyfunctional agent B (-V) _z core, where z is an integer from 3 to 6;
Each V is a group containing a terminal group that reacts with a thiol group,
Each -V'- is a group derived from the reaction of -V and thiol)
A thiol-terminated metal ligand-containing prepolymer selected from
(B) a reaction product of a reaction product containing a polyalkenyl compound.

  In certain embodiments, the polyalkenyl compound is selected from divinyl ethers or mixtures of divinyl ethers including any divinyl ether disclosed herein, alkenyl-terminated polyfunctionalizing agents, and combinations thereof.

  In certain embodiments of the above reaction, (a) is a polythioether of formula (29a) and (b) is a polyvinyl ether selected from divinyl ethers, alkenyl terminated polyfunctionalizing agents, and combinations thereof. is there.

  In certain embodiments of the above reaction, (a) is a polythioether of formula (29a) and (b) is a polyalkenyl selected from diethylene glycol divinyl ether (DEG-DVE), TAC, and combinations thereof Ether.

Prepolymers containing capped bis (sulfonyl) alkanols and prepolymers containing capped metal ligands Bis (sulfonyl) alkanol-containing polythioethers and metal ligand-containing prepolymers contain thiol-terminated bis (sulfonyl) alkanols Use in specific curing chemistries by capping or terminating bis (sulfonyl) alkanol containing polythioether or metal ligand containing prepolymers, such as polythioether or thiol terminated metal ligand containing prepolymers, with appropriate functional groups May be adapted. Capped analogs of thiol-terminated polythioethers are disclosed, for example, in US Pat. No. 6,172,179 and US Patent Application Publication No. 2011/0319559.

  For example, in certain embodiments, bis (sulfonyl) alkanol-containing polythioethers or metal ligand-containing prepolymers have terminal groups other than unreacted thiol groups, such as hydroxyl, alkenyl, isocyanate, amine, epoxy, hydrolysable It has a functional group, for example, a polyalkoxysilyl group, a Michael acceptor group, or an epoxy group.

  Capped analogs can be prepared by a number of methods known to those skilled in the art. For example, to obtain a polythioether containing a capped bis (sulfonyl) alkanol or a prepolymer containing a capped metal ligand, a thiol terminated bis (sulfonyl) alkanol containing polythioether or a thiol terminated metal ligand containing prepolymer The polymer may be reacted with a compound having a terminal group that reacts with a thiol group.

  To obtain an alkenyl-terminated bis (sulfonyl) alkanol-containing polythioether or alkenyl-terminated metal ligand-containing prepolymer, the thiol-terminated bis (sulfonyl) alkanol-containing polythioether or thiol-terminated metal ligand-containing prepolymer is obtained in the presence of a dibutyltin dilaurate catalyst. And may be reacted with a compound containing an isocyanate group and a terminal alkenyl group, such as a group derived from TMI, 2-isocyanatoethyl methacrylate, or allyl isocyanate.

  Polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers and polyalkoxysilyl-terminated metal ligand-containing prepolymers, for example, containing thiol-terminated bis (sulfonyl) alkanol-containing polythioethers or thiol-terminated metal ligands in the presence of dibutyltin dilaurate Can be prepared by reacting a prepolymer with an isocyanatoalkyltrialkoxysilane, such as 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane, containing the corresponding polyalkoxysilyl terminated bis (sulfonyl) alkanol Polythioethers or corresponding polyalkoxysilyl-terminated metal ligand-containing prepolymers are provided.

  Epoxy-terminated bis (sulfonyl) alkanol-containing polythioethers and epoxy-terminated metal ligand-containing prepolymers, for example, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers or thiol-terminated metal ligand-containing prepolymers, presence of monoepoxides such as allyl glycidyl ether To provide a corresponding epoxy-terminated bis (sulfonyl) alkanol-containing polythioether or a corresponding epoxy-terminated metal ligand-containing prepolymer.

Amine-terminated bis (sulfonyl) alkanol-containing polythioethers and amine-terminated metal ligand-containing prepolymers, for example, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers or thiol-terminated metal ligand-containing prepolymers, together with free radical initiators, are monofunctional It can be prepared by reacting with 4-aminobutyl vinyl ether. Alternatively, an amine-terminated bis (sulfonyl) alkanol-containing polythioether or an amine-terminated metal ligand-containing prepolymer is an isocyanate-terminated bis (sulfonyl) alkanol-containing polythioether or an isocyanate-terminated metal ligand-containing prepolymer. It may be obtained by reaction with a diamine, such as aniline, to provide a corresponding amine-terminated bis (sulfonyl) alkanol-containing polythioether or a corresponding amine-terminated metal ligand-containing prepolymer. Amine-terminated bis (sulfonyl) alkanol-containing polythioethers and amine-terminated metal ligand-containing prepolymers can also be used in the presence of Bu ₂ SnO or NaOMe, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers, or alkanol-terminated or hydroxy-terminated metal ligands. Containing prepolymers may be obtained by reacting an amino-substituted benzoate such as ethyl-4-aminobenzoate with an elevated temperature and corresponding amine-terminated bis (sulfonyl) alkanol-containing polythioether or corresponding amine-terminated A metal ligand-containing prepolymer is provided.

Isocyanate-terminated bis (sulfonyl) alkanol-containing polythioethers and isocyanate-terminated metal ligand-containing prepolymers, for example, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers or thiol-terminated, optionally in the presence of a catalyst such as dibutyltin dilaurate Metal ligand-containing prepolymers were prepared from TDI, Isonate ™ 143L (polycarbodiimide modified diphenylmethane diisocyanate), Desmodur ™ N3400 (1,3-bis (6-isocyanatohexyl) -1,3-diazetidine- 2,4-dione), IPDI (isophorone diisocyanate), or Desmodur (be prepared by reacting a registered _{trademark) W (H} 12 MDI), such as diisocyanate . Isocyanate-terminated bis (sulfonyl) alkanol-containing polythioethers and isocyanate-terminated metal ligand-containing prepolymers include certain amine-terminated and thiol-terminated bis (sulfonyl) alkanol-containing polythioethers, amine-terminated and thiol-terminated metal ligand-containing prepolymers, etc. It can be used as an intermediate in the synthesis of other end-modified bis (sulfonyl) alkanol-containing polythioethers and end-modified metal ligand-containing prepolymers.

  Hydroxyl-terminated bis (sulfonyl) alkanol-containing polythioethers and hydroxy-terminated metal ligand-containing prepolymers include, for example, thiol-terminated bis (sulfonyl) alkanol-containing polythioethers or thiol-terminated metal ligand-containing prepolymers with groups and terminals that react with thiol groups. It can be prepared by reacting with a compound having a hydroxyl group.

In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether and the metal ligand-containing prepolymer can be terminated with a Michael acceptor group. In certain embodiments, the Michael acceptor group is a group derived from vinyl sulfone and has the formula (27):
—CH ₂ —C (R ¹³ ) ₂ —S (O) ₂ —CR ¹³ ═CH ₂ (27)
Wherein each R ¹³ is independently selected from hydrogen and C _1-3 alkyl.
It has the structure of. In certain embodiments of formula (27), each R ¹³ is hydrogen. In certain embodiments, the Michael acceptor-terminated bis (sulfonyl) alkanol-containing polythioether reacts with a thiol group such as divinylsulfone, for example, in the presence of an amine catalyst. It can be prepared by reacting with a compound having a group and a terminal Michael acceptor group. Michael acceptor / polythioether chemistry and compounds are disclosed in US patent application Ser. No. 13 / 529,237, filed Jun. 13, 2012, which is incorporated by reference in its entirety. Examples of methods for preparing isocyanate-capped polythioethers and epoxy-capped polythioethers, and isocyanate-capped polythioethers and epoxy-capped polythioethers are described in US Pat. , 879, 955 B2.

Compositions Provided by the present disclosure are one or more bis (sulfonyl) alkanol-containing polythioethers and / or one or more bis (sulfonyl) alkanol-containing polythioether prepolymers, and / or one or more. Of metal ligand-containing prepolymers. The curable composition may further include a curing agent. The composition may further comprise additives, catalysts, fillers, and / or other sulfur-containing prepolymers including, for example, polythioethers, sulfur-containing polyformals, and / or polysulfides.

  Suitable curing agents are selected to react with the end groups of the bis (sulfonyl) alkanol containing polythioether, the metal ligand containing prepolymer, and optionally the sulfur containing prepolymer.

  In certain embodiments where the bis (sulfonyl) alkanol-containing polythioether, its prepolymer, or metal ligand-containing prepolymer is terminated with a thiol group, a suitable curing agent is a polyepoxide. Examples of suitable polyepoxides include, for example, hydantoin diepoxide, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, Novolac® type epoxides such as DEN ™ 438 (Dow Chemical Company), certain epoxides And polyepoxide resins such as fluorinated unsaturated resins and any combination of the foregoing. Polyepoxide means a compound having two or more reactive epoxy groups. In certain embodiments, the epoxy curing agent is selected from EPON ™ 828 (Momentary Specialty Chemicals, Inc), DEN ™ 431 (Dow Chemical Company), and combinations thereof. Examples of useful curing agents that react with thiol groups include diepoxides.

  In certain embodiments, the polyepoxy curing agent comprises an epoxy functional polymer. Examples of suitable epoxy functional polymers include epoxy functional sulfur-containing polyformal polymers disclosed in US Patent Application No. 13 / 050,988 and epoxy disclosed in US Patent No. 7,671,145. Functional polythioether polymers are mentioned. Generally, when used as a curing agent, the epoxy functional polymer is less than about 2,000 daltons, less than about 1,500 daltons, less than about 1,000 daltons, and in certain embodiments, less than about 500 daltons. Has a molecular weight.

  In certain embodiments, the polyepoxy is about 0.5 wt% to about 20 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt% of the composition, and In certain embodiments, it comprises about 3 wt% to about 5 wt%, where wt% is based on the total solids weight of the composition.

  In certain embodiments where the bis (sulfonyl) alkanol-containing polythioether, its prepolymer, or the metal ligand-containing prepolymer is terminated with a thiol group, a suitable curing agent is an acrylate or methacrylate ester of a polyol, synthesis Or an unsaturated compound such as an olefin-terminated derivative of a sulfur-containing compound such as a natural unsaturated resin compound, triallyl cyanurate, and polythioether.

  In certain embodiments, for example, when using amine and / or hydroxyl-terminated bis (sulfonyl) alkanol-containing polythioethers, prepolymers thereof, or amine and / or hydroxyl-terminated metal ligand-containing prepolymers, the present disclosure provides The composition may include an isocyanate curing agent, such as a diisocyanate and / or a triisocyanate curing agent. Examples of suitable isocyanate curing agents include toluene diisocyanate and any combination of the foregoing. Isocyanate curing agents are commercially available, for example, Baydur® (Bayer Material Science), Desmodur® (Bayer Material Science), Solbond® (DSM), ECCO (ECCO), Vestan. Examples are products with the trade names of (Evonik), Irodur (R) (Huntsman), Rhocoat (R) (Perstorp), and Vanchem (R) (VT Vanderbilt). In certain embodiments, the polyisocyanate curing agent includes isocyanate groups that react with thiol groups and are less reactive with Michael acceptor groups. Examples of useful curing agents that react with amine groups include polymeric polyisocyanates, non-limiting examples of which are urethane bonds (—NH—C (O) —O—), thiourethane bonds (—NH—). C (O) -S-), a thiocarbamate bond (-NH-C (S) -O-), a dithiourethane bond (-NH-C (S) -S-), and any combination of the foregoing. Polyisocyanates having a selected bond in the main chain can be mentioned.

  In certain embodiments, the isocyanate curing agent comprises an isocyanate functional polymer. Examples of suitable isocyanate functional polymers include the isocyanate functional sulfur-containing polyformal polymers disclosed in US patent application Ser. No. 13 / 051,002. Generally, when used as a curing agent, the isocyanate functional polymer is less than about 2,000 daltons, less than about 1,500 daltons, less than about 1,000 daltons, and in certain embodiments, less than about 500 daltons. Having a molecular weight of

  In such compositions, the isocyanate hardener is about 0.5 wt% to about 20 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt% of the composition. And in certain embodiments, comprises from about 3 wt% to about 5 wt% of the composition, where wt% is based on the total solids weight of the composition.

  In certain embodiments, such as when using an isocyanate-terminated bis (sulfonyl) alkanol-containing polythioether, a prepolymer thereof, or an isocyanate-terminated metal ligand-containing prepolymer, the composition provided by the present disclosure comprises an amine curing agent. including. Examples of useful curing agents that react with isocyanate groups include diamines, polyamines, polythiols, and polyols, including those disclosed herein.

  In certain embodiments, such as when using a Michael acceptor-terminated bis (sulfonyl) alkanol-containing polythioether, a prepolymer thereof, or a Michael acceptor-terminated metal ligand-containing prepolymer, the composition provided by the present disclosure is a simple composition. A curing agent selected from monomeric thiols, polythiols, polyamines, and blocked polyamines is included.

  Curing agents useful in the compositions provided by the present disclosure include compounds that react with end groups of bis (sulfonyl) alkanol-containing polythioethers or metal ligand-containing prepolymers, such as hydroxyl groups, alkenyl groups, epoxy groups, thiol groups, Examples thereof include a compound that reacts with an amine group or an isocyanate group.

  Examples of useful curing agents that react with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are disclosed herein.

  Examples of useful curing agents that react with alkenyl groups include dithiols and polythiols, examples of which are disclosed herein.

  The polyalkoxysilyl terminated bis (sulfonyl) alkanol-containing polythioether or metal ligand-containing prepolymer provided by the present disclosure can be hydrolyzed in the presence of water, including self-polymerization by condensation. Catalysts for use with polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers or polyalkoxysilyl-terminated metal ligand-containing prepolymers include organic titanium compounds such as tetraisopropoxy titanium, tetra-tert-butoxy titanium, titanium di (isopropoxy) ) Bis (ethylacetoacetate), and titanium di (isopropoxy) bis (acetylacetoacetate); organotin compounds dibutyltin dilaurate, dibutyltin bisacetylacetoacetate, and tin octylate; metal dicarboxylates such as Lead dioctylates; organozirconium compounds such as zirconium tetraacetylacetonate; and organoaluminum compounds such as aluminum triacetylacetonate It is below. Examples of other catalysts suitable for moisture curing include diisopropoxybis (ethylacetoacetonate) titanium, diisopropoxybis (acetylacetonato) titanium, and dibutoxybis (methylacetoacetonate) titanium. For polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers or polyalkoxysilyl-terminated metal ligand-containing prepolymers, moisture in the atmosphere can serve as a curing agent, so polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers or poly It can be appreciated that a curable composition containing an alkoxysilyl-terminated metal ligand-containing prepolymer need not include a curing agent. Accordingly, a composition comprising a polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether or a polyalkoxysilyl-terminated metal ligand-containing prepolymer, and a polyalkoxysilyl group curing agent means moisture in the atmosphere.

  In certain embodiments where the bis (sulfonyl) alkanol-containing polythioether, its prepolymer, or metal ligand-containing prepolymer is terminated with an epoxy group, a suitable curing agent is a polythiol, polyalkylene, or polyamine. Examples of other useful curing agents that react with terminal epoxy groups include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine (N -AEP), isophoronediamine (IPDA), m-xylenediamine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), amines, aromatic amines, ketimines, polyamines, polyamides, phenolic resins, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tet Hydrophthalic acid anhydride, anhydrides such endomethylene tetrahydrophthalic acid anhydride, polymercaptans, polysulfides, and other known curing agents to those skilled in the art.

  The compositions provided by this disclosure include selected curing agent (s) from about 90% to about 150%, from about 95% to about 125%, and in certain embodiments, in stoichiometric amounts. It may be included in an amount from about 95% to about 105%.

Additional Sulfur-Containing Prepolymers In certain embodiments, the compositions provided by the present disclosure are disclosed in bis (sulfonyl) alkanol-containing polythioethers, prepolymers, metal ligand-containing prepolymers, or herein. In addition to the reaction product of any one reaction, or any combination of the foregoing, includes one or more additional sulfur-containing prepolymers. The sulfur-containing prepolymer can be any prepolymer having at least one sulfur atom in its repeating unit, examples include polymeric thiols, polythiols, thioethers, polythioethers, sulfur-containing polyformals, and polysulfides, It is not limited to this. As used herein, a “thiol” is a compound that contains a thiol or mercaptan group, ie, an “SH” group, as the only functional group or in combination with other functional groups such as hydroxyl groups, such as thioglycerol. Means. Polythiol means a compound that has multiple SH groups, such as dithiol or higher functionality thiols. Such groups are generally terminal and / or pendant groups that have active hydrogens that react with other functional groups. The polythiol can contain both terminal and / or pendant sulfur (—SH) and non-reactive sulfur atoms (—S— or —S—S—). Thus, the term polythiol generally includes polythioethers and polysulfides.

Examples of additional sulfur-containing prepolymers useful in the compositions provided by the present disclosure are disclosed, for example, in US Pat. Nos. 6,172,179, 6,509,418, and 7,009,032. What is being done is mentioned. In certain embodiments, a composition provided by this disclosure has formula (30):
—R ¹ — [— S— (CH ₂ ) ₂ —O — [— R ² —O—] _m — (CH ₂ ) ₂ —S—R ¹ —] _n — (30)
Wherein each R ¹ is C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 cycloalkanealkanediyl, — [(— CH ₂ —) _s —X—] _q — (— CH _{2 -) r} -, and at least one -CH ₂ - unit is substituted with a methyl group _{- [(- CH 2 -)} s -X-] q - (- CH 2 -) r - is selected from, R ² _{C 2 to 6 alkanediyl, C 6-8 cycloalkanediyl, C 6 to 10} cycloalkane alkanediyl, and _{- [(- CH 2 -)} s -X-] q - (- CH 2 -) r - X is selected from O, S, and —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl, m is an integer from 0 to 10, and n is an integer from 1 to 60. , P is an integer from 2 to 6, q is an integer from 1 to 5, r is an integer from 2 to 10)
A polythioether having the structure: Such polythioethers are described in US Pat. No. 6,172,179, second column, line 29 to fourth column, line 34.

  The one or more additional sulfur-containing prepolymers may be difunctional, or multifunctional having, for example, 3 to 6 end groups, or combinations thereof.

  In certain embodiments, the compositions provided by the present disclosure comprise from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, from about 30 wt% to about 70 wt%, And in certain embodiments, from about 40 wt% to about 60 wt%, where wt% is based on the total weight (ie, dry weight) of the non-volatile components of the composition.

The term polysulfides used herein, one or more sulfide bonds, i.e. -S x _- bond (where x is 2 to 4), the polymer main chain and / or polymer chain on the pendant Means a polymer contained in the position. In certain embodiments, the polysulfide polymer will have more than one sulfur-sulfur bond. Suitable polysulfides are commercially available, for example, from Akzo Nobel and Toray Fine Chemical Co., under the product names Thioplast® and Thiokol-LP. Thioplast® products are available in a wide range of molecular weights, for example ranging from less than 1,100 to more than 8,000 (molecular weight is the average molecular weight in grams per mole). The polysulfide may have a number average molecular weight of 1,000 to 4,000 daltons. The crosslink density of these products also varies depending on the amount of crosslinker used. The -SH content of these products, i.e. the thiol or mercaptan content, can also vary. The mercaptan content and molecular weight of the polysulfide can affect the cure rate of the polymer, with the cure rate increasing with molecular weight.

  Sulfur-containing polyformal prepolymers useful for aerospace sealant applications are disclosed, for example, in US Patent Application Publication No. 2012/0234205 and US Patent Application Publication No. 2012/0238707.

  In certain embodiments, the sulfur-containing polymer is selected from polythioethers and polysulfides, and combinations thereof. In certain embodiments, the sulfur-containing polymer comprises a polythioether, and in certain embodiments, the sulfur-containing polymer comprises a polysulfide. The sulfur-containing polymer may comprise a mixture of different polythioethers and / or polysulfides, where the polythioethers and / or polysulfides may have the same functionality or different functionality. In certain embodiments, the sulfur-containing polymer has an average functionality of 2 to 6, 2 to 4, 2 to 3, and in certain embodiments, 2.05 to 2.5. For example, the sulfur-containing polymer can be selected from a bifunctional sulfur-containing polymer, a trifunctional sulfur-containing polymer, and combinations thereof.

  The composition provided by the present disclosure may include one or more catalysts. A catalyst suitable for the curing chemistry employed can be selected. In certain embodiments, for example, when curing thiol-terminated bis (sulfonyl) alkanol-containing polythioethers, prepolymers, or thiol-terminated metal ligand-containing prepolymers, and polyepoxides, the catalyst is an amine catalyst. The curing catalyst can be present in an amount of 0.1 to 5 weight percent, based on the total weight of the composition. Examples of suitable catalysts include 1,4-diazabicyclo [2.2.2] octane (commercially available from DABCO®, Air Products, Chemical Additives Division, Allentown, Pa.), And DMP -30 (registered trademark) (a reaction accelerator composition containing 2,4,6-tris (dimethylaminomethyl) phenol).

  In certain embodiments, the compositions provided by the present disclosure include one or more adhesion promoters. The one or more additional adhesion promoters may be from 0.1 wt% to 15 wt%, less than 5 wt%, less than 2 wt%, and in certain embodiments, 1 wt% based on the total dry weight of the composition It can be present in less than amounts. Examples of adhesion promoters include phenolic compounds such as Methylon® phenolic resins, and epoxy, mercapto, or aminofunctional silanes such as Silquest® A-187 and Silquest® A-1100 And organosilane compounds such as Other useful adhesion promoters are known in the art.

The compositions provided by the present disclosure may include one or more different types of fillers. Suitable fillers include those commonly known in the art, including inorganic fillers such as carbon black and calcium carbonate (CaCO ₃ ), silica, polymer powders, and lightweight fillers. Suitable lightweight fillers include those described, for example, in US Pat. No. 6,525,168. In certain embodiments, the composition is 5 wt% to 60 wt%, 10 wt% to 50 wt%, and in certain embodiments, 20 wt% to 40 wt% filler or filler, based on the total dry weight of the composition. Including a combination of The compositions provided by the present disclosure may further comprise one or more colorants, thixotropic agents, accelerators, flame retardants, adhesion promoters, solvents, masking agents, or any combination of the foregoing. As will be appreciated, the fillers and additives used in the composition can be selected to have an affinity for each other, as well as for the polymeric components, curing agents, and / or catalysts. Examples of non-conductive fillers include calcium carbonate, mica, polyamide, fumed silica, molecular sieve powder, microspheres, titanium dioxide, lime, alkali black, cellulose, zinc sulfide, barite, alkaline earth Examples thereof include, but are not limited to, oxides and alkaline earth hydroxides.

  In certain embodiments, the compositions provided by the present disclosure include low density filler particles. As used herein, low density, when used with respect to such particles, in certain embodiments, wherein the particles do not exceed 0.7, in certain embodiments, does not exceed 0.25. , 0.1, and having a specific gravity. Suitable lightweight filler particles are often classified into two categories: microspheres and amorphous particles. The specific gravity of the microspheres can range from 0.1 to 0.7, for example, polystyrene foam, polyacrylate and polyolefin microspheres, and particle sizes in the range of 5 to 100 microns and specific gravity of 0.25 ( Examples include silica microspheres with Ecospheres®). As another example, alumina / silica microspheres having a particle size in the range of 5 to 300 microns and a specific gravity of 0.7 (Fillete®), an aluminum silicate with a specific gravity of about 0.45 to about 0.7 Microspheres (Z-Light®), calcium carbonate-coated polyvinylidene copolymer microspheres with a specific gravity of 0.13 (Dualite® 6001AE), and an average particle size of about 40 μm and a density of 0.135 g / Calcium carbonate coated acrylonitrile copolymer microspheres such as cc Dualite® E135 (Henkel). Suitable fillers for reducing the specific gravity of the composition, for example, hollow microspheres such as Expandel® microspheres (available from AkzoNobel), or Dualite® low density polymeric microspheres (available from Henkel) ). In certain embodiments, the compositions provided by the present disclosure are thin, such as those described in paragraphs [0016] to [0052] of US Patent Application Publication No. 2010/0041839, which is incorporated herein by reference. Includes lightweight filler particles including an outer surface coated with a coating.

  In certain embodiments, the low density filler is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.75 wt%, less than 0.7 wt% of the composition, and In certain embodiments, it comprises less than 0.5 wt% of the composition, where wt% is based on the total dry weight of the composition.

  In certain embodiments, the compositions provided by the present disclosure include at least one filler that is effective in reducing the specific gravity of the composition. In certain embodiments, the specific gravity of the composition is 0.8 to 1, 0.7 to 0.9, 0.75 to 0.85, and in certain embodiments, 0.8. In certain embodiments, the specific gravity of the 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.

  In certain embodiments, the compositions provided by the present disclosure include a conductive filler. By incorporating a conductive material into the polymer, conductivity and EMI / RFI shielding effects can be imparted to the composition. The conductive component can include, for example, metal or metal plated particles, fabrics, meshes, fibers, and combinations thereof. The shape of the metal can be, for example, a filament, particle, flake, or sphere. Examples of metals include copper, nickel, silver, aluminum, tin, and steel. Other conductive materials that can be used to impart conductivity and EMI / RFI shielding effects to the polymer composition include conductive particles or fibers including carbon or graphite. Conductive polymers such as polythiophene, polypyrrole, polyaniline, poly (p-phenylene) vinylene, polyphenylene sulfide, polyphenylene, and polyacetylene can also be used. The conductive filler also includes high band gap materials such as zinc sulfide and inorganic barium compounds.

  Other examples of conductive fillers include conductive noble metal fillers such as pure silver; noble metal plated noble metals such as silver plated gold; noble metal plated non-noble metals such as silver plated copper, nickel or aluminum, such as silver plated aluminum cores. Particles or platinum plated copper particles; noble metal plated glass, plastic or ceramic, such as silver plated glass microspheres, noble metal plated aluminum or noble metal plated plastic microspheres; noble metal plated mica; and other such noble metal conductive fillers. . Non-noble metal based materials can also be used, for example, non-noble metal plated non-noble metals such as copper-coated iron particles or nickel-plated copper; non-noble metals such as copper, aluminum, nickel, cobalt; non-noble metal plated non-metals such as Nickel-plated graphite; and non-metallic materials such as carbon black and graphite. A combination of conductive fillers can also be used to achieve the desired conductivity, EMI / RFI shielding effectiveness, hardness, and other properties appropriate for the particular application.

  The shape and size of the conductive filler used in the composition of the present disclosure can be any shape and size suitable for imparting conductivity and EMI / RFI shielding effects to the cured composition. For example, the filler can be of any shape commonly used in the production of conductive fillers, including spheres, flakes, platelets, particles, powders, irregular shapes, fibers, and the like. In certain sealant compositions of the present disclosure, the base composition can include Ni-coated graphite as particles, powders or flakes. In certain embodiments, the amount of Ni-coated graphite in the base composition can range from 40 wt% to 80 wt% based on the total weight of the base composition, and in certain embodiments, 50 wt% To 70 wt%. In certain embodiments, the conductive filler can include Ni fibers. The Ni fibers can have a diameter in the range of 10 μm to 50 μm and a length in the range of 250 μm to 750 μm. The base composition can include, for example, Ni fibers in an amount ranging from 2 wt% to 10 wt%, and in certain embodiments, from 4 wt% to 8 wt%, based on the total weight of the base composition.

  Carbon fibers, especially graphite carbon fibers, can also be used to impart conductivity to the compositions of the present disclosure. Carbon fibers formed by vapor phase pyrolysis and graphitized by heat treatment are hollow or solid with a fiber diameter in the range of 0.1 to several microns and have high conductivity. Carbon microfibers, nanotubes, or carbon fibrils having an outer diameter of less than 0.1 μm to several tens of nanometers, as disclosed in US Pat. No. 6,184,280, should be used as conductive fillers Can do. Examples of graphitized carbon fibers suitable for the conductive composition of the present disclosure include 0.921 μm diameter circular fibers having an electrical resistivity of 0.00055 Ω · cm, Panex® 3 OMF (Zoltek Companies, Inc., St. Louis, Missouri).

The average particle diameter of the conductive filler can be within a range useful for imparting conductivity to the polymer-based composition. For example, in certain embodiments, the particle size of one or more fillers can be in the range of 0.25 μm to 250 μm, and in certain embodiments, in the range of 0.25 μm to 75 μm. And in certain embodiments can range from 0.25 μm to 60 μm. In certain embodiments, compositions of the present disclosure, 1,000 mg / g iodine absorption of 11,500mg / g from (J0 / 84-5 test method), and from 480 cm ^3/100 g of 510 cm ^3/100 g fine A conductive carbon black characterized by pore volume (DBP absorption, KTM 81-3504), Ketjenblack® EC-600JD (Akzo Nobel, Inc., Chicago, Ill.) Can be included. In certain embodiments, the conductive carbon black filler is Black Pearls® 2000 (Cabot Corporation, Boston, Mass.).

  In certain embodiments, the conductive polymer can be used to impart conductivity to the composition of the present disclosure or to alter the conductivity of the composition of the present disclosure. Polymers having sulfur atoms incorporated into aromatic groups or adjacent double bonds, such as polyphenylene sulfide and polythiophene, are known to be electrically conductive. Examples of other conductive polymers include polypyrrole, polyaniline, poly (p-phenylene) vinylene, and polyacetylene. In certain embodiments, the sulfur-containing polymer forming the base composition can be a polysulfide and / or a polythioether. Thus, to increase the conductivity of the composition of the present disclosure, the sulfur-containing polymer can include sulfur atoms adjacent to aromatic sulfur groups and conjugated double bonds.

The composition of the present disclosure can include a plurality of conductive fillers, which can be of the same or different materials and / or shapes. For example, the sealant composition can include conductive Ni fibers and conductive Ni-coated graphite in the form of powder, particles, or flakes. The amount and type of conductive filler is a sealant that when cured exhibits a sheet resistance of less than 0.50 Ω / cm ² (4-point resistance), and in certain embodiments, a sheet resistance of less than 0.15 Ω / cm ^2. One can choose to produce the composition. In order to seal the aperture using the sealant composition of the present disclosure, the amount and type of filler can also be selected to provide effective EMI / RFI shielding over frequencies from 1 MHz to 18 GHz.

  In certain embodiments, the conductive base composition can include non-conductive filler in an amount ranging from 2 wt% to 10 wt% based on the total weight of the base composition, and in certain embodiments, The amount of non-conductive filler can range from 3 wt% to 7 wt%. In certain embodiments, the curing agent composition is in an amount in the range of less than 6 wt%, and in certain embodiments in the range of 0.5 wt% to 4 wt%, based on the total weight of the curing agent composition. Non-conductive fillers can be included.

  Electrolytic corrosion of conductive compositions and dissimilar metal surfaces of the present disclosure can be minimized or prevented by adding corrosion inhibitors to the compositions and / or by selecting appropriate conductive fillers. Can do. In certain embodiments, strontium chromate, calcium chromate, magnesium chromate, and combinations thereof are listed as corrosion inhibitors. US Pat. No. 5,284,888 and US Pat. No. 5,270,364 disclose the use of aromatic triazoles to inhibit corrosion of aluminum and steel surfaces. In certain embodiments, a sacrificial oxygen scavenger such as Zn can be used as a corrosion inhibitor. In certain embodiments, the corrosion inhibitor may comprise less than 10% by weight of the total weight of the conductive composition. In certain embodiments, the corrosion inhibitor may constitute an amount ranging from 2% to 8% by weight of the total weight of the conductive composition. Corrosion between dissimilar metal surfaces can also be minimized or prevented by selecting the type, amount, and properties of the conductive fillers that make up the composition.

  In certain embodiments, the bis (sulfonyl) alkanol-containing polythioether and / or bis (sulfonyl) alkanol-containing polythioether prepolymer, and / or the metal ligand-containing prepolymer is about 50 wt% to about 90 wt% of the composition, From about 60 wt% to about 90 wt%, from about 70 wt% to about 90 wt%, and in certain embodiments, may comprise from about 80 wt% to about 90 wt% of the composition, where wt% is the total dry solids of the composition Based on minute weight.

  If desired, the composition can include any number of additives. Examples of suitable additives include plasticizers, pigments, surfactants, adhesion promoters, thixotropic agents, flame retardants, masking agents, and accelerators (eg, 1,4-diazabicyclo [2.2.2] octane, DABCO (Such as amines, including (registered trademark)), and any combination of the foregoing. When used, the additive may be present in the composition in an amount ranging, for example, from about 0% to 60% by weight. In certain embodiments, the additive may be present in the composition in an amount ranging from about 25% to 60% by weight.

Uses The compositions provided by the present disclosure can be used, for example, in sealants, coatings, encapsulants, and potting compositions. Composition that can produce a film that is resistant to operating conditions such as humidity and temperature and that has the ability to at least partially block the movement of materials such as water, fuel, and other liquids and gases. Things are listed as sealants. For example, a coating applied to the surface of a substrate to improve the properties of the substrate, such as appearance, adhesion, wettability, corrosion resistance, abrasion resistance, fuel oil resistance, and / or scratch resistance, may be used as a coating composition. Can be mentioned. Materials useful for electronic assemblies that provide impact and vibration resistance and remove moisture and corrosives are listed as potting compositions. In certain embodiments, the sealant compositions provided by the present disclosure are useful as, for example, aerospace sealants and fuel tank linings.

  In certain embodiments, a composition such as a sealant can be provided as a multi-part composition, such as a two-part composition, wherein one container is a polythiol-containing metal ligand-containing poly hydride provided by the present disclosure. The second container contains one or more thioether or thiol-terminated metal ligand-containing prepolymers and the second container contains one or more polyfunctional sulfur-containing epoxies provided by the present disclosure. Additives and / or other materials may be added to any container as desired or required. The two containers can be formulated or mixed before use. In certain embodiments, the pot life of one or more mixed thiol-terminated polythioethers and epoxies is at least 30 minutes, at least 1 hour, at least 2 hours, and in certain embodiments, 2 hours. Over. Pot life here means the period during which the mixed composition is still suitable for use as a sealant after mixing.

  A composition comprising a sealant provided by the present disclosure can be applied to any of a variety of substrates. Examples of substrates on which the composition may be applied include any metal such as titanium, stainless steel, aluminum, and alloys thereof, which may be anodized, primed, organic coated, or chromium coated, epoxy, urethane , Graphite, fiberglass composites, Kevlar®, acrylic, and polycarbonate. In certain embodiments, the compositions provided by the present disclosure can be applied to a coating on a substrate, such as a polyurethane coating. In certain embodiments, a composition comprising a bis (sulfonyl) alkanol-containing polythioether or metal ligand-containing prepolymer provided by the present disclosure comprises aluminum, aluminum oxide, anodized aluminum, titanium, titanium oxide, and / or Shows enhanced adhesion to Alodine® surfaces. In particular, compositions comprising bis (sulfonyl) alkanol-containing polythioethers or metal ligand-containing prepolymers provided by the present disclosure exhibit enhanced adhesion to bare metal and anodized metal surfaces.

  The compositions provided by the present disclosure may be applied directly on the substrate surface or from above the underlayer by any suitable application process known to those skilled in the art.

  Further provided is a method of sealing an opening utilizing the composition provided by the present disclosure. These methods include, for example, applying a composition provided by the present disclosure to a surface to seal the opening, and curing the composition. In certain embodiments, a method of sealing an opening comprises: (a) applying a sealant composition provided by the present disclosure to one or more surfaces defining the opening; and (b) an applied sealant composition. Curing the object to provide a sealed opening.

  In certain embodiments, an opening sealed with a sealant composition of the present disclosure is provided.

  In certain embodiments, the composition may be cured under atmospheric conditions, where atmospheric conditions mean a temperature between 20 ° C. and 25 ° C. and atmospheric humidity. In certain embodiments, the composition may be cured under conditions including a temperature of 0 ° C. to 100 ° C. and a humidity of 0% relative humidity to 100% relative humidity. In certain embodiments, the composition may be cured at higher temperatures, such as at least 30 ° C., at least 40 ° C., and in certain embodiments, at least 50 ° C. In certain embodiments, the composition may be cured at room temperature, eg, 25 ° C. In certain embodiments, the composition may be cured by actinic radiation, such as ultraviolet radiation. As will be appreciated, the method can be used to seal openings on aerospace vehicles, including aircraft and aerospace vehicles.

  In certain embodiments, the composition has a temperature of less than about 200 ° F. for less than about 2 hours, less than about 4 hours, less than about 6 hours, less than about 8 hours, and in certain embodiments, about In less than 10 hours, tack-free cure is achieved.

  The time to form a practically functioning seal using the curable composition of the present disclosure can depend on several factors, as will be appreciated by those skilled in the art, and the requirements of the standards and specifications to be applied It depends on. In general, the adhesive strength of the curable compositions of the present disclosure increases within 24 to 30 hours, and 90% of the maximum adhesive strength is achieved 2 to 3 days after mixing and application to the surface. In general, the cured compositions of the present disclosure fully demonstrate their maximum adhesive strength and other properties within 7 days after mixing and applying the curable composition to the surface.

  Cured compositions disclosed herein, such as cured sealants, exhibit properties commensurate with use in aerospace applications. In general, sealants for use in aerospace and aerospace applications should exhibit the following properties: Aerospace Material Specification (AMS) 3265B test specifications on AMS 3265B substrate, JRF Type I Peel strength greater than 20 pounds per linear inch (pli); between 300 pounds per square inch (psi) and 400 psi, as measured under dry conditions after soaking in 7 days in 3% NaCl solution A tensile strength of greater than 50 pounds per linear inch (pli); an elongation between 250% and 300%; and a hardness of greater than 40 with an A-type durometer. These or other cured sealant properties suitable for aviation and aerospace applications are disclosed in AMS 3265B, which is hereby incorporated by reference in its entirety. When cured, after immersing in JRF Type I at 60 ° C. (140 ° F.) and atmospheric pressure for one week, the composition exhibits an expansion that is less than 25% by volume, for use in aviation and aircraft applications It is also desirable. Other properties, ranges, and / or thresholds may be suitable for other sealant applications.

  Accordingly, in certain embodiments, the compositions provided by the present disclosure are fuel oil resistant. As used herein, the term “fuel oil resistance” refers to ASTM D792 (American Society for Testing and Materials) or AMS 3269 (Aerospace Materials Standard) when a composition is applied to a substrate and cured. In a volume percentage after immersion in Jet Reference Fluid (JRF) Type I at 140 ° F. (60 ° C.) and atmospheric pressure according to a method similar to that described in Aerospace Material Specification. It means that a cured product such as a sealant can be provided which exhibits an expansion of 40% or less, optionally 25% or less, optionally 20% or less, and in other cases 10% or less. The jet reference fluid JRF Type I used to determine fuel oil resistance has the following composition: 28% by volume of toluene ± 1% by volume, 34% by volume of cyclohexane (industrial) ± 1% by volume, 38% by volume of isooctane ± 1% by volume and tertiary dibutyl disulfide 1% by volume ± 0.005% by volume (available from SAE (Society of Automotive Engineers), issued July 1, 1989, AMS2629, § 3.1.1 etc.) .

  In certain embodiments, when measured according to the procedures described in AMS 3279, §3.3.7.1, test procedure AS5127 / 1, §7.7, the compositions provided herein are at least A cured composition, such as a sealant, is provided that exhibits 100% elongation and a tensile strength of at least 400 psi.

  In certain embodiments, the composition has a lap shear strength of greater than 200 psi, such as at least 220 psi, at least 250 psi, and optionally at least 400 psi, as measured according to the procedure set forth in SAE AS5127 / 1, Section 7.8. A cured product, such as a sealant, is provided.

  In certain embodiments, a cured sealant comprising a composition provided by the present disclosure meets or exceeds the requirements of an aerospace sealant as described in AMS 3277.

  Apertures, including aerospace aircraft apertures, sealed with the compositions provided by the present disclosure are also disclosed.

  In certain embodiments, the cured sealant provided by the present disclosure exhibits the following properties when cured at room temperature for 2 days, 140 ° F. for 1 day, and 200 ° F. for 1 day: dry hardness 49, tensile Strength 428 psi and elongation 266%, and after soaking in JRF Type I for 7 days, hardness 36, tensile strength 312 psi, and elongation 247%.

  In certain embodiments, the compositions provided by the present disclosure are greater than 10, greater than 20, greater than 30, and in certain embodiments greater than 40 Shore A type hardness (7 day cure). Greater than 10 psi, greater than 100 psi, greater than 200 psi, and in certain embodiments, greater than 500 psi tensile strength, and greater than 100%, greater than 200%, greater than 500%, and in certain embodiments Elongation greater than 1,000%, and swelling after exposure to JRF Type I (7 days) is less than 20%.

  Cured sealants prepared from metal ligand-containing prepolymers provided by the present disclosure exhibit enhanced tensile strength and enhanced adhesion to metal and / or metal oxide surfaces. Metal ligands incorporated into the main chain of the prepolymer can function as multidentate ligands in the metal chelate.

  The embodiments provided by the present disclosure are further illustrated by reference to the following examples, whereby specific bis (sulfonyl) alkanol-containing polythioethers and metal ligand-containing prepolymers, and bis (sulfonyl) alkanols The synthesis, properties and uses for compositions containing the containing polythioether or metal ligand containing prepolymer are described. It will be apparent to those skilled in the art that many modifications can be made to both materials and methods without departing from the scope of the disclosure.

Example 1
Thiol-terminated polythioether 1,8-dimercapto-3,6-dioxaoctane (DMDO; 1995.60 g; 10.95 mol) was charged into a 5-liter 4-neck round bottom flask. The flask was equipped with a nitrogen gas adapter, a paddle stirrer and a temperature probe. The flask was flushed with nitrogen and the contents were heated to 60 ° C. with stirring. A free radical initiator Vazo®-67 (0.41 g) was added into the flask. Diethylene glycol divinyl ether (1154.51 g; 7.30 mol) was introduced into the reaction mixture over a period of 6.25 hours while maintaining the temperature at 60-65 ° C. The reaction temperature was raised to 77 ° C. and two portions of Vazo®-67 (0.045 g each) were added at 3 hour intervals. The reaction mixture was heated at 94 ° C. for 2 hours, cooled to 66 ° C. and then evacuated at 66 ° C. to 74 ° C./15 mmHg for 1 hour. The resulting polymer, dithiol, had a mercaptan equivalent weight of 430.

Example 2
Thiol-terminated bis (sulfonyl) alkanol-containing polythioether The dithiol of Example 1 (55.04 g; 0.064 mol) was charged to a 250 mL 3-neck round bottom flask. The flask was equipped with a nitrogen gas adapter and a paddle stirrer. The contents were evacuated at 7 mm for 30 minutes and then the vacuum was released under nitrogen. While stirring, the base catalyst DBU (1,8-diazabicycloundec-7-ene; 0.013 g) was added followed by ethanol (10 g) and the flask was equipped with a temperature probe. While cooling (in a water bath), a solution of 1,3-bis (vinylsulfonyl) -2-propanol (7.69 g; 0.032 mol) in tetrahydrofuran (90 g) was added at a temperature of 19 ° C. to 20 ° C. over 2 hours. And dripped. The water bath was removed and the reaction was stirred at ambient temperature for an additional 2 hours. Mercaptan equivalents were used to determine when the reaction was complete. After removal of the solvent, a liquid bifunctional polymer was obtained having a mercaptan equivalent weight of 1,166 and a viscosity of 81 poise.

Example 3
Thiol-terminated bis (sulfonyl) alkanol-containing polythioether prepolymer The dithiol of Example 2 (62 g; 0.0177 mol) was charged into a 250 mL 3-neck round bottom flask. While stirring, a solution of triallyl cyanurate (TAC) (0.93 g; 0.0037 mol) and diethylene glycol divinyl ether (0.22 g; 0.0014 mol) in toluene (1.0 g) was introduced into the reaction mixture. The contents were heated to 77 ° C. The radical initiator Vazo®-67 was added in 7 portions (each 0.016 grams) at 1 hour intervals to complete the reaction. Removal of the solvent under vacuum yielded a polymer with a theoretical thiol functionality of 2.21, a mercaptan equivalent weight of 1,659 and a viscosity of 195 poise.

Example 4
Bis (sulfonyl) alkanol-containing polythioether sealant The prepolymer of Example 3 (14.93 grams; 0.009 equivalents) and calcium carbonate (Socal® N2R; 4.48 grams) were added to a Hauschild mixer (Model: DAC600FVZ) In a mixing cup (volume: 60 grams). The contents were combined by manual mixing and then mixed with a Hauschild mixer for 30 seconds (speed: 2300 RPM). The contents were manually mixed again and then mixed in a Hauschild mixer for an additional 30 seconds. Epoxy accelerator S-5304 (available from PPG Aerospace; 3.60 g, 0.009 eq) was added. The contents were combined by manual mixing and then mixed with a Hauschild mixer for 30 seconds. Base catalyst DABCO33-LV (0.12 g) was added. The contents were mixed manually and then mixed with a Hauschild mixer for 30 seconds.

  Using a portion of the mixture to produce a hardened plug for hardness and using the remainder of the mixture, the following seven surface adhesion test specimens (approximate dimensions: 4 cm x 1.4 cm x 0.3 cm) Made: Scotch-Brite® treated bare aluminum; Mil-C-27725; Scotch-Brite® treated titanium B; Scotch-Brite® treated titanium C; Alodine® ) 1200; anodized SAA; anodized CAA. All specimens were subjected to a curing cycle of room temperature / 20 hours, 60 ° C./27 hours. After the sample was cured, the hardness was 40 (Shore A). The adhesion evaluated by peeling / cutting the cured sealant from the metal surface was very good for 6 out of 7 surfaces (100% cohesive failure). However, the cured test specimen did not adhere to Alodine® 1200 (0% cohesive failure).

Example 5
Thiol-terminated bis (sulfonyl) alkanol-containing bifunctional polythioether The dithiol of Example 1 (636.40 g; 0.74 mol) was charged to a 2 liter 4-neck round bottom flask. The flask was equipped with a nitrogen gas adapter and a paddle stirrer. The contents were evacuated at 8 mm for 1 hour and then the vacuum was released under nitrogen. While stirring, ethanol (116 g) was added followed by base catalyst DBU (0.145 g) and the flask was equipped with a temperature probe. Under cooling (in a water bath), a solution of 1,3-bis (vinylsulfonyl) -2-propanol (88.91 g; 0.37 mol) in tetrahydrofuran (1.04 kg) was added at a temperature of 23 ° C. to 27 ° C. for about 2 It was added dropwise over time. The progress of the reaction was measured using the mercaptan equivalent. The water bath was removed and the reaction was stirred for an additional 3 hours at room temperature. Removal of the solvent gave a bifunctional polymer having a mercaptan equivalent weight of 1,296 and a viscosity of 107 poise.

Example 6
Thiol-terminated bis (sulfonyl) alkanol-containing polythioether prepolymer The bifunctional polymer of Example 5 (725.29 g; 0.2798 mol) was charged to a 2 liter 4-neck round bottom flask. The flask was equipped with a nitrogen gas adapter and a paddle stirrer. The contents were flushed with nitrogen. While stirring, a solution of triallyl cyanurate (10.22 g; 0.041 mol) and diethylene glycol divinyl ether (0.49 g; 0.0031 mol) in toluene (5.0 mL) was introduced into the reaction mixture and the contents were Heated to 70 ° C. Fifteen portions (0.084 g each) of radical initiator Vazo®-67 were added at 1 hour intervals to complete the reaction. The solvent was removed under vacuum to give a polymer with a theoretical functionality of 2.21, a mercaptan equivalent weight of 1675 and a viscosity of 238 poise.

Example 7
Bis (sulfonyl) alkanol-containing polythioether sealant The prepolymer of Example 6 (30 g; 0.0179 eq) and calcium carbonate (Socal® N2R; 9.00 g) are placed in a mixing cup (volume 100 g) of a Hauschild mixer. I put it in. The contents were mixed manually and mixed for 30 seconds in a Hauschild mixer (speed: 2300 RPM). The contents were subjected to manual mixing and then 2 rounds of mixing for 4 minutes in a Hauschild mixer. The contents were cooled to ambient temperature. An epoxy accelerator, S-5304 (available from PPG Aerospace, 0.0179 equivalents) was added. The contents were subjected to two rounds of manual mixing followed by 30 seconds of mixing in a Hauschild mixer. Base catalyst DABCO33-LV (0.24 g) was added. The contents are mixed manually, then mixed for 30 seconds in a Hauschild mixer, poured into a grid and flowed out (approximate dimensions: length: 6 inches, width: 3.2 inches, thickness: 0.1 inches). ) Was produced. The sealant sample was subjected to a room temperature / 7 day cure cycle and cured at 140 ° F./24 hours. The cured sealant had a 48 Shore A hardness, a tensile strength of 373 psi, and an elongation of 472%.

Comparative Example 1
Permapol® 3.1E polymer (10 g, a thiol-terminated polythioether prepolymer commercially available from PRC-Desoto International, Sylmar, Calif.) And calcium carbonate (5.0 g) in a Hauschild mixer at 2300 rpm for 30 seconds. Mixed. Subsequently, accelerator (S-5304, 2.6 g, epoxy paste commercially available from PRC-Desoto International, Sylmar, CA) and catalyst (triethylenediamine; 0.08 g) were added and mixed. Samples varied from anodized CAA, anodized SAA, Mil-C-27725, Alodine® 1200, titanium C, bare aluminum, and bare aluminum treated with Scotch-Brite®. And then cured at room temperature for 24 hours, followed by curing at 140 ° F. for 48 hours. The% probability of cohesive failure was measured by peeling the sample from the substrate. Each of the samples showed 0% cohesive failure.

Example 8
Calculation of Density Functional Theory Gibbs Free Energy (Li et al., “Structural determination of” of interaction between various functional groups and Al ₄ O ₆ clusters constituting aluminum surface oxides of typical aerospace substrates (Al ₂ O ₃ ) _n (n = 1-7) clusters based on density functional calculation, ”(“ (Al ₂ O ₃ ) _n (n = 1-7) Cluster Structure Determination Based on Density Function Calculation) ”Computational and Theoretical Chemistry 2012, 996, 125-131) was calculated using a method based on density functional theory (DFT). All structures were optimized using Gaussian09 / B3LYP / 6-31g (d), and the vibration frequency was calculated with the same level of theory in order to confirm that these structures existed at local minimum values. The energy in the aquatic environment was calculated using a single point energy calculation by the CPCM rescue scheme. The Gibbs free energy of the interaction was calculated under standard conditions of pressure and temperature (1 atm and 25 ° C.) without correction.

These functional groups were analyzed for their unique properties, including HOMO (highest occupied molecular orbital), LUMO (lowest unoccupied molecular orbital) energy, and the energy gap between HOMO and LUMO. Typically, functional groups with higher HOMO energy are more electron donating and functional groups with lower LUMO energy are more electron accepting. When comparing the various functional groups shown in Table 1, 3-hydroxy-1,2-dimethylpyridin-4 (1H) -one (HOPO) has the highest HOMO energy, indicating that HOPO has the largest electrons. It means donation. On the other hand, the functional group bis (sulfonyl) -2-propanol (BSP) has the lowest HOMO energy, which means that the functional group is the least electron donating.

The interaction between various functional groups and aluminum oxide clusters was measured. The Gibbs free energy (ΔG _g ) of interaction in the gas phase and the Gibbs free energy (ΔG _w ) of interaction in water are calculated, and the results are shown in FIG. 1 together with the contribution from the enthalpy of reaction (ΔH). Shown in In FIG. 1, a larger negative ΔG corresponds to a more stable complex or a stronger interaction between the functional group and the aluminum oxide. BSP and HOPO have a stronger interaction with aluminum oxide than acetoacetate, both in the gas phase and in the simulated water environment. Acetoacetate binds to Al ₄ O ₆ through coordination of electron-rich carbonyl oxygen (in acetoacetate) to electron deficient aluminum (in Al ₄ O ₆ ). HOPO interacts with Al ₄ O ₆ as a bidentate ligand. That is, carbonyl oxygen (in HOPO) is bonded to aluminum (in Al ₄ O ₆ ), and a hydroxyl group (in HOPO) is hydrogen bonded to oxygen (in Al ₄ O ₆ ). A tridentate mode of binding between BSP and Al ₄ O ₆ has been identified, but here, in addition to hydrogen bonding between the hydroxyl group (in BSP) and the oxygen atom (in Al ₄ O ₆ ), (in BSP) ) Two sulfonyl groups are bonded to two aluminum atoms (in Al ₄ O ₆ ). Although BSP is not very electron donating (as shown by the low HOMO energy in Table 1), strong binding with Al ₄ O ₆ at three coordination sites is observed. .

  In conclusion, it was shown that the functional group of BSP binds to aluminum oxide in a tridentate manner, resulting in a very strong interaction (adhesion). Unlike other strong binding ligands such as HOPO, BSP is not easily oxidized and is expected to have good stability. Structures with binding motifs similar to BSP can also result in strong binding to aluminum oxide.

  Suitable for enhancing adhesion to certain metal surfaces and may be incorporated into the prepolymer backbone described in this disclosure and / or provided as end groups of the prepolymer Similar methods can be used to identify other metal ligands.

Finally, it should be noted that there are alternative methods for implementing the embodiments disclosed herein. Therefore, this embodiment should be understood as an illustration and should not be understood as a limitation. Further, the claims should not be limited to the details described herein, but the entire scope and equivalents thereof should be entitled.
The aspects that can be included in the present invention are summarized as follows.
[Aspect 1]
A metal ligand-containing prepolymer comprising a metal ligand incorporated in the main chain of the prepolymer.
[Aspect 2]
The prepolymer according to embodiment 1, comprising a sulfur-containing prepolymer.
[Aspect 3]
The prepolymer of embodiment 2, wherein the sulfur-containing prepolymer comprises a polythioether.
[Aspect 4]
The prepolymer according to aspect 1, wherein the metal ligand is bidentate or tridentate.
[Aspect 5]
The prepolymer according to aspect 1, wherein the metal ligand has a coordination ability to Al (III).
[Aspect 6]
The prepolymer according to embodiment 1, wherein the metal ligand is derived from a metal chelator comprising bis (sulfonyl) alkanol, hydroxypyridinone, and / or acetylacetonate.
[Aspect 7]
The prepolymer according to aspect 1, wherein the metal ligand comprises at least two heteroatom groups having coordination ability to a plurality of surfaces of aluminum (III).
[Aspect 8]
At least two heteroatom groups are —OH, —PO ₄ , —P (O) ₂ —, —SO ₄ , —S (O) ₂ —, —COOH, —C═O, —NH ₂ , —NH. -And / or the prepolymer of aspect 7 comprising any combination thereof.
[Aspect 9]
The pre-treatment according to aspect 1, wherein the metal ligand comprises the following formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and / or any combination thereof: polymer:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
Wherein each X is independently —C (O) — or —S (O) ₂ —, n is 1, 2 or 3, and R ⁵ is C _1-3 alkane-diyl. .)
[Aspect 10]
The prepolymer according to Aspect 9, wherein each X is —C (O) — and each n is 1.
[Aspect 11]
The prepolymer according to Aspect 9, wherein each X is —S (O) ₂ — and each n is 1.
[Aspect 12]
A prepolymer according to embodiment 1 above comprising a moiety of the following formula (26):
^{-A-R 9 '-L-R} 9' -A- (26)
(Wherein each R ^{9 'is} independently a moiety derived from the reaction between the ^{R 9} and the thiol group of the metal chelating agent ^R 9 ^{-L-R 9,} wherein each ^{R 9} is a thiol Containing a reactive end group, L containing a metal ligand,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X independently includes —O—, —S— and NR ⁵ — (wherein R ⁵ is selected from hydrogen and methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. )).
[Aspect 13]
The prepolymer of embodiment 12, wherein the metal chelator comprises bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and / or any combination thereof.
[Aspect 14]
The prepolymer of embodiment 1, comprising a metal ligand-containing polythioether of formula (28a), a metal ligand-containing polythioether of formula (28b), or a combination thereof:
^{R 6 -A - [- R 9} '-L-R 9' -A-] N -R 6 (28a)
^{{R 6 -A - [- R} 9 '-L-R 9' -A-] N -V'-} z B (28b)
(In the formula, N is an integer of 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction between the R ⁹ and the thiol group of the metal chelating agent R ⁹ -L-R ^9, wherein each R ⁹ is terminated reactive with thiol A group, L includes a metal ligand,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S—, and NR ⁵ — (wherein R ⁵ includes hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction of -V and thiol,
Each R ⁶ independently includes a moiety having hydrogen and / or a terminal reactive group. ).
[Aspect 15]
The prepolymer according to embodiment 14, wherein each R ⁶ is hydrogen.
[Aspect 16]
Each R ⁶ is the same and the terminal reactive group is from —SH, —CH═CH ₂ , —NH ₂ , —OH, an epoxy group, a polyalkoxysilyl group, an isocyanate group, and a Michael acceptor group. The prepolymer according to the embodiment 14, which contains a selected group.
[Aspect 17]
(A) A thiol-terminated polythioether of formula (18a) below, a thiol-terminated polythioether of formula (18b) below, or a combination thereof:
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH
(18a)
{HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SV′—} _z B (18b )
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S— or NR ⁵ — (wherein R ⁵ is selected from hydrogen and methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction between -V and thiol. ), And
(B) Metal chelator R ⁹ -LR ⁹ (wherein each R ⁹ independently comprises a terminal group reactive with thiol and -L- contains a metal ligand)
A thiol-terminated metal ligand-containing polythioether comprising a reaction product of a reactant comprising:
[Aspect 18]
In aspect 15, wherein the metal ligand comprises a moiety selected from the following formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and any combination thereof: Polythioether described:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(In the formula, each X is independently —C (O) — or —S (O) ₂ —, each n is 1, 2 or 3, and R ⁵ is C _1-3 alkane— It is diyl.)
[Aspect 19]
The polythioether of embodiment 17, wherein the metal chelator comprises bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or any combination thereof.
[Aspect 20]
The polythioether according to embodiment 17, wherein the polythioether of formula (18a) comprises a reaction product of dithiol and divinyl ether.
[Aspect 21]
The polythioether according to embodiment 17, wherein the polythioether of formula (18a) comprises a reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether.
[Aspect 22]
The polythioether of embodiment 17, wherein the polythioether of formula (18b) comprises a reaction product of dithiol, divinyl ether and a polyfunctionalizing agent.
[Aspect 23]
The polythioether according to embodiment 17, wherein the polythioether of formula (18b) comprises a reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether and triallyl cyanurate.
[Aspect 24]
(A) A thiol-terminated metal ligand-containing polythioether of formula (29a), a thiol-terminated metal ligand-containing polythioether of formula (29b), or a combination thereof:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
(In the formula, N is an integer of 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction between the R ⁹ and the thiol group of the metal chelating agent R ⁹ -L-R ^9, wherein each R ⁹ is terminated reactive with thiol A group, L includes a metal ligand,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S— or NR ⁵ — (wherein R ⁵ is hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent alkenyl-terminated polyfunctionalizing agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal alkenyl group. )
Each -V'- is derived from the reaction between -V and thiol. ) And
(B) Polyalkenyl compound
A thiol-terminated metal ligand-containing polythioether prepolymer comprising a reaction product of a reactant comprising
[Aspect 25]
In embodiment 24 above, the metal ligand comprises a moiety selected from the following formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and any combination thereof: The described polythioether prepolymer:
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(In the formula, each X is independently —C (O) — or —S (O) ₂ —, each n is 1, 2 or 3, and R ⁵ is C _1-3 alkane— It is diyl.)
[Aspect 26]
25. The polythioether prepolymer according to embodiment 24, wherein the polyalkenyl compound comprises a divinyl ether, a polyalkenyl compound, or a combination thereof.
[Aspect 27]
(N + 1) moles of the following thiol-terminated polythioether of formula (18a) with (N) moles of metal chelator R ⁹ -LR ⁹ thiol of formula (29a) Methods for preparing terminal metal ligand-containing polythioethers:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH
(18a)
(In the formula, N is an integer of 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction between the R ⁹ and the thiol group of the metal chelating agent R ⁹ -L-R ^9, wherein each R ⁹ is terminated reactive with thiol A group, L includes a metal ligand,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S—, or NR ⁵ — (wherein R ⁵ includes hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. ).
[Aspect 28]
The method of aspect 27, wherein the metal ligand comprises the following formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and / or any combination thereof: :
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(In the formula, each X is independently —C (O) — or —S (O) ₂ —, each n is 1, 2 or 3, and R ⁵ is C _1-3 alkane— It is diyl.)
[Aspect 29]
A metal chelator,
A metal ligand comprising bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and / or any combination thereof, and
Comprising at least two end groups that are reactive towards thiol groups,
28. A method according to aspect 27 above.
[Aspect 30]
(Z) a thiol-terminated metal ligand of the formula (29b) comprising reacting a mole of a polythioether containing a thiol-terminated metal ligand of the following formula (29a) with 1 mol of the polyfunctionalizing agent B {V} _z Method for preparing a polythioether containing:
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
(In the formula, N is an integer of 1 to 10,
Each R ^{9 'is} independently a moiety derived from the reaction between the R ⁹ and the thiol group of the metal chelating agent R ⁹ -L-R ^9, wherein each R ⁹ is terminated reactive with thiol A group, L includes a metal ligand,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− ^{_{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X independently includes —O—, —S—, and NR ⁵ — (wherein R ⁵ includes hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction between -V and thiol. ).
[Aspect 31]
The method according to aspect 30, wherein the metal ligand comprises the following formula (25a), formula (25b), formula (25c), formula (25d), formula (25e), and / or any combination thereof: :
_{-X- (CH 2) n -CH (} -OH) - (25a)
_{-X- (CH 2) n -CH (} -OH) - (CH 2) n -X- (25b)
_{-CH (-OH) - (CH 2} ) n -X- (CH 2) n -CH (-OH) - (25c)
—CH (—OH) —R ⁵ —CH (—OH) — (25d)
^{-C (O) -R 5 -C (} O) - (25e)
(In the formula, each X is independently —C (O) — or —S (O) ₂ —, each n is 1, 2 or 3, and R ⁵ is C _1-3 alkane— It is diyl.)
[Aspect 32]
A metal chelator,
A metal ligand selected from bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and any combination thereof, and
Comprising at least two end groups that are reactive towards thiol groups,
The polythioether according to aspect 30 above.
[Aspect 33]
A composition comprising the metal ligand-containing prepolymer according to the first aspect.
[Aspect 34]
The composition according to the above aspect 33, which is a blend as a sealant composition.
[Aspect 35]
Including a sulfur-containing prepolymer,
34. The composition of aspect 33, wherein the sulfur-containing prepolymer comprises a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, and / or any combination thereof.
[Aspect 36]
34. The composition according to aspect 33, comprising a curing agent.
[Aspect 37]
A cured sealant comprising the composition according to aspect 33 above.

Claims (19)

A metal ligand-containing prepolymer comprising a metal ligand incorporated in the main chain of the prepolymer, wherein the prepolymer comprises a moiety of formula (26):
^{-A-R 9 '-L-R} 9' -A- (26)
^{(Wherein, -R 9 '-L-R 9} ' - has the following structure:
— (CH ₂ ) ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ — (CH ₂ ) ₂ — (wherein each R ¹⁰ is independently a is selected from _{C 1 to 3} alkanediyl and substituted _{C 1 to 3} alkanediyl, wherein one or more substituents are -OH).;
Each A independently represents formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12),
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(— CHR _{^{3 -) s -X-] q -}} (- CHR 3 -) r -
(Wherein s is an integer from 2 to 6,
q is an integer from 1 to 5;
r is an integer from 2 to 10,
Each R ³ independently contains hydrogen or methyl;
Each X independently includes —O—, —S—, or —NR ⁵ —, wherein R ⁵ is selected from hydrogen and methyl. )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ^3- ) _r- (where s, q, r, R ³ and X are as defined for R ¹ ),
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer of 2 to 6. ) The prepolymer of claim 1, wherein each R ¹⁰ is —CH ₂ — . The prepolymer of claim 1 comprising a metal ligand-containing polythioether of formula (28a), a metal ligand-containing polythioether of formula (28b), or a combination thereof:
^{R 6 -A - [- R 9} '-L-R 9' -A-] N -R 6 (28a)
^{{R 6 -A - [- R} 9 '-L-R 9' -A-] N -V'-} z B (28b)
(In the formula, N is an integer of 1 to 10 ,
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction of -V and thiol,
Each R ⁶ independently includes a moiety having hydrogen and / or a terminal reactive group. ). Each R ⁶ is hydrogen, prepolymer of claim 3. Each R ⁶ is the same and the terminal reactive group is from —SH, —CH═CH ₂ , —NH ₂ , —OH, an epoxy group, a polyalkoxysilyl group, an isocyanate group, and a Michael acceptor group. 4. A prepolymer according to claim 3 , comprising selected groups. (A) A thiol-terminated polythioether of formula (18a) below, a thiol-terminated polythioether of formula (18b) below, or a combination thereof:
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH
(18a)
{HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SV′—} _z B (18b )
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− _{^{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S— or NR ⁵ — (wherein R ⁵ is selected from hydrogen and methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction between -V and thiol. ), And
(B) Bis (vinylsulfonyl) alkanol having the following structure:
_{^{CH 2 = CH-S (O}} ) 2 -R 10 -CH (-OH) -R 10 -S (O) in ₂ -CH = CH 2 (wherein each ^{R 10} is, _{C 1 to 3} alkanediyl independently And substituted C _1-3 alkanediyl, wherein one or more substituents is —OH.)
Including reaction products of reactants, including
Thiol-terminated metal ligand-containing polythioether. The polythioether of claim 6 , wherein the polythioether of formula (18a) comprises a reaction product of dithiol and divinyl ether. The polythioether of claim 6 , wherein the polythioether of formula (18a) comprises a reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether. The polythioether of claim 6 , wherein the polythioether of formula (18b) comprises the reaction product of dithiol, divinyl ether and a polyfunctionalizing agent. The polythioether of claim 6 , wherein the polythioether of formula (18b) comprises a reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether and triallyl cyanurate. (A) The metal-ligand-containing prepolymer according to claim 3, wherein each R ⁶ is hydrogen.
And
(B) A thiol-terminated metal ligand-containing polythioether prepolymer comprising a reaction product of a reactant comprising a polyalkenyl compound. The polythioether prepolymer according to claim 11 , wherein the polyalkenyl compound comprises a divinyl ether, a polyalkenyl compound, or a combination thereof. (N + 1) moles of the following thiol-terminated polythioether of formula (18a) with (N) moles of metal chelator R ⁹ -LR ⁹ thiol of formula (29a) Methods for preparing terminal metal ligand-containing polythioethers:
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
HS—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —SH
(18a)
(In the formula, N is an integer of 1 to 10,
R ⁹ -LR ⁹ has the following structure:
_{^{CH 2 = CH-S (O}} ) 2 -R 10 -CH (-OH) -R 10 -S (O) in ₂ -CH = CH 2 (wherein each ^{R 10} is, _{C 1 to 3} alkanediyl independently And substituted C _1-3 alkanediyl, wherein one or more substituents is —OH.
R ^{9 ′} -LR ^{9 ′} has the following structure:
_{^{- (CH 2) 2 -S (}} O) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 - (CH 2) 2 - has,
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− _{^{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X is independently —O—, —S—, or NR ⁵ — (wherein R ⁵ includes hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. ). (Z) a thiol-terminated metal ligand of the formula (29b) comprising reacting a mole of a polythioether containing a thiol-terminated metal ligand of the following formula (29a) with 1 mol of the polyfunctionalizing agent B {V} _z Method for preparing a polythioether containing:
{H-A - [- R 9 '-L-R 9' -A-] N -V'-} z B (29b)
^{H-A - [- R 9} '-L-R 9' -A-] N -H (29a)
(In the formula, N is an integer of 1 to 10,
R ^{9 ′} -LR ^{9 ′} has the following structure:
— (CH ₂ ) ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ — (CH ₂ ) ₂ — (wherein each R ¹⁰ is independently C _{1 ˜3} alkanediyl and substituted C _1-3 alkanediyl, wherein one or more substituents is —OH.
Each A is independently part of the following formula (12):
—S—R ¹ — [— S— (CH ₂ ) _p —O— (R ² —O) _m — (CH ₂ ) ₂ —S—R ¹ —] _n —S— (12):
Wherein each R ¹ is independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanecycloalkanediyl, C _5-8 heterocycloalkanediyl, or — [(− _{^{CHR 3 -) s -X-] q}} - (- CHR 3 -) r -):
(In the formula, s is an integer of 2 to 6,
q is an integer of 1 to 5,
r is an integer of 2 to 10,
Each R ³ independently comprises hydrogen or methyl;
Each X independently includes —O—, —S—, and NR ⁵ — (wherein R ⁵ includes hydrogen or methyl). )
Each R ² is independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkanecycloalkanediyl, or — [(— CHR ³ —) _s —X—] _q — (— CHR ³ —) _r —), wherein s, q, r, R ³ and X are as defined above for R ¹ ;
m is an integer of 0-50,
n is an integer of 1-60,
p is an integer of 2-6. );
B represents the core of the z-valent polyfunctional agent B (-V) _z :
(In the formula, z is an integer of 3 to 6,
Each V is a group containing a terminal group reactive to the terminal thiol group. )
Each -V'- is derived from the reaction between -V and thiol. ).   A composition comprising the metal ligand-containing prepolymer according to claim 1. The composition according to claim 15, which is a blend as a sealant composition. Including a sulfur-containing prepolymer,
The sulfur-containing prepolymer, polythioether prepolymer, polysulfide prepolymer, sulfur-containing poly formal prepolymer also includes a combination of any of these, the composition of claim 15. 16. A composition according to claim 15 comprising a curing agent. A cured sealant comprising the composition of claim 15 .