RU2670957C2 - Ligand-containing prepolymers capable of binding to metal, methods for synthesis thereof and compositions containing same - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to prepolymers, to compositions containing prepolymers, to methods of producing prepolymers, and to the use of prepolymers in sealants in the aerospace industry. Prepolymer in a backbone contains a ligand capable of binding to a metal.EFFECT: invention makes it possible to obtain cured sealants having improved tensile strength and improved adhesion to metal surfaces.45 cl, 1 dwg, 1 tbl, 9 ex

Description

This application is a partial continuation of patent application US No. 13/923,903, filed June 21, 2013; partial continuation of application for US patent No. 13/923,941, filed June 21, 2013, and partial continuation of application for US patent No. 13/833,827, filed March 13, 2013, each of which is fully incorporated into this text by reference.

The technical field to which the invention relates.

The present invention relates to prepolymers containing a ligand capable of binding to a metal, compositions containing prepolymers containing a ligand capable of binding to a metal, methods of synthesizing prepolymers containing a ligand capable of binding to a metal, and using prepolymers containing a ligand capable of binding to a metal, in sealants for the aerospace industry. Prepolymers containing a ligand capable of binding to a metal include, for example, such ligands capable of binding to a metal, such as a bis (sulfonyl) alkanol, acetylacetonate, or hydroxypyridinone groups included in the main chain of prepolymers, such as polythioether prepolymers or polysulfide prepolymers.

Background of the invention

Sealants that can be used in the aerospace industry and other applications should comply with strict mechanical, chemical and environmental requirements. For example, it is desirable that sealants for the aerospace industry operate in a temperature range such as from about -67 ° F to about 360 ° F, and are resistant to fuels. As described in US Patent Application No. 13/923,903 and US Patent Application No. 13/923,941, sealants made using polythioether prepolymers containing bis (sulfonyl) alkanol groups included in the backbone and / or present as terminal groups, have increased adhesion to metal surfaces and meet other work requirements for sealants for the aerospace industry.

Aerospace ships often have light surfaces made of aluminum and titanium alloys. Previous works by the present inventors have shown that compositions having improved adhesion to such surfaces can be obtained using prepolymers in which bis (sulfonyl) alkanol fragments are included in the prepolymer main chain. Expanding this work to include other ligands capable of binding to metal provides additional opportunities for increasing adhesion to surfaces in the aerospace industry and to other surfaces.

It is desirable to develop sulfur-containing prepolymers that have improved adhesion to metal surfaces and that meet other working requirements for sealants for aerospace and other areas.

A brief description of the invention

In the first aspect, prepolymers are described comprising a ligand capable of binding to a metal in which a ligand capable of binding to a metal is included in the main chain of the prepolymer.

In the second aspect, thiol-terminal polythioethers containing a ligand capable of binding to a metal containing a reaction product of reagents are described, including:

(a) a thiol-terminal polythioether, including a thiol-terminal polythioether of Formula (18a), a thiol-terminal polythioether of Formula (18b), or a combination of them:

Where

each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and

each X independently includes —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given 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; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with terminal thiol groups; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a metal chelating agent R ⁹ -LR ⁹ , where each R ⁹ independently includes a terminal group capable of reacting with a thiol; and -L- contains a ligand capable of binding to the metal.

In the third aspect, polythioether prepolymers containing a thiol-terminal ligand capable of binding to a metal containing a reaction product of reactants are described, comprising:

(a) a thiol-terminal polythioether containing a ligand capable of binding to a metal, including a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal, a thiol-terminal polythioether of Formula (29b) containing a ligand capable of binding to a metal , or their combination:

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L contains a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and

each X independently includes —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent, alkenyl-terminal polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6; and

each V is a group containing a terminal alkenyl group; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a polyalkenyl compound.

In the fourth aspect, methods are described for preparing a thiol-terminal polythioethers of Formula (29a) containing a ligand capable of binding to a metal, including the reaction of (N + 1) moles of the thiol-terminal polythioether of Formula (18a) with (N) moles of the metal-chelating agent R ⁹ -LR ⁹ :

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L contains a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and

each X independently includes —O—, —S—, or —NR ⁵ -, where R ⁵ includes a hydrogen atom or methyl; and

each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

In the fifth aspect, methods are described for preparing a thiol-terminal polythioethers of Formula (29b) containing a ligand capable of binding to a metal, comprising reacting (z) moles of a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal with one (1 ) we pray polyfunctionalizing agent B {V} _z :

Where

N is an integer from 1 to 10;

each R ^{9 ′ is} independently a fragment formed by the reaction of R ^{9 of the} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ containing a terminal group capable of reacting with a thiol; and L contains a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and

each X independently includes —O—, —S—, or —NR ⁵ -, where R ⁵ includes a hydrogen atom or methyl;

each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with a terminal thiol group; and

each -V'- is formed by the reaction of -V with a thiol.

In the sixth aspect, compositions containing prepolymers containing a ligand capable of binding to a metal are described.

In the seventh aspect, a cured sealant is described comprising compositions containing prepolymers containing a ligand capable of binding to a metal.

Brief Description of the Drawings

FIG. 1 is a table that presents the calculated values of the energy of interaction of ligands with aluminum (III) surfaces, described in Example 4.

The following describes private embodiments of the compositions and methods. The described embodiments do not limit the scope of the claims. On the contrary, the claims cover all possible alternatives, modifications and equivalents.

Detailed description

Definitions

In the context of the present description, it should be understood that the embodiments described in the present application allow various alternative embodiments and sequence of steps, unless otherwise specified. In addition, with the exception of examples or cases where otherwise expressly stated, all figures reflecting, for example, the quantities of ingredients used in the description and in the claims, should be understood as being preceded by the term “about.” Accordingly, unless otherwise indicated, the numerical parameters given in the present description and the claims are approximate values, which may vary depending on the target characteristics to be achieved. Finally, without aiming to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in light of the number of significant figures given and using standard rounding techniques.

Although the numerical ranges and parameters describing the broad scope of the present invention are approximate values, the numerical values given in the specific examples are given as accurately as possible. However, any numerical value, by its nature, contains certain errors, which are the inevitable result of standard deviations with appropriate test measurements.

It should also be understood that any numerical range given in this text includes all sub-intervals included in it. For example, the interval “from 1 to 10” includes all sub-intervals between (and including) a given lower value of about 1 and a lower value of about 10, that is, having a minimum value of about 1 or more, and a maximum value of equal to about 10 or less. Also in this text, the use of the term “or” means “and / or” unless specifically indicated otherwise, even though in some cases “and / or” may be used explicitly.

A dash (“-”), not located between two letters or symbols, is used to indicate the point of covalent bonding of a substituent or bonding between atoms. For example, the chemical group —CONH ₂ is linked to another fragment through a carbon atom.

"Acetylacetonate group" means a group having the structure of Formula (1):

In some embodiments, acetylacetonate means a metal chelating agent containing an acetylacetonate group and one or more reactive functional groups. In some embodiments, said one or more reactive functional groups may be capable of reacting with a thiol group, such as, for example, an epoxy group, an alkenyl group, a Michael acceptor group, or a group containing a saturated carbon atom that carries a leaving group that is well suited for nucleophilic substitution, such as, for example, -Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), etc.

The term "alkanarene" refers to a hydrocarbon group containing one or more aryl and / or arenediyl groups and one or more alkyl and / or alkanediyl groups, where aryl, arenediyl, alkyl and alkanediyl correspond to the definitions given in this text. In some embodiments, each aryl and / or arenediyl group (s) is C _6-12 , C _6-10 , and in some embodiments, phenyl or benzenediyl. In some embodiments, each aryl and / or arediyl group (s) is C _1-6 , C _1-4 , C _1-3 , and in some embodiments, methyl, methanediyl, ethyl, or ethane-1,2-diyl . In some embodiments, the alkanarene group is a C _4-18 alkanarene, C _4-16 alkanarene, C _4-12 alkanarene, C _4-8 alkanarene, C _6-12 alkanarene, C _6-10 alkanarene, and in some embodiments C _6-9 alkanarin. Examples of alkanarene groups include diphenylmethane.

The term “alkanarenediyl” refers to the diradical of an alkanarene group. In some embodiments, the alkanarendyl group is a C _4-18 alkanarendyl, C _4-16 alkanarendyl, C _4-12 alkanarendyl, C _4-8 alkanarendyl, C _6-12 alkanarendyl, C _6-10 alkanarendyl, and in some embodiments C _6-9 alkanarendyl. Examples of alkane-diene groups include diphenylmethane-4,4'-diyl.

The term "alkanediyl" refers to a diradical of a saturated branched or linear acyclic hydrocarbon group containing, for example, from 1 to 18 carbon atoms (C _1-18 ), from 1 to 14 carbon atoms (C _1-14 ), from 1 to 6 atoms carbon (C _1-6 ), from 1 to 4 carbon atoms (C _1-4 ) or from 1 to 3 carbon atoms (C _1-3 ). Branched alkanediyl contains at least three carbon atoms. In certain embodiments, alkanediyl is C _2-14 alkanediyl, C _2-10 alkanediyl, C _2-8 alkanediyl, C _2-6 alkanediyl, C _2-4 alkanediyl, and, in certain embodiments, C _2-3 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 (for example, -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-1,8- diyl, nonan-1,9-diyl, decane-1,10-diyl, to decan-1,12-diyl, etc.

The term “alkancycloalkane” refers to a saturated hydrocarbon group containing one or more cycloalkyl and / or cycloalkanediyl groups and one or more alkyl and / or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl and alkanediyl correspond to the definitions in this text. 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 of the implementation of the alkancycloalkane group is a C _4-18 alkancycloalkane, C _4-16 alkancycloalkane, C _4-12 alkancycloalkane, C _4-8 alkancycloalkan, C _6-12 alkancycloalkane, C _6-10 alkancycloalkan, and in certain embodiments , C _6-9 alkancycloalkane. Examples of alkane cycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

The term "alkancycloalkanediyl" refers to the diradical of an alkancycloalkane group. In certain embodiments of the implementation of the alkancycloalkanediyl group is a C _4-18 alkancycloalkanediyl, C _4-16 alkancycloalkanediyl, C _4-12 alkanocycloalkanediyl, C _4-8 alkancycloalkanediyl, C _6-12 alkancycloalkanediyl, C _6-10 alkanocycloalkanediyl, and in certain embodiments C _6-9 alkancycloalkanediyl. Examples of alkanecycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.

The term "alkenyl" group refers to a group having the structure -CR = C (R) ₂ , where the alkenyl group is terminal and is attached to a larger molecule. In such scenarios, the implementation of each R can be selected, for example, from a hydrogen atom and a C _1-3 alkyl. In some embodiments, each R is a hydrogen atom, and the alkenyl group has the structure —CH═CH ₂ .

The term "alkoxy" refers to an -OR group, where R is an alkyl, as defined in this text. 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.

The term "alkyl" refers to a mono radical of a saturated, branched or linear acyclic hydrocarbon group containing, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, from 1 to 4 carbon atoms or from 1 up to 3 carbon atoms. It should be understood that a branched alkyl group contains at least three carbon atoms. In some embodiments, the implementation of the alkyl group is a C _1-6 alkyl, C _1-4 alkyl, and in some embodiments, the implementation of C _1-3 alkyl. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like. In certain embodiments, the alkyl group is C _1-6 alkyl, C _1-4 alkyl, and in certain embodiments, C _1-3 alkyl. It should be understood that a branched alkyl group contains at least three carbon atoms.

The term "bis (sulfonyl) alkanol group" refers to a group having the general Formula (2):

wherein each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH. In some embodiments, the bis (sulfonyl) alkanol group has the structure —CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH ₂ —CH ₂ -,

In some embodiments, the implementation of the "bis (sulfonyl) alkanol group" may be a monovalent bis (sulfonyl) alkanol group or a divalent bis (sulfonyl) alkanol group. In some embodiments, the monovalent bis (sulfonyl) alkanol may be a terminal bis (sulfonyl) alkanol group, such as a "1- (ethylene sulfonyl) -n- (vinyl sulfonyl) alkanol group." The terminal bis (sulfonyl) alkanol group can be obtained by reacting a bis (sulfonyl) alkanol and can have a terminal fragment with the general structure -R ^{8 '} -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O ) ₂ -R ⁸ where R ^{8 '} is a fragment resulting from the reaction of R ⁸ with a fragment capable of reacting with R ⁸ ; each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH. In some embodiments, each R ⁸ contains a reactive functional group, and in some embodiments, the implementation is —CH═CH ₂ . In some embodiments, the terminal bis (sulfonyl) alkanol group is a 1- (ethylene sulfonyl) -n- (vinylsulfonyl) alkanol group, such as 1- (ethylene sulfonyl) -3- (vinylsulfonyl) propan-2-ol, i.e. —CH ₂ —CH ₂ —S (O) ₂ —CH ₂ —CH (—OH) —CH ₂ —S (O) ₂ —CH═CH ₂ . In some embodiments, the terminal bis (sulfonyl) alkanol group has the structure —CH ₂ —CH ₂ —S (O) ₂ —R ¹⁰ —CH (—OH) —R ¹⁰ —S (O) ₂ —CH═CH ₂ .

In some embodiments, the implementation of the bis (sulfonyl) alkanol group can also be divalent, as in the case when this group is included in the main chain of a prepolymer, such as the polythioethers described in US patent application No. 13 / 923,903. In some embodiments, the bivalent bis (sulfonyl) alkanol group may have the general structure -R ^{8 '} -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -R ^8' -; in some embodiments, -CH ₂ -CH ₂ -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -CH ₂ -CH ₂ -, in some embodiments, -R ^{8 ′} —S (O) ₂ —CH ₂ —CH (—OH) —CH ₂ —S (O) ₂ —R ^{8 ′} - and in some embodiments, —CH ₂ —CH ₂ —S (O) ₂ —CH ₂ -CH (-OH) -CH ₂ -S (O) ₂ -CH ₂ -CH ₂ -, where R ^{8 '} and R ¹⁰ correspond to the definitions in this text. In some embodiments, a 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.

The term "bis (sulfonyl) alkanol" refers to a compound of the general formula R ⁸ -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -R ⁸ , where each R ⁸ is a fragment containing a terminal reactive functional group; and each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH. In some embodiments, each R ⁸ contains a terminal group capable of reacting with a thiol group, such as, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or a group containing a saturated carbon atom that carries a leaving group that is well suited for nucleophilic substitution such as, for example, -Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), etc. In some embodiments, the implementation of the bis (sulfonyl) alkanol can be a bis (vinylsulfonyl) alkanol containing terminal alkenyl groups. In some embodiments, the implementation of the bis (sulfonyl) alkanol can be a bis (vinylsulfonyl) alkanol, in which R ⁸ contains a terminal alkenyl group, such as a compound having the formula CH ₂ = CH-S (O) ₂ -R ¹⁰ -CH (- OH) -R ¹⁰ -S (O) ₂ -CH = CH ₂ . In some embodiments, the bis (vinylsulfonyl) alkanol is 1,3-bis (vinylsulfonyl) -2-propanol. In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing compound can be obtained by reacting a bis (vinylsulfonyl) alkanol with a compound containing a reactive terminal functional group and a terminal group capable of reacting with the terminal alkenyl groups of a bis (vinylsulfonyl) alkanol, such as a thiol group or epoxy group. In such scenarios, the implementation of the bis (sulfonyl) alkanol may have the structure R ^{8 '} -CH ₂ -CH ₂ -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -CH ₂ -CH ₂ -R ^{8 '} , where each R ^8' is a fragment resulting from the reaction of a compound with terminal alkenyl groups of a bis (vinylsulfonyl) alkanol.

"Bis (sulfonyl) alkanol-containing" polymer, prepolymer or adduct means a polymer, prepolymer or adduct in which one or more divalent bis (sulfonyl) alkanol groups are included in the main chain of the polymer, prepolymer or adduct.

The divalent bis (sulfonyl) alkanol group can be included in the prepolymer by reaction, for example, in a suitable ratio, of a polythiol monomer or of a prepolymer of Formula (3a) with a bis (sulfonyl) alkanol of Formula (4a):

where R is an organic fragment, w is an integer not less than 2, and each R ⁸ contains a terminal group capable of reacting with a thiol group, such as, for example, an alkenyl group, an epoxy group, a Michael-acceptor group or a group containing a saturated carbon atom carrying a leaving group well suited for nucleophilic substitution, such as, for example, -Cl, -Br, -I, -OSO ₂ CH ₃ (mesilate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate ) etc. In some embodiments, the implementation of the bis (sulfonyl) alkanol of Formula (4A) may be a bis (vinylsulfonyl) alkanol having the structure of Formula (4b):

wherein each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH. In some embodiments, the implementation of the bis (sulfonyl) alkanol may be a 1,3-bis (vinylsulfonyl) -2-propanol. Alternatively, the bis (sulfonyl) alkanol group can be introduced into the prepolymer main chain by reacting, in a suitable ratio, the thiol-terminal bis (sulfonyl) alkanol of Formula (4c) with a reagent of Formula (3b):

where R is an organic fragment, w is an integer not less than 2, R ^{8 '} is a fragment formed by the reaction of R ⁸ with a fragment capable of reacting with R ⁸ ; each R ¹⁰ corresponds to the definition given in this text, and each R ⁷ contains a terminal group capable of reacting with a thiol group, such as, for example, an alkenyl group, an epoxy group, a Michael acceptor group, or a group consisting of a saturated carbon atom carrying a leaving group well suited for nucleophilic substitution, such as, for example, -Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), etc. .

By selecting the desired ratio of Formula (3a) and Formula (4a), or Formula (4c) and Formula (3b), one or more bis (sulfonyl) alkanol groups can be introduced into the prepolymer, as a chain segment, as a terminal reactive group, or both are implemented. For example, a bis (vinylsulfonyl) alkanol can be used to introduce one or more 1, n-bis (ethylene sulfonyl) alkanol groups into the main chain of a prepolymer chain, one or more terminal 1- (ethylene sulfonyl) -n- (vinyl sulfonyl) alkanol groups, or both of these options.

In some embodiments, the implementation of bis (vinylsulfonyl) -2-propanol can be introduced into the reaction with thiol-terminal monomers / polymers for the introduction of 1,3-bis (ethylene sulfonyl) -2-propanol groups in the polymer chain.

In some embodiments, the implementation of bis (vinylsulfonyl) -2-propanol can be entered into reaction with thiol-terminal monomers / polymers to obtain 1- (ethylenesulfonyl) -3- (vinyl sulfonyl) -2-propanol terminal groups, where the terminal alkenyl group is well known Michael acceptor.

The fragment formed by the reaction of a bis (sulfonyl) alkanol with a thiol group is a reaction product of a thiol group and a fragment containing a terminal group capable of reacting with a thiol group. Examples of terminal groups capable of reacting with thiol groups include epoxy groups, ethylene groups, and Michael acceptor groups. In some embodiments, the fragment formed by the reaction of a bis (sulfonyl) alkanol with a thiol group has the structure: -CH ₂ -CH ₂ -R-, -CH (-OH) -CH ₂ -R-, -CH ₂ -CH ( -OH) -R- or -CH ₂ -CH ₂ -SO ₂ -R-, where R is a covalent bond or an organic moiety bound to a sulfonyl group.

The fragment formed by the reaction of a bis (sulfonyl) alkanol with a thiol group is also referred to as the R ^{8 '} fragment, which is formed by the reaction of the R ⁸ group with a thiol group, where R ⁸ is a terminal group capable of reacting with the thiol group.

In some embodiments, the implementation of R ^{8 '} is formed during the reaction of a bis (sulfonyl) alkanol with a compound having a terminal group capable of reacting with a thiol group and a group capable of reacting with a bis (sulfonyl) alkanol. In some embodiments, the implementation of R ^{8 '} is formed during the reaction of a bis (ethylene sulfonyl) alkanol with a compound having a terminal group capable of reacting with a thiol group and a group capable of reacting with an ethylene group. In this embodiment, the implementation of R ^{8 '} can have the structure: -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 -, where R ′ is an organic fragment obtained by reacting a compound used to introduce a terminal functional group into a bis (ethylene sulfonyl) alkanol, such as an ethylene group, an epoxy group, a Michael-acceptor group or a group containing a saturated carbon atom that carries a leaving group that is well suited for nucleophilic substitution, such as, for example, - Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), - OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), etc.

In some embodiments, the implementation of R ^{8 'is} selected from C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted C _2-10 heteroalkanediyl, C _4-14 alkancycloalkanediyl, substituted C _4-14 alkancycloalkanediyl, C _{4 -14} heteroalkancycloalkanediyl, substituted C _4-14 heteroalkancycloalkanediyl, C _4-14 alkanarendiyl, substituted C _4-14 alkanarenediyl, C _4-14 heteroalkanarendiyl, and substituted C _4-14 heteroalkanarendyl. In some embodiments, the implementation of R ^{8 '} represents ethane-diyl.

In some embodiments, the implementation of R ⁸ selected from C _2-10 alkyl, substituted C _2-10 alkyl, C _2-10 heteroalkyl, substituted C _2-10 heteroalkyl, C _4-14 alkancycloalkyl, substituted C _4-14 alkancycloalkyl, C _{4- 14} heteroalkancycloalkyl, substituted C _4-14 heteroalkancycloalkyl, C _4-14 alkanaryl, substituted C _4-14 alkanaryl, C _4-14 heteroalkanaryl, and substituted C _4-14 heteroalkanaryl. In some embodiments, R ⁸ is ethylene, i.e. -CH = CH ₂ .

The term "cycloalkanediyl" refers to the 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.

The term "cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon monoradical group. 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.

The term “heteroalkanediyl” refers to an alkanediyl group in which one or more of the carbon atoms is replaced with a heteroatom, such as N, O, S, or P. In some embodiments, the heteroalkanediyl heteroatom is selected from N and O.

The term “heteroalkan-adandyl” refers to an alkane-dandyl group in which one or more of the carbon atoms is replaced with a heteroatom, such as N, O, S, or P. In some embodiments of the heteroalkanarendiyl, the heteroatom is selected from N and O.

The term “heterocycloalkanediyl” refers to a cycloalkanediyl group in which one or more of the carbon atoms is replaced by a heteroatom, such as N, O, S, or P. In some embodiments, the hetero cycloalkanediyl is selected from N and O.

The term "Michael acceptor" refers to substituted alkene / alkyne compounds in which at least one alkene / alkyne group is directly attached to one or more electron-acceptor groups, such as carbonyl (-CO), nitro (-NO ₂ ), nitrile (-CN), alkoxycarbonyl (-COOR), phosphonate (-PO (OR) ₂ ), trifluoromethyl (-CF ₃ ), sulfonyl (-SO ₂ -), trifluoromethanesulfonyl (-SO ₂ CF ₃ ), p-toluenesulfonyl (- SO ₂ -C ₆ H ₄ -CH ₃ ), etc. The types of compounds that work as Michael's acceptors are vinyl ketones, quinones, nitroalkenes, acrylonitriles, acrylates, methacrylates, cyanoacrylates, acrylamides, maleimides, dialkyl vinyl phosphonates and vinyl sulfones. Other examples of Michael acceptors are described in Mather et al., Prog. Polym. Set 2006, 31, 487-531. Also well-known are Michael acceptors, having more than one Michael acceptor group. 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) dimimimide and 1,1' - (methylene di-4, 1-phenylene) bismaleimide, vinyl sulfones, such as divinyl sulfone and 1,3-bis (vinyl sulfonyl) -2-propanol, etc. In some embodiments, the implementation of the Michael-acceptor group has the structure of Formula (7a) or Formula (7b):

wherein each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH.

The term "Michael acceptor compound" refers to a compound containing at least one Michael acceptor terminal group. In some embodiments, the Michael acceptor compound is divinyl sulfone, and the Michael acceptor group is vinyl sulfonyl, i.e. -S (O) ₂ -CH = CH ₂ . In some embodiments, the Michael acceptor compound is a bis (vinyl sulfonyl) alkanol, and the Michael acceptor group is 1- (ethylene sulfonyl) -n- (vinyl sulfonyl) alkanol (-CH ₂ -CH ₂ -S (O) ₂ -R ^10- CH (-OH) -R ¹⁰ -S (O) ₂ -CH = CH ₂ ), and in some embodiments, the implementation of 1- (ethylene sulfonyl) -3- (vinylsulfonyl) propan-2-ol (-CH ₂ -CH ₂ -S (O) ₂ -CH ₂ -CH (-OH) -CH ₂ -S (O) ₂ -CH = CH ₂ ).

The term "hydroxypyridinone groups" includes groups such as 3-hydroxy-4-pyridinone and 3-hydroxy-2-pyridinone, having the structure of Formula (8a) or Formula (8b), respectively:

where R represents an organic group, such as an alkyl group. The hydroxypyridinone metal chelating agent contains a hydroxypyridinone group and one or more reactive functional groups, such as terminal thiol groups.

The term "ligand capable of binding to a metal" refers to an ion or molecule that binds to a metal atom and, potentially, to other atoms to form a coordination complex. Binding between a metal and / or atoms usually involves donating one or more pairs of electrons to the metal, and the nature of such binding may consist, for example, in a covalent, ionic or hydrogen bond. The ligands capable of binding to the metal described in this text are capable of forming coordination complexes with surfaces used in the aerospace field, such as aluminum and titanium surfaces, which can oxidize. In the case of oxidized surfaces, the ligand capable of binding to the metal can form a coordination complex with a metal, such as Al (III), and oxygen atoms. The coordination complex can increase adhesion to the surface of a metal or oxidized metal.

Ligands capable of binding to the metal may be included in the main chain of the prepolymer, as described in the present text. In addition to the fragment capable of forming a coordination complex, for introducing a prepolymer into the main chain, the ligand capable of binding to the metal includes or is modified to include at least two groups capable of reacting with the group of the prepolymer subfragment. Such reactive ligands capable of binding to the metal may be commercially available or may be derivatized to include suitable reactive substituent groups in their composition, using methods known to those skilled in the art.

The term "polyalkoxysilyl group" refers to a group having the formula:

where p is selected from 0, 1 and 2; and each R ^{4 is} independently selected from C _1-4 alkyl. In some embodiments, the polyalkoxysilyl group p is 0, p is 1, and in some embodiments, the implementation of p is 2. In some embodiments, the polyalkoxysilyl group each R ^{4 is} independently selected from ethyl and methyl. In some embodiments of the polyalkoxysilyl group, each R ⁴ is ethyl, and in some embodiments, each R ⁴ is methyl. In some embodiments of the polyalkoxysilyl group, this group is selected from -Si (-OCH ₂ CH ₃ ) ₃ , -Si (-OCH ₃ ) ₃ , -Si (-CH ₃ ) (- OCH ₃ ) ₂ , -Si (-CH ₃ ) ₂ (-OCH ₃ ), -Si (-CH ₃ ) (- OCH ₂ CH ₃ ) ₂ , -Si (-CH ₃ ) ₂ (-OCH ₂ CH ₃ ), -Si (-CH ₂ CH ₃ ) (- OCH ₃ ) and -Si (-CH ₂ CH ₃ ) ₂ (-OCH ₃ ).

The term “substituted” refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituents. In certain embodiments, the substituent is selected from halogen, -S (O) ₂ OH, -S (O) ₂ , -SH, -SR, where R is C _1-6 alkyl, -COOH, -NO ₂ , -NR ₂ where each R is independently selected from a hydrogen atom and C _1-3 alkyl, —CN, —C═O, C _1-6 alkyl, —CF ₃ , —OH, phenyl, C _2-6 heteroalkyl, C _5-6 heteroaryl , C _1-6 alkoxy groups and —COR, where R is C _1-6 alkyl. In certain embodiments, the substituent is selected from —OH, —NH _2, and C _1-3 alkyl.

When used in this text, the term "polymer" refers to oligomers, homopolymers and copolymers. Unless otherwise specified, molecular weights are the number average molecular weights for polymeric materials, denoted by "M _n " and are determined, for example, by gel permeation chromatography using polystyrene standards by known methods.

The following are particular variants of prepolymers containing a ligand capable of binding to a metal, such as polythioethers containing a ligand capable of binding to a metal, their compositions and methods of synthesis. The described embodiments do not limit the scope of the claims. On the contrary, the claims cover all alternatives, modifications and equivalents.

To increase the tensile strength and adhesion of hardened aerospace sealants to surfaces, such as bare or anodized metal surfaces, ligands capable of binding to the metal, such as bis (sulfonyl) alkanols, are included in the main chain of sulfur-containing prepolymers. Prepolymers containing a ligand capable of binding to a metal, such as bis (sulfonyl) alkanol-containing sulfur-containing prepolymers, can be adapted to any suitable curing chemistry. For example, polythioether prepolymers containing a thiol-terminal ligand capable of binding to metal, and polyepoxide hardeners provide sealants that can be used in the aerospace industry.

Bis (sulfonyl) alkanol-containing polythioethers

Bis (sulfonyl) alkanol-containing polythioethers described in this text are distinguished by the presence of one or more bis (sulfonyl) alkanol groups included in the main chain of the polythioether.

Polythioethers that can be used in sealants for the aerospace industry are described, for example, in US Pat. No. 6,172,179. Polythioether refers to compounds containing at least two thioester-C-S-C-bonds. Polythioethers can be prepared, for example, by dithiol reaction with divinyl ethers. In general, bis (sulfonyl) alkanol-containing polythioethers can be obtained by reacting a monomeric bis (sulfonyl) alkanol having terminal groups capable of reacting with the polythioether.

In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing polythioether contains a fragment of Formula (10):

wherein each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH.

In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing polythioethers are the structure of Formula (11):

Where

each R ^{8 ′} is a fragment resulting from the reaction of a bis (sulfonyl) alkanol with thiol groups;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH; and

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; and

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r , where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

In some embodiments of Formula (11) and Formula (12), each R ¹ is - [- (CHR ³ ) _s —X—] _q - (CHR ³ ) _r -, where each X is independently selected from —O— and —S -. In some embodiments, where R is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, each X is -O- and in some embodiments, each X is -S-. In some embodiments, each R is a hydrogen atom.

In some embodiments of Formula (11) and Formula (12), each R ¹ is - [- (CH ₂ ) _s —X—] _q - (CH ₂ ) _r -, where each X is independently selected from —O— and —S -. In some embodiments, implementation, where R ¹ represents - [- (CH ₂ ) _s -X-] _q - (CH ₂ ) _r -, each X represents -O-, and in some embodiments, the implementation of each X represents-S -.

In some embodiments of Formula (11) and Formula (12), 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 some embodiments of Formula (11) and Formula (12), each R ¹ is derived from dimercaptodioxaoctane (DMDO), and in some embodiments, each R ¹ is derived from dimercaptodiethyl sulfide (DMDS).

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

In some embodiments of Formula (11) and Formula (12), n is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, and in some embodiments, an integer from 1 to 5. Except In addition, in some embodiments, the implementation of n can be any integer from 1 to 60.

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

In Formula (11), each R ^{8 '} is a group obtained by reacting a thiol group and a group capable of reacting with a thiol group, such as a terminal alkenyl group, a terminal epoxy group, or a Michael-acceptor terminal group. In some embodiments of Formula (11) and Formula (12), each R ^{8 'is} independently selected from C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted C _4-10 heteroalkanediyl, C _4-14 alkancycloalkanediyl , substituted C _4-14 alkancycloalkanediyl, C _4-14 heteroalkancycloalkanediyl, substituted C _4-14 heteroalkancycloalkanediyl, C _2-14 alkanarenediyl, substituted C _4-14 alkanarendiyl, C _4-14 heteroalkane alkylene, and substituted C _4-14 heteroalkanarendiyl. In some embodiments, the implementation of all R ^{8 'are the} same. In some embodiments, each R ^{8 ′} is ethane-diyl, i.e. -CH ₂ -CH ₂ -.

In some embodiments of Formula (11), each R ^{10 is} independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In some embodiments, the implementation of each R ¹⁰ represents methane-diyl, in some embodiments, the implementation of ethane-diyl, and in some embodiments, the implementation of 1,3-propane-diyl.

In some embodiments of Formula (11), each R ^{8 '} is ethane-diyl, and each R ¹⁰ is methane-diyl.

In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing polythioether is selected from a bis (sulfonyl) alkanol-containing polythioether of Formula (13a), a bis (sulfonyl) alkanol-containing polythioether of Formula (13b) and their combinations:

Where

N is an integer from 1 to 10;

each R ^{8 ′} is a fragment resulting from the reaction of a bis (sulfonyl) alkanol with thiol groups;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6; and

each V is a group containing a terminal group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol; and

each R ^{6 is} independently selected from a hydrogen atom and a moiety having a terminal reactive group.

In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) N is 1, 2, 3, 4, 5, 6, 7, 8, 9, and in some embodiments, the implementation of N is 10. In In some embodiments, bis (sulfonyl) alkanol-containing polymers of Formula (13a) and Formula (13b) have a molecular weight ranging from 400 Daltons to 20,000 Daltons. In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) are a combination of bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) with different values of N. In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula ( 13b) are a combination of bis (sulfonyl) alkanol-containing polythioethers of Formula (13b) with different values of N. In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) N are 1.

In some embodiments of Formula (13a) and Formula (13b), each R ^{8 '} is a group obtained by reacting a thiol group and a group capable of reacting with a thiol group, such as a terminal alkenyl group, a terminal epoxy group, or a terminal acceptor group Michael In some embodiments of Formulas (13a) and Formula (13b), each R ^{8 ′ is} independently selected from C _2-10 alkanediyl, substituted C _2-10 alkanediyl, C _2-10 heteroalkanediyl, substituted C _2-10 heteroalkanediyl, C _4-14 alkancycloalkanediyl , substituted C _4-14 alkancycloalkanediyl, C _4-14 heteroalkancycloalkanediyl, substituted C _4-14 heteroalkancycloalkanediyl, C _4-14 alkanarendiyl, substituted C _4-14 alkanarendiyl, C _4-14 heteroalkanarene and substituted C _4-14 heteroalkanediyl. In some embodiments, each R ^{8 ′ is the} same. In some embodiments, each R ^{8 ′} is ethane-diyl, i.e. -CH ₂ -CH ₂ -.

In some embodiments of Formulas (13a) and Formula (13b), each R ^{10 is} independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In some embodiments, the implementation of each R ¹⁰ represents methane-diyl, in some embodiments, the implementation of ethane-diyl, and in some embodiments, the implementation of 1,3-propane-diyl.

In some embodiments of Formula (13a) and Formula (13b), each R ^{8 '} is ethane-diyl, and each R ¹⁰ is methane-diyl.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers 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 some embodiments, implementation, where R ¹ represents - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, each X represents-O-, and in some embodiments, the implementation of each X is-S -. In some embodiments, each R ³ is a hydrogen atom.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers 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 some embodiments, implementation, where R ¹ represents - [- (CH ₂ ) _s -X-] _q - (CH ₂ ) _r -, each X represents -O-, and in some embodiments, the implementation of each X represents-S -.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers 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 some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), each R ¹ is derived from DMDO, and in some embodiments, each R ¹ is derived from DMDS.

In some embodiments, each m is independently an integer from 1 to 3. In some embodiments, all m are the same and equal to 1, 2, and in some embodiments, 3.

In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers 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, and in some embodiments, an integer from 1 to 5. In addition, in some embodiments, the implementation of n can be any integer from 1 to 60.

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

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers 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 some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), each R ^{1 is} selected from C _2-6 alkanediyl and - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -.

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

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), where 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 some embodiments, s is 2, q is 2, r is 2, and X is —O—; and in some embodiments, s is 2, r is 2, q is 1, and X is -O-.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), where R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r , each R ³ is is a hydrogen atom, and in some embodiments, at least one R ³ is methyl.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), all R ^{1 are the} same, and in some embodiments, the implementation of at least one R ¹ is different.

In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) are all R ^{6 the} same, and the terminal reactive group is selected from -SH, -CH = CH ₂ , -NH ₂ , -OH, epoxy , polyalkoksisilyl group and Michael acceptor group.

In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing polythioether Formula (13a) has the structure of Formula (14):

where each R ^{8 '} corresponds to the definition given in this text; 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-, where each R ¹² represents-CH ₂ -CH ₂ -.

In some embodiments, the implementation of the bis (sulfonyl) alkanol-containing polythioether Formula (13a) has the structure of Formula (15):

where 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-, where each R ¹² represents-CH ₂ -CH ₂ -.

In some embodiments, bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) each R ⁶ is a hydrogen atom, and bis (sulfonyl) alkanol-containing polythioethers are thiol-terminal, having the structures of Formula (16a), Formula (16b), Formulas (16c) or Formulas (16d):

where A, N, R ^{8 '} , R ¹⁰ , V', z and B correspond to the data in this text definitions.

B (-V) _z is a polyfunctionalizing agent. A polyfunctionalizing agent may be one type of polyfunctionalizing agent or a combination of different types of functionalizing agents that may have the same or different functionality. In some embodiments, z is 3, 4, 5, or 6. Suitable polyfunctionalizing agents include trifunctionalizing agents, i.e. compounds where z is 3. Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), modified-1,2,3 -propanthritiol, modified-isocyanurate-containing trithiols, 1,2,4-trivinylcyclohexane, and combinations of any of the listed components, as described, for example, in US Patent Publication No. 2010/0010133 in paragraphs [0102] - [0105], quoted a fragment of which includes in the present text by reference. Other suitable polyfunctionalizing agents include trimethylolpropane trivinyl ether. Mixtures of polyfunctionalizing agents can also be used. Suitable isocyanurate-containing functionalizing agents are described, for example, in US Patent Application Publication No. 2011/0319559.

R ⁶ is a moiety having a terminal reactive group. The terminal reactive group can be chosen in such a way that it fits the specific chemistry of curing. For example, in some embodiments, the implementation of all R ^{6 are the} same, and the reactive group is selected from -SH, -CH = CH ₂ , -NH ₂ , -OH, epoxy, polyalkoxysilyl group and Michael acceptor group. You can choose a specific curing chemistry to achieve, for example, the desired curing time of the composition, method of application, compatibility with the surface, shelf life, lifetime and / or properties of the cured sealing composition. For example, in some embodiments, the implementation of a bis (sulfonyl) alkanol-containing polythioether of Formula (13a) and / or Formula (13b) is thiol-terminal, and R ⁶ is a hydrogen atom or a fragment terminated by a thiol group. In some embodiments, B (-V) _z is an alkenyl-terminal polyfunctionalizing agent, wherein each -V contains a terminal alkenyl group, and accordingly, each -V'- is a fragment obtained by reacting an alkenyl group and a group capable of entering into reaction with alkenyl groups.

In some embodiments, the polyfunctionalizing agent may include one or more bis (sulfonyl) alkanol groups. For example, in some embodiments, a polyfunctionalizing agent can be reacted with a bis (sulfonyl) alkanol having a terminal group capable of reacting with a terminal group of the polyfunctionalizing agent, and a terminal group capable of reacting with a thiol group. Thus, in some embodiments, the implementation of a bis (sulfonyl) alkanol-containing polyfunctionalizing agent of Formula (17) can be obtained by reacting a bis (sulfonyl) alkanol of Formula (4a) with a polyfunctionalizing agent having the formula B (-V) _z :

where R ⁸ , R ^{8 '} , R ¹⁰ , B and V' correspond to the definitions given in this text.

In some embodiments, bis (sulfonyl) alkanol containing polythioethers of Formula (13a) and Formula (13b) R ⁶ is a hydrogen atom, and bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) are thiol-terminal.

In some embodiments, the bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b) are thiol-terminal, for example, each R ⁶ is a hydrogen atom and can be called non-blocking bis (sulfonyl) alkanol-containing polythioethers. In some embodiments, the implementation of unblocked bis (sulfonyl) alkanol-containing polythioether is a liquid at room temperature. In addition, in some embodiments, the implementation of unblocked bis (sulfonyl) alkanol-containing polythioether has a viscosity at 100% solids content less than 500 poises, for example, from 100 poises to 300 poises or, in some cases, from 100 poises to 200 poises at about 25 ° C and a pressure of about 760 mmHg, as determined according to ASTM D-2849 §79-90 and measured using a Brookfield CAP 2000 viscometer. Any end point in the specified ranges of values can also be used in the present invention. In some embodiments, an unblocked bis (sulfonyl) alkanol-containing polythioether has a number average molecular weight from 400 grams per mole to 10,000 grams per mole, for example, from 1000 grams per mole to 8000 grams per mole, where the molecular weight is determined, for example, by gel penetrating chromatography using polystyrene standard. Any end point in the specified ranges of values can also be used in the present invention. In some embodiments, the implementation of T _g unblocked bis (sulfonyl) alkanol-containing polythioether is not higher than -55 ° C., For example, not higher than -60 ° C.

In some embodiments, the implementation of bis (sulfonyl) alkanol-containing polythioether can be blocked or terminated at the ends of the chain with a specific reactive group to adapt the bis (sulfonyl) alkanol-containing polythioether to use with different curing chemistry.

Bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) and Formula (13b), in which R ⁶ is a fragment containing a terminal reactive group, can be obtained by introducing into the corresponding thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a ) and Formula (13b), where each R ⁶ represents a hydrogen atom, an end fragment having a terminal reactive group and a group capable of reacting with a thiol group. Such blocked polythioether analogs and methods for producing blocked polythioether analogs that can be used in sealants for the aerospace industry are described, for example, in US Patent No. 6,172,179 and in US Patent Application Publication No. 2011/0319559, each of which is incorporated into this text by reference . In some embodiments, R ⁶ contains a terminal alkenyl group, a terminal epoxy group, a terminal polyalkoxysilyl group, a terminal amino group, or a Michael acceptor terminal group. The end group of R ⁶ may have a molecular weight less than 500 daltons.

Terminal-modified bis (sulfonyl) alkanol-containing polythioethers. described in this text can be obtained in a number of ways known to those skilled in the art. For example, to obtain a terminal-modified bis (sulfonyl) alkanol-containing polythioether of Formula (13a) and Formula (13b), the thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a) or Formula (16b) described in this text, it is possible to react with a compound having a terminal functional group and a terminal group capable of reacting with thiol groups.

For example, to obtain an alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a), the thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a) can be reacted with a compound containing a terminal alkenyl group and an isocyanate group, such as a group derived from TMI, 2-isocyanatoethyl methacrylate or allyl isocyanate, in the presence of a catalyst - dibutyl tin dilaurate. As another example, a bis (sulfonyl) alkanol-containing polythioether of Formula (13a) can be reacted with an alkenem, such as 3-butene-1-ol, and an aldehyde, such as formaldehyde, in the presence of sulfonic acid (for example, 4.7 meq. / g H ⁺ ), such as Amberlyst ™ 15, in an organic solvent, such as toluene, to obtain an alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a). In some embodiments, an alkenyl terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a) can be obtained by reacting a polyalkenyl compound, such as a dialkenyl compound, with a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a).

Polyalkoxy-silyl-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing abysses with the help of a polyalkoxysilane, such as 3-isocyanatopropyltrimethocyscischistocyscischistocistocistocistocistocistocistocistocistocistocistocistocistocistocistocistocistocisto (a), with the help of a polyalkoxysilane, such as 3-isocyanatopropyltrimethocyscisch in the presence of dibutyltin dilaurate, to obtain the corresponding polyalkoxysilyl terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a). In some embodiments, the implementation of polyalkoxysilyl-terminal bis (sulfonyl) alkanol-containing polythioether Formula (13a) can be obtained by the reaction of vinyl alkoxysilane with a thiol-terminal bis (sulfonyl) alkanol-containing polythioether.

Epoxy-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a) with a mono-epoxide, such as epichlorohydrin, or with an alkenyl-glycidyl compound such as allyl-glycidyl ether, obtaining the corresponding epoxy-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a).

The amine-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can be obtained, for example, by reacting an activated alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a) or an acceptor of the Michael-terminal bis (sulfonyl) alkanol-containing polythioether Formulas (13a) with a diamine as an amino-substituted aniline, such as 4- (aminomethyl) aniline, or with an alkylamine, such as n-butylamine, optionally in the presence of a catalyst, such as 1,8-diazabicyclo [5.4.0] undec -7-ene (DBU), in an organic solvent, floor tea corresponding amine-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a). Alternatively, the amine-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can be obtained by reacting an isocyanate-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a) with a diamine, such as 4- (aminomethyl) aniline, to obtain the corresponding amine -terminal bis (sulfonyl) alkanol-containing polythioether Formula (13a). The amine terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can also be obtained by reacting a hydroxyl-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a) with an amino-substituted benzoate, such as ethyl 4-aminobenzoate, in the presence of Bu ₂ SnO or NaOMe, at elevated temperature, obtaining the corresponding amine-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (13a).

The isocyanate-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (13a) can be obtained, for example, by reacting the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (16a) with a diisocyanate, such as TDI, Isonate ™ 143L diphenylmethane diisocyanate), Desmodur ^® N3400 (1,3-diazetidin-2,4-dione, 1,3-bis (6-isocyanatohexyl) -), IPDI (isophorone diisocyanate), or Desmodur ^® W (H ₁₂ MDI), optional in the presence of a catalyst, such as dibutyl tin dilaurate. Isocyanate-terminal sulfur-containing polymers can be used as intermediates in the synthesis of other terminal-modified sulfur-containing polymers, such as some amine-terminal and thiol-terminal bis (sulfonyl) alkanol-containing polythioethers described in this text.

Similar reactions can be used to obtain blocked bis (sulfonyl) alkanol-containing prepolymers of Formula (13b).

In some embodiments, the implementation of the thiol-terminal bis (sulfonyl) alkanol-containing polythioether is a reaction product of the reagents, which are:

(a) a thiol-terminal polythioether selected from the thiol-terminal polythioether of Formula (18a), a thiol-terminal polythioether of Formula (18b) and their combinations:

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given 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; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6; and

each V is a group containing a terminal group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) bis (sulfonyl) alkanol of Formula (19):

Where

each R ^{8 is} independently selected from a moiety containing a terminal group capable of reacting with a terminal thiol group; and

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH.

In some embodiments, the thiol-terminal polythioethers of Formula (18a) and Formula (18b), each R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r , where each X is independently selected from -O - and -S-. In some embodiments, implementation, where R ¹ represents - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r , each X represents -O- and in some embodiments, the implementation of each X represents -S-. In some embodiments, each R ³ is a hydrogen atom.

In some embodiments, the thiol terminal polythioethers of Formula (18a) and Formula (18b), each R ¹ is - [- (CH ₂ ) _s —X–] _q - (CH ₂ ) _r -, where each X is independently selected from - O- and -S-. In some embodiments, implementation, where R ¹ represents - [- (CH ₂ ) _s -X-] _q - (CH ₂ ) _r -, each X represents -O- and in some embodiments, the implementation of each X is -S- .

In some embodiments of the thiol terminal polythioethers of Formula (18a) and Formula (18b), each R ¹ is - [(- CH ₂ -) _p -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 some embodiments of the thiol terminal polythioethers of Formula (18a) and Formula (18b), each R ¹ is derived from DMDO, and in some embodiments, each R ¹ is derived from DMDS.

In some embodiments of the thiol-terminal polythioethers of Formula (18a) and Formula (18b), each m is independently an integer from 1 to 3. In some embodiments, all m are the same and equal to 1, 2, and in some embodiments, 3.

In some embodiments, the thiol-terminal 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 in some embodiments, the implementation is an integer from 1 to 5. In addition, in some embodiments, the implementation of n can be any integer from 1 to 60.

In some embodiments of the thiol-terminal polythioethers of Formula (18a) and Formula (18b), each p is independently selected from 2, 3, 4, 5, and 6. In some embodiments, all p are the same and equal to 2, 3, 4, 5, or 6 .

In some embodiments, the thiol terminal polythioethers of Formula (18a) and Formula (18b), R ¹ is a derivative of DMDO, R ² is a derivative of divinyl ether, and the polyfunctionalizing agent is TAC.

In some embodiments, implementation, polythioether prepolymer of Formula (18a) has the structure of Formula (20):

In some embodiments of Formula (19), each R ^{10 is} independently selected from methane-diyl, ethane-diyl, and 1,3-propane-diyl. In some embodiments, each R ¹⁰ is methane-diyl, in some embodiments, ethan-diyl, and in some embodiments, 1,3-propan-diyl.

In some embodiments of Formula (19), R ⁸ contains a group capable of reacting with a thiol group selected from an alkenyl group, an epoxy group, and a Michael acceptor group. In some embodiments, each R ⁸ terminates in an alkenyl group. In certain embodiments, R ^{8 is} selected from C _2-10 alkyl, substituted C _2-10 alkyl, C _2-10 heteroalkyl, substituted C _2-10 heteroalkyl, C _4-14 alkancycloalkyl, substituted C _4-14 alkancycloalkyl, C _{4 -14} heteroalkancycloalkyl, substituted C _4-14 heteroalkancycloalkyl, C _4-14 alkanaryl, substituted C _4-14 alkanaryl, C _4-14 heteroalkanaryl, and substituted C _4-14 heteroalkanaryl. In some embodiments, R ⁸ is ethylene, i.e. -CH = CH ₂ .

In some embodiments, the bis (sulfonyl) alkanol of Formula (19) is bis (vinyl sulfonyl) alkanol. In some embodiments, the implementation, bis (vinylsulfonyl) alkanol has the structure of Formula (21):

where R ¹⁰ has the meaning specified in this text.

In some embodiments, the implementation, the bis (vinylsulfonyl) alkanol of Formula (19) is a 1,3-bis (vinylsulfonyl) -2-propanol and has the structure of Formula (22):

The thiol-terminal polythioethers of Formula (18a) and Formula (18b) and bis (vinylsulfonyl) alkanol Formula (19) can be reacted in the presence of a basic 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), dimethyl ethanol amine (DMEA), bis- (2-dimethylaminoethyl) ether, N-ethylmorpholine, triethylamine, 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU), pentamethylethylene tetraamine (PMDETA), benzyldimethylamine (BDMA), N, N, N'-trimethyl-N'-hydroxyethyl-bis (aminoethyl) ether and N '- (3- (dimethylamino) propyl) -N, N-dimethyl-1,3-propanediamine.

In some embodiments, the implementation described in this text, bis (sulfonyl) alkanol-containing polythioethers are characterized by an equivalent weight of mercaptan (MEW) from about 400 to 4000.

You can apply various methods of obtaining such polythioethers. Examples of suitable thiol-functional polythioethers and methods of preparation suitable for use in the compositions described herein are described in US Pat. No. 6,172,179. 2, line 29 - count. 4, line 22; count 6, line 39 - count. 10, line 50; and count 11, line 65 - count. 12, line 22, quoted fragments of which are incorporated into this text by reference. Such thiol-functional polythioethers can be difunctional, that is, linear polymers having two terminal thiol groups, or polyfunctional, that is, branched polymers having three or more terminal thiol groups. Such thiol-functional polythioethers are commercially available, for example, under the brand name Permapol® P3.1E from PRC-DeSoto International Inc., Sylmar, CA.

In some embodiments, the implementation of the thiol-terminal polythioether can be obtained by the reaction of a polythiol and a diene, such as divinyl ether, and the appropriate amounts of reagents used to make the polythioether are selected so that terminal thiol groups are formed. So, in some cases, (n or> n, for example n + 1) mol of a polythiol, such as dithiol or a mixture of at least two different dithiols, and from about 0.05 mol to 1 mol, for example, from 0.1 mol to The 0.8 mol of thiol-terminal polyfunctionalizing agent can be reacted with (n) moles of a diene, such as divinyl ether, or mixtures of at least two different dienes, such as divinyl ether. In some embodiments, the implementation of the thiol-terminal polyfunctionalizing agent is present in the reaction mixture in an amount sufficient to obtain a thiol-terminal polythioether having an average functionality of 2.05 to 3, for example, from 2.1 to 2.8.

The reaction used to obtain the thiol-terminal polythioether can be catalyzed by a free-radical catalyst. Suitable free radical catalysts include azo compounds, for example azobenitrile, such as azo (bis) isobutyronitrile (AIBN); organic peroxides, such as benzoyl peroxide and t-butyl peroxide; and inorganic peroxides, such as hydrogen peroxide. The reaction can also be accelerated by ultraviolet irradiation, with or without a cationic photoinitiator moiety. You can also apply the methods of ion catalysis using inorganic or organic bases, such as triethylamine.

Suitable thiol terminal polythioethers can be prepared by reacting divinyl ether or a mixture of divinyl ethers with an excess of dithiol or a mixture of dithiols.

So, in some embodiments, implementation, thiol-terminal polythioether is a reaction product of the reagents, which are:

(a) dithiol of Formula (23):

Where

R ^{1 is} selected from C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, C _5-8 heterocycloalkanediyl, and - [- (CHR ³ ) _s —X—] _q - (CHR ³ ) _r -; Where

each R ^{3 is} independently selected from hydrogen and methyl;

each X is independently selected from -O-, -S-, -NH-, and -NR-, where R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5; and

r is an integer from 2 to 10; and

(b) Divinyl ether of Formula (24):

Where

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given above;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

And, in some embodiments, the reagents may include (c) a polyfunctional compound, such as the polyfunctional compound B (-V) _z , where B, -V, and z correspond to the definitions in this text.

In some embodiments, dithiols suitable for use in the preparation of thiol-terminal polythioethers include dithiols having Formula (23), other dithiols described herein, or combinations of any dithiols described herein. In some embodiments, the implementation, the dithiol has the structure of Formula (23):

Where

R ^{1 is} selected from C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, C _5-8 heterocycloalkanediyl, and - [- (CHR ³ ) _s —X—] _q - (CHR ³ ) _r -;

Where

each R ^{3 is} independently selected from hydrogen and methyl;

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5; and

r is an integer from 2 to 10.

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

In some embodiments, the compounds of Formula (23), X is selected from -O- and -S-, and thus - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r - in Formula (23) represents - [(- CHR ³ -) _s -O-] _q - (CHR ³ ) _r - or - [(- CHR ³ ₂ -) _s -S-] _q - (CHR ³ ) _r -. In some embodiments, implementation, p and r are equal, for example, where p and r are both equal to 2.

In some embodiments, the dithiol of Formula (23), R ^{1 is} selected from C _2-6 alkanediyl and - [- (CHR ³ ) _s —X—] _q - (CHR ³ ) _r -.

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

In some embodiments, implementation, where R ¹ represents - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, s is 2, r is 2, q is 1, and X is -S- ; in some embodiments, s is 2, q is 2, r is 2, and X is —O—; and in some embodiments, s is 2, r is 2, q is 1, and X is -O-.

In some embodiments, the implementation, where R ¹ represents - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, each R ³ represents a hydrogen atom, and in some embodiments, the implementation of at least one R ³ is methyl.

Examples of suitable dithiols include, for example, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propandithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-pentanedithiol, 1 , 5, ps, hey, hey, hey, hey, hey? oxapentane and a combination of any of the above. The polythiol may have one or more groups in the side chains selected from a lower (eg, C _1-6 ) alkyl group, a lower alkoxy group, and a hydroxyl group. Suitable alkyl groups in the side chains include, for example, C _1-6 linear alkyl, C _3-6 branched alkyl, cyclopentyl and cyclohexyl.

Other examples of suitable dithiols include dimercaptodiethyl sulfide (DMDS) (in 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 -S-); dimercaptodioxaoctane (DMDO) (in Formula (23), R ¹ is - [(- CH ₂ -) _{s -} X -] _q - (CH ₂ ) _r -, where s is 2, q is 2, r is 2, and X represents -O-); and 1,5-dimercapto-3-oxapentane (in Formula (23), R ¹ is - [(- CH ₂ -) _{s -} X -] _q - (CH ₂ ) _r -, where s is 2, r is equal to 2, q is 1, and X is -O-). Dithiols, which contain both heteroatoms in the carbon backbone and side alkyl groups such as methyl groups, can also be used. Such compounds include, for example, methyl-substituted DMDS, such as HS-CH ₂ CH (CH ₃ ) -S-CH ₂ CH ₂ -SH, HS-CH (CH ₃ ) CH ₂ -S-CH ₂ CH ₂ -SH and dimethyl substituted DMDS, such as HS-CH ₂ CH (CH ₃ ) -S-CHCH ₃ CH ₂ -SH and HS-CH (CH ₃ ) CH ₂ -S-CH ₂ CH (CH ₃ ) -SH.

Suitable divinyl ethers for the preparation of polythioethers include, for example, the divinyl ethers of Formula (24):

wherein R ² in Formula (24) is selected from C _2-6 n-alkanediyl group, C _3-6 branched alkanediyl group, C _6-8 cycloalkanediyl group, C _6-10 alkancycloalkanediyl group and - [(- CH ₂ -) _s -O-] _q - (- CH ₂ -) _r -, where s is an integer from 2 to 6, q is an integer from 1 to 5, and r is an integer from 2 to 10. In some embodiments of 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, a C _6-10 alkanocycloalkanyl group, and in some cases In the implementation of - [(- CH ₂ -) _s -O-] _q - (- CH ₂ -) _r -.

Suitable divinyl esters include, for example, compounds containing at least one hydroxyalkandiyl group, for example, 1-4 hydroxyalkandiyl groups, i.e. compounds in which m in Formula (24) is an integer from 1 to 4. In some embodiments, m in Formula (24) is an integer from 2 to 4. You can also use commercially available mixtures of divinyl ethers that have a non-integer the average number of oxyalkanediyl fragments per molecule. Thus, m in Formula (24) can also take rational values from 0 to 10.0, such as from 1.0 to 10.0, from 1.0 to 4.0, or from 2.0 to 4.0.

Examples of suitable vinyl esters 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) (R ² in Formula (24) 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) (R ² in Formula ( 24) is an ethanediyl, and m is 2), triethylene glycol divinyl ether (R ² in Formula (24) represents ethanediyl and m is 3), tetraethylene glycol ivinilovy ester (R ² in Formula (24) represents ethanediyl and m is 4), cyclohexanedimethanol divinyl ether, polytetrahydrofuryl divinyl ether; trivinyl ether monomers such as trimethylolpropane trivinyl ether; tetrafunctional ester monomers, such as pentaerythritol tetravinyl ether; and combinations of two or more such polyvinyl ether monomers. The polyvinyl ether may have one or more side groups selected from alkyl groups, hydroxyl group, alkoxy group, and amino groups.

In some embodiments, divinyl ethers, in which R ² in Formula (24) is a C _3-6 branched alkanediyl, can be obtained by reacting a polyhydroxy compound with acetylene. Examples of divinyl ethers of this type include compounds in which R ² in Formula (24) is an alkyl-substituted methanediyl group, such as —CH (—CH ₃ ) -, for which R in Formula (24) is ethanyl, and m equal to 3.8) or alkyl-substituted ethanediyl.

Other suitable divinyl esters include compounds in which R ² in Formula (24) is polytetrahydrofuryl (poly-THF) or polyoxyalkanediyl, such as compounds containing on average about 3 monomeric fragments.

Two or more types of polyvinyl ether monomers of Formula (24) may be used. Thus, in some 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), two dithiol of Formula (23) and two divinyl ether monomers of Formula (24), and more than two compounds having one or more of Formulas (23) and (24), to obtain different thiol-functional polythioethers.

In some embodiments, the implementation of the polyvinyl ether monomer is from 20 to less than 50 mole percent of the reagents used to obtain the thiol-functional polythioether, and, in some embodiments, from 30 to less than 50 mole percent.

In some embodiments described in the present text, the relative amounts of dithiols and divinyl ethers are selected in such a way as to obtain terminal thiol groups. Thus, the dithiol of Formula (23), or a mixture of at least two different dithiols of Formula (23), is reacted with divinyl ether of Formula (24) or a mixture of at least two different divinyl ethers of Formula (24) in such relative amounts that the molar the ratio of thiol groups to vinyl groups was higher than 1: 1, for example, from 1.1: 1.0 to 2.0: 1.0.

The reaction between dithiols and divinyl ethers and / or polythiols and polyvinyl ethers can be catalyzed by a free-radical catalyst. Suitable free radical catalysts include, for example, azo compounds, for example azobisonitriles, such as azo (bis) isobutyronitrile (AIBN); organic peroxides, such as benzoyl peroxide and t-butyl peroxide; and inorganic peroxides, such as hydrogen peroxide. The catalyst may be a free radical catalyst, an ionic catalyst, or ultraviolet radiation. In some 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 azo-type catalysts such as Vazo®-57 (Du Pont), Vazo®-64 (Du Pont), Vazo®-67 (Du Pont), V-70® (Wako Specialty Chemicals) and V-65B® (Wako Specialty Chemicals). Examples of other free radical catalysts are alkyl peroxides, such as t-butyl peroxide. The reaction can also be accelerated by irradiation with ultraviolet light, with or without a cationic photoinitiator.

The thiol-terminal polythioethers described in this text can be obtained by combining at least one compound of Formula (23) and at least one compound of Formula (24), followed by adding a suitable catalyst and carrying out the reaction at a temperature of from 30 ° C to 120 ° C, for example at 70 ° C - 90 ° C, for 2-24 hours, for example 2-6 hours.

As described in this text, thiol-terminal polythioethers can be a polyfunctional polythioether, i.e. may have an average functionality of more than 2.0. Suitable polyfunctional thiol-terminal polythioethers include, for example, compounds having the structure of Formula (28a):

where z has an average value greater than 2.0, and, in some embodiments, a value between 2 and 3, a value between 2 and 4, a value between 3 and 6, and in some embodiments, the implementation is an integer from 3 to 6.

Polyfunctionalizing agents suitable for use in preparing such polyfunctional thiol-terminal polymers include trifunctionalizing agents, i.e., compounds where z is 3. Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), 1,2,3-propanthritiol, isocyanurate-containing trithiols and combinations thereof, as described in US Patent Application Publication No. 2010/0010133 in paragraphs [0102] - [0105], the quoted fragment of which is incorporated by reference into this text, and the isocyanurates described, for example, Example, in the publication of the application for US patent No. 2011/0319559, which is incorporated into this text by reference. Other suitable polyfunctionalizing agents include trimethylolpropane trivinyl ether and the polythiols described in US Pat. Nos. 4,366,307; 4,609,762 and 5,225,472, each of which is incorporated into this text by reference. You can also use a mixture of polyfunctionalizing agents. As a result, the bis (sulfonyl) alkanol-containing polythioethers described in this text may have a wide range of average functionality. For example, trifunctionalizing agents can provide an average functionality of 2.05 to 3.0, for example, 2.1 to 2.6. A wider range of average functionality can be achieved by using tetra-functional polyfunctionalizing agents or polyfunctionalizing agents with an even higher value of functionality. Factors such as stoichiometry can also affect functionality, as is understood by those skilled in the art.

Thiol-terminal polythioethers and bis (sulfonyl) alkanol-containing polythioethers having a functionality greater than 2.0 can be obtained similarly to difunctional thiol-terminal polythioethers, as described in the publication of the application US Patent No. 2010/0110133, the publication of the US Patent Application No. 2011 / 0319559 and in US patent No. 6,172,179, each of which is incorporated into this text by reference. In some embodiments, the polythioethers can be obtained by combining (i) one or more dithiols described in this text with (ii) one or more divinyl ethers described in this text, and (iii) one or more polyfunctionalizing agents. Then the reaction in the mixture takes place, optionally in the presence of a suitable catalyst, to produce a thiol-terminal polythioether or a bis (sulfonyl) alkanol-containing polythioether having a functionality greater than 2.0.

In some embodiments, the polythioethers, including thiol-terminal polythioethers, bis (sulfonyl) alkanol-containing polythioethers, and blocked analogues of any of the above, are polythioethers having a certain molecular weight distribution. In some embodiments, the implementation, suitable polythioethers can have a number average molecular weight in the range from 500 daltons to 20,000 daltons, in some embodiments, from 2000 daltons to 5000 daltons, and in some embodiments, from 3000 daltons to 4000 daltons. In some embodiments, implementation, suitable polythioethers have polydispersity (M _w / M _n ; srednevekovoi molecular weight / srednecenovogo molecular weight) in the range from 1 to 20, and in some embodiments, implementation from 1 to 5. The distribution of molecular weights of polythioethers can be determined, for example, by gel permeation chromatography.

Prepolymers containing a ligand capable of binding to metal

Bis (sulfonyl) alkanols are one type of ligand capable of binding to metal, which can be incorporated into the main chain of a polymer, such as a sulfur-containing prepolymer, to improve adhesion to the surface. Other ligands capable of binding to the metal may also be incorporated into the polymer backbone to improve adhesion to the surface. In some embodiments, such as for use in a sealant for the aerospace industry, ligands capable of binding to metal can be selected from ligands that can coordinate with the surfaces of aluminum, aluminum oxide, Al (III), anodized aluminum, titanium, titanium oxide and / or Alodine®. A ligand capable of binding to a metal can form a bidentate, tridentate or higher-order coordination complex with surface atoms. Thus, prepolymers containing a ligand capable of binding to a metal include any bis (sulfonyl) alkanol-containing prepolymers described in this text, in which the bis (sulfonyl) alkanol group is replaced by another ligand capable of binding to the metal. Similarly, methods for synthesizing prepolymers containing a ligand capable of binding to metal, their derivatives and blocked analogs include any of those described in the present text for the preparation of bis (sulfonyl) alkanol-containing prepolymers that employ the appropriate metal chelating agent. In addition to containing a fragment of an -L-ligand capable of binding to the metal, the metal chelating agent R ⁹ -LR ⁹ includes the groups R ⁹ containing terminal groups capable of reacting with the precursors of the sulfur-containing polymer. In some embodiments, each R ⁹ contains terminal groups capable of reacting with thiol groups, such as an alkenyl, epoxy, or Michael acceptor group.

The ligands capable of binding to the metal, and in particular the ligands for aluminum (III) capable of binding to the metal, include rigid Lewis bases such as —OH, —PO ₄ , —SO ₄ , —COOH, —C═O, and —NH ₂ groups that are able to act as electron donors for vacant metal orbitals. The main donor groups that effectively form multidentate coordination complexes with aluminum (III) include anions of aliphatic monohydroxy acids, catecholates, anions of aromatic hydroxy acids, 3-hydroxy-4-pyridinones, hydroxamates, and 3-hydroxy-2-pyridinones. Stable aluminum (III) complexes are formed with multidentate ligands having negatively charged oxygen electron donors. A ligand capable of binding to a metal can form a multidentate complex, such as a bidentate complex or a tridentate complex with metals.

In some embodiments, the implementation, the functional group of the ligand capable of binding to the metal, is derived from a metal chelating agent selected from bis (sulfonyl) alkanol, hydroxypyridinone and acetylacetonate.

Examples of ligands for aluminum, alumina and Al (III) include 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy-2-pyridinone, 2-2'-dihydroxyazobenzene, 8-hydroxyquinoline , oxalate, 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, acetylacetonate, catecholate, hydro . Samat and quinone Other chelators for aluminum and alumina are described in, for example, in Yokel, Coordination Chemistry Reviews 2002, 228, 97-113; and Martell et al, Coordination Chemistry Reviews 1996, 149, 311-328..

Examples of ligands for titanium or titanium oxide include H2O2, acetoacetonate (CH ₂ (COCH ₃ ) ₂ ), EDTA, trans-1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid (GEDTA, (CH ₂ OCH ₂ CH ₂ N (CH ₂ COOH) ₂ ) ₂ ), diethylenetriamine pentaacetic 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, acetylacetonate, triethanolamine, and a combination of any of the above.

In some embodiments, the implementation, the ligand capable of binding to the metal, contains at least two heteroatomic groups that can coordinate with the surface of aluminum (III). In some embodiments, the implementation, the ligand capable of contact with the metal contains at least two heteroatomic groups selected from -OH, -PO ₄ , -P (O) ₂ - -SO ₄ , -S (O) ₂ - -COOH, -C = O, -NH ₂ , -NH-, and combinations of any of the above.

In some embodiments, the implementation, the functional group of the ligand capable of contacting the metal, is a fragment selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e) and combinations of any of the above :

Where -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. In some embodiments, each X is —C (O) -, and each n is 1; and in some embodiments, each X is —S (O) ₂ -, and each n is 1.

As for bis (sulfonyl) alkanol-containing polythioethers, other ligands capable of binding to the metal may be included in the backbone of a prepolymer, such as sulfur-containing prepolymers, including polythioethers. Accordingly, in some: embodiments, a prepolymer containing a ligand capable of binding to a metal contains a fragment of Formula (26):

Where

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X is independently —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; and

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

The metal chelating agent R ⁹ -LR ⁹ contains groups R ⁹ that can react, for example, with thiol groups, and a ligand capable of binding to the metal, -L-. A ligand capable of binding to a metal, —L-, may contain, for example, a fragment of Formula (25a) - (25e). In some embodiments, the metal chelating agent is selected from bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and a combination of any of the above.

In some embodiments, the implementation of the prepolymer containing a ligand capable of binding to the metal is a polythioether of Formula (28a) containing a ligand capable of binding to the metal, the polythioether of Formula (28b) containing a ligand capable of binding to the metal, or a combination of these:

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X is independently —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with terminal thiol groups; and

each -V'- is formed by the reaction of -V with a thiol; and

each R ⁶ independently represents a hydrogen atom or a fragment having a terminal reactive group.

In some embodiments of the prepolymer of Formula (28a) and Formula (28b), each R ⁶ is a hydrogen atom.

In some embodiments of the prepolymer of Formula (28a) and Formula (28b), each R ^{6 is the} same, and the terminal reactive group is selected from -SH, -CH = CH ₂ , -NH ₂ , -OH, epoxy, polyalkoxysilyl group, isocyanate group and Michael acceptor groups.

In some embodiments, the implementation of the thiol-terminal polythioether containing a ligand capable of binding to the metal, is a reaction product of the reagents, which are:

(a) a thiol-terminal polythioether, which is a thiol-terminal polythioether of Formula (18a), a thiol-terminal polythioether of Formula (18b), or a combination of these:

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X is independently —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given 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; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with terminal thiol groups; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a metal chelating agent R ⁹ -LR ⁹ , where each R ^{9 is} independently a moiety containing a terminal group capable of reacting with a thiol group; and -L- is a fragment containing a ligand capable of binding to a metal.

In some embodiments of Formula (18a) and Formula (18b), the ligand capable of binding to the metal may be a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e ) and combinations of any of the above:

Where

-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 a C _1-3 alkanediyl.

In some embodiments of Formula (18a) and Formula (18b), the ligand capable of binding to the metal is a bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or a combination of any of the above.

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

In some embodiments, the polythioether of Formula (18b) is the reaction product of 1,8-dimercapto-3,6-dioxoctane, divinyl ether diethylene glycol and triallyl cyanurate.

In some embodiments, the implementation, the thiol-terminal polythioether prepolymer containing a ligand capable of binding to the metal, is a reaction product of the reagents, which are:

(a) a thiol-terminal polythioether containing a ligand capable of binding to the metal, a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to the metal, a thiol-terminal polythioether of Formula (29b) containing a ligand capable of binding metal, or their combination:

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkanocycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X is independently —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent, alkenyl-terminal polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6; and

each V is a group containing a terminal alkenyl group; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a polyalkenyl compound.

In some embodiments, the polythioethers of Formula (29a) and Formula (29b), the ligand capable of binding to the metal is a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e ) and combinations of any of the above:

Where

-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 a C _1-3 alkanediyl.

In some embodiments of the thiol-terminal polythioethers of Formula (29a) and Formula (29b) containing a ligand capable of binding to a metal, the polyalkenyl compound is diethylene glycol divinyl ether, triallyl cyanurate, or a combination thereof.

In some embodiments, a method for producing a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal involves reacting (N + 1) moles of the thiol-terminal polythioether of Formula (18a) with (N) moles of a metal-chelating agent, containing -L- and terminal groups capable of reacting with thiol groups:

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X independently represents -O-, -S-, or -NR ⁵ -, where R ⁵ is a hydrogen atom or methyl; and

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

In some embodiments of the method described above, the ligand capable of binding to the metal is a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and combinations of any of the above :

Where

-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 a C _1-3 alkanediyl.

In some embodiments of the above process, the metal chelating agent is bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or a combination of any of the above.

In some embodiments, methods for producing a thiol-terminal polythioether of Formula (29b) containing a ligand capable of binding to a metal include reacting (z) moles of a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal with one ( 1) we pray polyfunctionalizing agent B {V} _z :

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 represents a hydrogen atom or methyl; and

each X independently represents -O-, -S-, or -NR ⁵ -, where R ⁵ is a hydrogen atom or methyl;

each R ^{2 is} independently C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r , where s, q, k, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with a terminal thiol group; and

each -V'- is formed by the reaction of -V with a thiol.

In some embodiments of the method described above, the ligand capable of binding to the metal is a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and combinations of any of the above :

Where

-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 a C _1-3 alkanediyl.

In some embodiments of the above process, the metal chelating agent is selected from bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or a combination of any of the above.

Sulfur-containing prepolymers containing a ligand capable of binding to metal

In addition to the polythioether prepolymers, ligands capable of binding to the metal can 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 that has at least one sulfur atom in a repeating fragment, including (but not limited to, polymeric thiols, polythiols, thioethers, polythioethers, sulfur-containing polyformals and polysulfides. The term “thiol,” as used herein, refers to a compound containing a thiol or mercaptan group, i.e., “SH” group, as a single functional group or in combination with other functional groups, such as hydroxyl groups, as in the case for example, thioglycerols. Polythiol is a compound with more than one SH group, such as dithiol or thiol with greater functionality. Such groups are usually terminal and / or side, so that they contain active hydrogen, which can react with other functional groups. A polythiol can contain both terminal and / or lateral sulfur atoms (-SH), and non-reactive sulfur atoms (-S- or -S-S-). Thus, the term "politiol" generally covers polythioethers and polysulfides.

The term "polysulfide" means a polymer that contains one or more sulfide bridges, i.e. -S _x - bridges, where x is from 2 to 4, in the main polymer chain and / or in the lateral positions of the polymer chain. In some embodiments, the polysulfide polymer contains two or more sulfur-sulfur bridges. Suitable polysulfides are commercially available, for example, from Akzo Nobel and Toray Fine Chemicals under the names Thiokol-LP and Thioplast ^® . Thioplast ^® products are available in a wide range of molecular weights, for example, from less than 1,100 to over 8,000, where the molecular weight is the average molecular weight in grams per mole. In some cases, the poly sulfide has a number average molecular weight from 1000 daltons to 4000 daltons.

Sulfur-containing polyformal prepolymers that can be used in sealants for the aerospace industry are described, for example, in the publication of the application for US Patent No. 2012/0234205 and in the publication of the application for US Patent No. 2012/0238707.

Methods of synthesis of bis (sulfonyl) alkanol-containing polythioethers

In general, thiol-terminal bis (sulfonyl) alkanol-containing polythioethers can be obtained by reacting a thiol-terminal polythioether or a mixture of thiol-terminal polythioethers with a bis (sulfonyl) alkanol, such as a bis (vinylsulfonyl) alkanol. In some embodiments, implementation, thiol-terminal bis (sulfonyl) alkanol-containing polythioether can be obtained by the reaction of a difunctional thiol-terminal polythioether or a mixture of difunctional thiol-terminal polythioethers with a bis (sulfonyl) alkanol, such as a bis (vinylsulfonyl) alkanol or bis (sulfonyl) alkanol containing terminal groups capable of reacting with thiol groups.

In some embodiments, methods for producing a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a) include the reaction of (N + 1) moles of the thiol-terminal polythioether of Formula (18a) with (N) moles of bis (sulfonyl) alkanol of Formula ( 4a):

Where

N is an integer from 1 to 10;

each R ^{8 is} independently selected from a moiety containing a terminal group capable of reacting with a terminal thiol group;

each R ^{8 ′} is a fragment resulting from the reaction of a bis (sulfonyl) alkanol with thiol groups;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; and

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

In some embodiments, the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (16a), N is 1, 2, 3, 4, 5, 6, 7, 8, 9, and in some embodiments, N is 10. In some The variants of bis (sulfonyl) alkanol-containing polythioethers of Formula (16a), the molecular weight ranges from 200 daltons to 20,000 daltons. In some embodiments, the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers of Formula (16a) contain a combination of bis (sulfonyl) alkanol-containing polythioethers of Formula (16a) with different values of N. In some embodiments, the thiol-terminal bis (sulfonyl) alkanol -containing polythioethers of Formula (16a), N is 1. Thus, in practice, upon receipt of the thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a), the molar ratio of the thiol-terminal polythioether and bis (sulfonyl) alkanol is not necessarily o be an integer, so that the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers Formula (16a) is a mixture of the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers having different values of N.

In some embodiments, methods for producing a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16b) include reacting (z) moles of a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a) with one (1) mole of the polyfunctionalizing Agent B {V} _Z :

Where

each R ^{8 ′} is a fragment resulting from the reaction of a bis (sulfonyl) alkanol with thiol groups;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r , where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z where

z is an integer from 3 to 6;

each V is a group containing a group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol.

In some embodiments, the implementation, the reaction between the thiol-terminal bis (sulfonyl) alkanol-containing polythioether and bis (sulfonyl) alkanol, such as bis (vinylsulfonyl) alkanol, is carried out in the presence of a catalyst, such as an amine catalyst, including, for example, any of in the present text amine catalysts.

Methods of synthesis of thiol-terminal prepolymers containing a ligand capable of binding to metal

In some embodiments, a prepolymer containing a thiol-terminal ligand capable of binding to a metal, such as a thiol-terminal polythioether containing a ligand capable of binding to a metal, can be obtained by reacting a difunctional thiol-terminal prepolymer or a mixture of difunctional thiol-terminal prepolymers with metal chelating agent having at least two groups capable of reacting with thiol groups, such as bis (sulfonyl) alkanol, hydroxypyridinone or acetylacetonate, soda At least two terminal groups capable of reacting with thiol groups.

In some embodiments, methods for preparing a prepolymer of Formula (29a) containing a thiol-terminal ligand capable of binding to a metal include reacting (N + 1) moles of the thiol-terminal polythioether of Formula (18a) with (N) moles of metal-chelating agent R ⁹ -LR ⁹ :

Where

N is an integer from 1 to 10;

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; and

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r , where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6.

In some embodiments, the thiol terminal polythioethers of Formula (29a) containing a ligand capable of binding to the metal, N is 1, 2, 3, 4, 5, 6, 7, 8, 9, and in some embodiments, the implementation of N is 10. In In certain embodiments of a prepolymer of Formula (29a) containing a ligand capable of binding to a metal, the molecular weight is from 200 daltons to 20,000 daltons. In some embodiments, implementation, thiol-terminal prepolymers of Formula (6) containing a ligand capable of binding to the metal, contain a combination of prepolymers of Formula (29a) containing a ligand capable of binding to the metal, with different values of N. In some embodiments, thiol-terminal prepolymers Formulas (29a) containing a ligand capable of binding to the metal, N is equal to 1. Thus, in practice, upon receipt of the thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (29a), the molar ratio of the thiol-terminal poly the thioether and metal chelating agent need not be an integer, so the thiol-terminal prepolymers of Formula (29a) containing a ligand capable of binding to a metal are a mixture of thiol-terminal prepolymers containing a ligand capable of binding to a metal having different N. values

In some embodiments, methods for producing a prepolymer of Formula (29b) containing a thiol-terminal ligand capable of binding to a metal include reacting (z) moles of a prepolymer of Formula (29a) containing a thiol-terminal ligand capable of binding to a metal with one ( 1) we pray polyfunctionalizing agent B {V} _z :

Where

each R ^{9 'is} independently a fragment formed by the reaction of R ^{9 of a} metal chelating agent R ⁹ -LR ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with a thiol; and L is a ligand capable of binding to the metal;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6; and

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol.

In some embodiments, the implementation of the reaction between the thiol-terminal polythioether containing a ligand capable of binding to the metal, and the metal chelating agent is carried out in the presence of a catalyst, such as an amine catalyst, including, for example, any of the amine catalysts described herein.

Alkenyl terminal bis (sulfonyl) alkanol-containing polythioether prepolymers

The thiol-terminal bis (sulfonyl) alkanol-containing polythioethers described in the present text can be reacted with polyalkenyls, such as dialkenyl ethers and / or alkenyl-terminal polyfunctionalizing agents, to produce alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether agents . Alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether prepolymers can be combined with a hardener to form a curable composition, such as a sealing composition.

For example, in some embodiments, the implementation, alkenyl-terminal bis (sulfonyl) alkanol-containing polythioether prepolymer is a reaction product of the reagents, which are:

(a) a thiol-terminal bis (sulfonyl) alkanol-containing polythioether selected from a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16a), a thiol-terminal bis (sulfonyl) alkanol-containing polythioether of Formula (16b) and combinations:

Where

N is an integer from 1 to 10;

each R ^{8 ′} is a fragment resulting from the reaction of a bis (sulfonyl) alkanol with thiol groups;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s , q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a polyalkenyl compound.

In some embodiments, the polyalkenyl compound is selected from a divinyl ether or a mixture of divinyl ethers, including any of the alkenyl terminal polyfunctionalizing agents described herein, and combinations thereof.

In some embodiments of the reaction described above, (a) is a polythioether of Formula (16a), and (b) is a polyvinyl ether selected from divinyl ether, an alkenyl-terminal polyfunctionalizing agent, and combinations thereof.

In some embodiments of the reaction described above, (a) is a polythioether of Formula (16a), and (b) is a polyachenyl ether selected from divinyl ether diethylene glycol (DEG-DVE), TAC, and combinations thereof.

Alkenyl-terminal polythioether prepolymers containing a ligand capable of binding to the metal

Thiol-terminal prepolymers described in the present text containing a ligand capable of binding to a metal can be reacted with polyalkenyls, such as dialkenyl ethers and / or alkenyl-terminal polyfunctionalizing agents, to produce alkenyl-terminal prepolymers containing a ligand capable of binding to a metal . Alkenyl-terminal prepolymers containing a ligand capable of binding to a metal can be combined with a hardener to form a curable composition, such as a sealing composition.

For example, in some embodiments, an alkenyl terminal prepolymer containing a ligand capable of binding to a metal is a reaction product of the reactants, which are:

(a) a prepolymer containing a thiol-terminal ligand capable of binding to a metal selected from a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding with a metal, a polythioether of Formula (29b) containing a ligand capable of binding to the metal, and Their combinations:

Where

N is an integer from 1 to 10;

each R ^{9 '} is a fragment formed by the reaction of the metal chelating agent R ⁹ -LR ⁹ with thiol groups, where -L- is a metal chelating group, and each R ⁹ contains a group capable of reacting with a thiol group;

each R ^{10 is} independently selected from C _1-3 alkanediyl and substituted C _1-3 alkanediyl, where one or more substituent groups are —OH;

each A is independently a fragment of Formula (12):

Where

each R ^{1 is} independently selected from C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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; and

each X is independently selected from —O—, —S—, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl;

each R ^{2 is} independently selected from C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl and - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r , where s, q, r, R ³ and X correspond to the definitions given for R ¹ ;

m is an integer from 0 to 50;

n is an integer from 1 to 60; and

p is an integer from 2 to 6;

B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where

z is an integer from 3 to 6;

each V is a group containing a terminal group capable of reacting with a thiol group; and

each -V'- is formed by the reaction of -V with a thiol; and

(b) a polyalkenyl compound.

In some embodiments, the polyalkenyl compound is selected from a divinyl ether or a mixture of divinyl ethers, including any of the alkenyl terminal polyfunctionalizing agents described herein, and combinations thereof.

In some embodiments of the reaction described above, (a) is a polythioether of Formula (29a), and (b) is a polyvinyl ether selected from divinyl ether, an alkenyl-terminal polyfunctionalizing agent, and combinations thereof.

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

Blocked bis (sulfonyl) alkanol-containing prepolymers containing a ligand capable of binding to metal

Bis (sulfonyl) alkanol-containing polythioethers and prepolymers containing a ligand capable of binding to the metal can be adapted for use with a specific curing chemistry by blocking or introducing a suitable functional group at the terminal position in the bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a ligand capable of binding to a metal, such as a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or a thiol-terminal prepolymer containing a ligand capable of binding by metal. Blocked analogs of thiol-terminal polythioethers are described, for example, in US patent No. 6,172,179 and in publication of US patent application No. 2011/0319559.

For example, in some embodiments, a bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a ligand capable of binding to a metal has terminal groups other than unreacted thiol groups, such as hydroxyl, alkenyl, isocyanate, amine, epoxide, hydrolyzable functional a group such as a polyalkoxysilyl group, a Michael acceptor group or an epoxy group.

Blocked analogues can be obtained in a number of ways known to those skilled in the art. For example, to obtain blocked bis (sulfonyl) alkanol-containing polythioethers or prepolymers containing a ligand capable of binding to a metal, a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-terminal ligand capable of binding to a metal can react with a compound having a terminal group capable of reacting with thiol groups.

To obtain an alkenyl terminal bis (sulfonyl) alkanol-containing polythioether or an alkenyl-terminal prepolymer containing a ligand capable of binding to a metal, a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-terminal ligand capable of binding metal, you can react with a compound containing a terminal alkenyl group and an isocyanate group, such as a group derived from TMI, 2-isocyanatoethyl methacrylate or allyl isocyanate, in the presence of a catalyst Ator - dibutyltin dilaurate.

Polyalkoxy-silyl-terminal bis (sulfonyl) alkanol-containing polythioethers and polyalkoxy-silyl-terminal prepolymers containing a ligand capable of binding to the metal can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-chiol-terminal (biol) (glycol) alkanol containing a polythioether or a prepolymer containing a thiol-terminated bis (sulfonyl) alkanol containing a polythioether or a polymethyl ester. capable of binding to metal, with isocyanatoalkyltrialkoxysilane, such as 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane, in the presence of dibutyltin dilaurate, obtaining corresponding etstvuyuschy polialkoksisilil terminal-bis (sulfonyl) alkanol-containing polythioether or corresponding polialkoksisilil-terminal prepolymer containing a ligand capable of binding with a metal.

Epoxy-terminal bis (sulfonyl) alkanol-containing polythioethers and epoxy-terminal prepolymers containing a ligand for a metal can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-terminal ligand capable of binding with a metal, in the presence of a mono-epoxide, such as allyl-glycidyl ether, to obtain the corresponding epoxy-terminal bis (sulfonyl) alkanol-containing polythioether or the corresponding epoxy-terminal prepolymer, containing ligand capable of binding to metal.

Amine-terminal bis (sulfonyl) alkanol-containing polythioethers and amine-terminal prepolymers containing a ligand capable of binding to the metal can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-terminal ligand capable of binding to metal with monofunctional 4-amino-butylvinyl ether with a free-radical initiator. Alternatively, the amine-terminal bis (sulfonyl) alkanol-containing polythioether or amine-terminal prepolymer containing a ligand capable of binding to the metal can be obtained by reacting the isocyanate-terminal bis (sulfonyl) alkanol-containing polythioether or isocyanate-terminal prepolymer containing the ligand, capable of binding to metal, with a diamine, such as 4- (aminomethyl) aniline, to obtain the corresponding amine-terminal bis (sulfonyl) alkanol-containing polythioether or the corresponding amine-terminal prepolymer, containing a ligand capable of binding to the metal. Amine-terminal bis (sulfonyl) alkanol-containing polythioethers and amine-terminal prepolymers containing a ligand capable of binding to the metal can also be obtained by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether or alkanol-terminal or hydroxy-terminal prepolymer, containing a ligand capable of binding to a metal, with an amino-substituted benzoate, such as ethyl 4-aminobenzoate, in the presence of Bu ₂ SnO or NaOMe at elevated temperature, obtaining the corresponding amine-terminal bis (sulfonyl ) alkanol-containing polythioether or the corresponding amine-terminal prepolymer containing a ligand capable of binding to the metal.

Isocyanate-terminal bis (sulfonyl) alkanol-containing polythioethers and isocyanate-terminal prepolymers containing a ligand capable of binding to a metal can be obtained, for example, by thiol-terminal bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a thiol-terminal ligand capable of binding to metal, with a diisocyanate, such as TTL, Isonate ™ 143L (polycarbodiimide-modified diphenylmethane diisocyanate), Desmodur ^® N3400 (1,3-diazetidin-2,4-dione, 1,3-bis (6-isocyanatohexyl) -), IPDI (isophorone diisocyanate), and whether Desmodur ^® W (H ₁₂ MDI), optionally in the presence of a catalyst, such as dibutyl tin dilaurate. Isocyanate-terminal bis (sulfonyl) alkanol-containing polythioethers and isocyanate-terminal prepolymers containing a ligand capable of binding to the metal can be used as intermediates in the synthesis of other terminal-modified bis (sulfonyl) alkanol-containing polythioethers and a terminal-modified prepolymer, containing a ligand capable of binding to a metal, such as certain amine-terminal and thiol-terminal bis (sulfonyl) alkanol-containing polythioether amine-terminal and thiol-term cial prepolymers containing ligand capable of binding with a metal.

The hydroxyl terminal bis (sulfonyl) alkanol-containing polythioethers and hydroxy-terminal prepolymers containing a ligand capable of binding to the metal can be obtained, for example, by reacting a thiol-terminal bis (sulfonyl) alkanol-containing polythioether prepolymer containing a thiol-terminal ligand, capable of binding to the metal, with a compound having a terminal hydroxyl group and a group capable of reacting with thiol groups.

In some embodiments, the implementation, bis (sulfonyl) alkanol-containing polythioethers and prepolymers containing a ligand capable of binding to the metal, can have terminal Michael-acceptor groups. In some embodiments, the implementation of the Michael-acceptor group is a derivative of vinyl sulfone and has the structure of Formula (27):

where each R ^{13 is} independently selected from a hydrogen atom and C _1-3 alkyl. In some embodiments of Formula (27), each R ¹³ is a hydrogen atom. In some embodiments, the implementation of the Michael acceptor-terminal bis (sulfonyl) alkanol-containing polythioethers can be obtained, for example, by the reaction of the thiol-terminal bis (sulfonyl) alkanol-containing polythioether with a compound having a terminal Michael-acceptor group and a group capable of reacting with thiol groups, such as divinylsulfone, in the presence of an amine catalyst. The Michael acceptor / polythioether chemistry and compounds are described in US Patent Application Publication No. 13 / 529,237, filed June 13, 2012, which is incorporated in its entirety by reference. Examples of isocyanate- and epoxy-terminal polythioethers and methods for producing isocyanate- and epoxy-terminal polythioethers are described in US Pat. No. 7,879,955 B2.

Compositions

The compositions described herein may contain one or more bis (sulfonyl) alkanol-containing polythioethers and / or one or more bis (sulfonyl) alkanol-containing polythioether prepolymers and / or one or more prepolymers containing a ligand capable of binding to the metal. Curable compositions may additionally contain a hardener. The compositions may additionally contain additives, catalysts, fillers and / or other sulfur-containing prepolymers, including, for example, polythioethers, sulfur-containing polyformals and / or polysulfides.

A suitable curing agent is chosen so that it reacts with the terminal groups of a bis (sulfonyl) alkanol-containing polythioether, a prepolymer containing a ligand capable of binding to the metal, and optional sulfur-containing prepolymers.

In some embodiments, in which a bis (sulfonyl) alkanol-containing polythioether, its prepolymer or prepolymer containing a ligand capable of binding to a metal, has terminal thiol groups, a suitable curing agent is a polyepoxide. Examples of suitable polyepoxides include, for example, polyepoxide resins, such as hydantoin diepoxide, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, epoxides type Novolac ^®, such as DEN ™ 438 (Dow Chemical Company), some of the epoxidized unsaturated resins, and combinations of any of the listed components. A polyepoxide is a compound containing two or more reactive epoxy groups. In some embodiments, the epoxy curing agent is selected from EPON ™ 828 (Momentive Specialty Chemicals, Inc.), DEN ™ 431 (Dow Chemical Company), and combinations thereof. Examples of suitable hardeners capable of reacting with thiol groups include diepoxides.

In some embodiments, the polyepoxide hardener is an epoxy-functional polymer. Examples of suitable epoxy-functional polymers include the epoxy-functional sulfur-containing polyformal polymers described in US Patent Application No. 13/050,988, and epoxy-functional polythioether polymers described in US Patent No. 7,671,145. In general, when used as a hardener, the epoxy-functional polymer has a molecular weight less than about 2000 daltons, less than about 1500 daltons, less than about 1000 daltons, and in some embodiments less than about 500 daltons.

In some embodiments, the implementation, polyepoxide may be from about 0.5 weight. % to 20 wt. % composition, from about 1 wt. % to 10 weight. %, from about 2 wt. % to 8 wt. %, from about 2 wt. % to 6 wt. %, and in some embodiments, the implementation of approximately 3 weight. % to 5 wt. %, where percentages by weight are calculated relative to the total weight of the solid residue of the composition.

In some embodiments, in which a bis (sulfonyl) alkanol-containing polythioether, its prepolymer or prepolymer containing a ligand capable of binding to a metal, has terminal thiol groups, a suitable curing agent is an unsaturated compound, such as an acrylic or methacrylic ester of a polyol, unsaturated synthetic or natural resinous compounds, triallyl cyanurate and olefin-terminal derivatives of sulfur-containing compounds, such as polythioethers.

In some embodiments, implementation, such as when used amine and / or hydroxyl-terminal bis (sulfonyl) alkanol-containing polythioethers, their prepolymer, or amine and / or hydroxyl-terminal prepolymers containing a ligand capable of binding to the metal described in The present text of the composition may contain an isocyanate hardener, such as a diisocyanate and / or triisocyanate hardener. Examples of suitable isocyanate hardeners include toluene diisocyanate and combinations of any of the listed components. Isocyanate curing agents are commercially available and include for example, products under the trademarks ^{Baydur ® (Bayer MaterialScience), Desmodur} ® (Bayer MaterialScience), Solubond ® (DSM), ECCO (ECCO), Vestanat ® (Evonik), Irodur ® (Huntsman), Rhodocoat ™ (Perstorp) and Vanchem ^® (VT Vanderbilt). In some embodiments, the polyisocyanate hardener contains isocyanate groups that are capable of reacting with thiol groups and that are less reactive with Michael acceptor groups. Examples of suitable hardeners capable of reacting with amino groups include polymeric polyisocyanates, non-limiting examples of which include polyisocyanates having bridges in the main chain selected from urethane bridges (-NH-C (O) -O-), thiourethane bridges (-NH-C ( O) -S-), thiocarbamate bridges (-NH-C (S) -O-), dithio-urethane bridges (-NH-C (S) -S-), and combinations of any of the listed components.

In some embodiments, the isocyanate curing agent is an isocyanate-functional polymer. Examples of suitable isocyanate-functional polymers include the isocyanate-functional sulfur-containing polyformal polymers described in US Patent Application No. 13/051,002. In general, when used as a hardener, the isocyanate-functional polymer has a molecular weight less than about 2000 daltons, less than about 1500 daltons, less than about 1000 daltons, and in some embodiments less than about 500 daltons.

In such compositions, the isocyanate hardener may be from about 0.5 wt. % to 20 wt. % composition, from about 1 wt. % to 10 weight. %, from about 2 wt. % to 8 wt. %, from about 2 wt. % to 6 wt. %, and in some embodiments, the implementation of approximately 3 weight. % to 5 wt. % composition, where percentages by weight are calculated relative to the total weight of the solid residue of the composition.

In some embodiments, such as when using isocyanate-terminal bis (sulfonyl) alkanol-containing polythioethers, their prepolymers or isocyanate-terminal prepolymer containing a ligand capable of binding to the metal, the compositions described in this text contain an amine hardener. Examples of suitable hardeners capable of reacting with isocyanate groups include diamines, polyamines, polythiols, and polyols, including those described in the present text.

In some embodiments, such as when using a Michael-terminal acceptor bis (sulfonyl) alkanol-containing polythioethers, their prepolymers or a Michael-terminal prepolymer containing a ligand capable of binding to the metal, the compositions described in this text contain a curing agent selected from monomeric thiol, polythiol, polyamine and blocked polyamine.

Hardeners that can be used in the compositions described herein include compounds that can react with the terminal groups of a bis (sulfonyl) alkanol-containing polythioether or prepolymer containing a ligand that can bind to the metal, such as compounds that can react with hydroxyl groups, alkenyl groups, epoxy groups, thiol groups, amino groups or isocyanate groups.

Examples of suitable hardeners capable of reacting with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are described in the present text.

Examples of suitable hardeners capable of reacting with alkenyl groups include dithiols and polythiols, examples of which are described in the present text.

The polyalkoxy-silyl-terminal bis (sulfonyl) alkanol-containing polythioethers or prepolymers described in this text, containing a ligand capable of binding to a metal, can be hydrolyzed in the presence of water, inducing self-polymerization through condensation. Catalysts for use with a polyalkoxy-silyl-terminal bis (sulfonyl) alkanol-containing polythioether or a polyalkoxy-silyl-terminal prepolymer containing a ligand capable of binding to a metal include organotanes, such as tetraisopropoxytitanium, tetra-tert-butoxytitane, and you can use the same type of material that you are using. a) titanium and di (isopropoxy) bis (acetylacetoacetate) titanium; organotin compounds of dibutyl tin dilaurate, dibutyl tin bisacetylacetoacetate and tin octylate; metal dicarboxylates, such as lead dioctylate; zirconium organic compounds such as zirconium tetraacetylacetonate; and organoaluminum compounds, such as aluminum, triacetyl-acetonate. Other examples of suitable catalysts for wet curing include diisopropoxy bis (ethyl acetoacetonate) titanium, diisopropoxy bis (acetylacetonate) titanium and dibutoxy bis (methyl acetoacetonate) titanium. It should be understood that since the curing agent for a polyalkoxysilyl terminal bis (sulfonyl) alkanol-containing polythioether or a polyalkoxy-silyl terminal prepolymer containing a ligand capable of binding to a metal may be atmospheric moisture, it is not necessary to include a hardener in the curable composition containing the polyalkoxy moiety, it is not necessary to incorporate the hardener. (sulfonyl) alkanol-containing polythioether or polyalkoxysilyl-terminal prepolymer containing a ligand capable of binding to the metal. Therefore, for compositions containing polyalkoxysilyl-terminal bis (sulfonyl) alkanol-containing polythioethers or polyalkoxy-silyl-terminal prepolymers containing a ligand capable of binding to the metal, the hardener for polyalkoxysilyl groups is atmospheric air moisture.

In some embodiments, in which a bis (sulfonyl) alkanol-containing polythioether, its prepolymer or prepolymer containing a ligand capable of binding to a metal, has terminal epoxy groups, a suitable curing agent is a polythiol, polyalkylene or polyamine. Other examples of suitable curing agents capable of reacting with terminal epoxy groups include amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine (N-AEP), isophoronediamine (IPDA ), m-xylene diamine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS); aromatic amines, ketimine; polyamines; polyamides; phenolic resins; anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitat, glycerol tristrimellitat, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride; polymercaptans; polysulfides; and other hardeners known to those skilled in the art.

The compositions described herein may contain from about 90% to about 150% of a stoichiometric amount, from about 95% to about 125%, and in some embodiments, from about 95% to about 105% of the amount of hardener (s) selected.

Additional sulfur-containing polymers

In some embodiments, the compositions described herein contain, in addition to the bis (sulfonyl) alkanol-containing polythioether, its prepolymer, the prepolymer containing the ligand for the metal, or the product of any of the reactions described herein, or a combination of any of the above , one or more additional sulfur-containing polymers. The sulfur-containing polymer can be any polymer that has at least one sulfur atom in a repeating fragment, including (but not limited to, polymeric thiols, polythiols, thioethers, polythioethers, sulfur-containing polyformals and polysulfides. The term “thiol,” as used herein, refers to a compound containing a thiol or mercaptan group, i.e., “SH” group, as a single functional group or in combination with other functional groups, such as hydroxyl groups, as in the case for example, thioglycerols. Polythiol is a compound with more than one SH group, such as dithiol or thiol with greater functionality. Such groups are usually terminal and / or side, so that they contain active hydrogen, which can react with other functional groups. A polythiol can contain both terminal and / or lateral sulfur atoms (-SH), and non-reactive sulfur atoms (-S- or -S-S-). Thus, the term "politiol" generally covers polythioethers and polysulfides.

Examples of additional sulfur-containing prepolymers that can be used in the compositions described herein include, for example, those described in US Pat. No. 6,172,179, 6,509,418, and 7,009,032. In some embodiments, the implementation described in the present text of the composition contain a polythioether having the structure of Formula (30):

where R ^{1 is} selected from C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 cycloalkanalkandiyl, - [(- CH ₂ -) _{s -} X -] _q - (- CH ₂ -) _r - and - [( -CH ₂ -) _s -X-] _q - (- CH ₂ -) _r -, where at least one -CH ₂ - fragment is replaced by a methyl group; R ^{2 is} selected from C _2-6 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 cycloalkanalkanediyl and - [(- CH ₂ -) _s -X-] _q - (- CH ₂ -) _r -; X is selected from O, S, and —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; m is an integer from 0 to 10; n is an integer from 1 to 60; p is an integer from 2 to 6; q is an integer from 1 to 5, and r is an integer from 2 to 10. Such polythioethers are described in US Pat. No. 6,172,179 col. 2, line 29 - count. 4, line 34.

These one or more additional sulfur-containing polymers can be difunctional or multifunctional, for example, contain 3-6 terminal groups, or be a mixture of them.

In some embodiments, the implementation described in the present text compositions contain from about 10 weight. % to 90 wt. % described in this text is a sulfur-containing polymer, from about 20 wt. % up to 80 wt. %, from about 30 wt. % to 70 wt. %, and in some embodiments, the implementation of about 40 weight. % to 60 wt. %, where the weight percentages are calculated relative to the total weight of all non-volatile components of the composition (i.e., dry weight).

When used in the present text, the term "polysulfide" means a polymer that contains one or more sulfide bridges, i.e. -S _x - bridges, where x is from 2 to 4, in the main polymer chain and / or in the lateral positions of the polymer chain. In some embodiments, the polysulfide polymer contains two or more sulfur-sulfur bridges. Suitable polysulfides are commercially available, for example, from Akzo Nobel and Toray Fine Chemicals under the names Thiokol-LP and Thioplast ^® . Thioplast ^® products are available in a wide range of molecular weights, for example, from less than 1,100 to over 8,000, where the molecular weight is the average molecular weight in grams per mole. In some cases, the polysulfide has a number average molecular weight from 1000 daltons to 4000 daltons. The density of crosslinks in these products also varies, depending on the amount of crosslinking agent used. The content is -SH, i.e. the content of thiols or mercaptans, in these products may also vary. The mercaptan content and the molecular weight of the polysulfide can affect the rate of solidification of the polymer, while the rate of solidification increases with molecular weight.

Sulfur-containing polyformal prepolymers that can be used in sealants for the aerospace industry are described, for example, in the publication of the application for US Patent No. 2012/0234205 and in the publication of the application for US Patent No. 2012/0238707.

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

Compositions described herein may include one or more catalysts. The catalyst can be selected in accordance with the applied curing chemistry. In some embodiments, for example, when curing the thiol-terminal bis (sulfonyl) alkanol-containing polythioethers, prepolymers or thiol-terminal prepolymers containing a ligand for the metal, and polyepoxides, the catalyst is an amine catalyst. The curing catalyst may be present in an amount of from 0.1 to 5 weight. %, based on the total weight of the composition. Examples of suitable catalysts include 1,4-diazabicyclo [2.2.2] octane (DABCO ^®, commercially available from Air Products, Chemical Additives Division, Allentown , Pa.) And DMP-30 ^® (accelerating composition comprising 2,4,6 tris (dimethylaminomethyl) phenol).

In some embodiments, the compositions described herein contain one or more than one adhesion promoter. One or more additional adhesion promoters may be present in an amount of from 0.1 weight. % to 15 wt. % composition, less than 5 wt. % less than 2 weight. %, and in some embodiments, the implementation of less than 1 weight. %, based on the total dry weight of the composition. Examples of adhesion promoters include phenolics such as Methylon ^® phenolic resins, and organosilanes such as epoxy, mercapto or amino functional silanes such as Silquest ^® A-187 and Silquest ^® A-1100. Other suitable adhesion promoters are known in the prior art.

Described in this text, the composition may contain one or more different types of fillers. Suitable fillers include those well known in the art, including inorganic fillers such as carbon black and calcium carbonate (CaCO ₃ ), silica gel, polymer powders and light fillers. Suitable lightweight fillers include, for example, those described in US Pat. No. 6,525,168. In some embodiments, the composition contains from 5 wt. % to 60 wt. % filler or combination of fillers, from 10 weight. % to 50 wt. %, and in some embodiments, the implementation of 20 wt. % to 40 wt. %, based on the total dry weight of the composition. The compositions described herein may additionally contain one or more colorants, thixotropic agents, accelerators, flame retardants, adhesion promoters, solvents, masking agents, or a combination of any of the above. It is clear that the fillers and additives used in the composition are selected so that they are compatible with each other, as well as with the polymer component, hardener and / or catalyst. Examples of non-conductive fillers include (but not limited to) such materials as calcium carbonate, mica, polyamide, silica gel, molecular sieve powder, microspheres, titanium dioxide, chalk, alkaline soot, cellulose, zinc sulfide, heavy spar, alkaline earth oxides, alkaline earth metal hydroxides, etc.

In some embodiments, the implementation described in this text, the compositions contain particles of low density filler. When used in this text, the term "low density" in relation to such particles means that the particles have a specific gravity of not more than 0.7, in some embodiments no more than 0.25, and in some embodiments no more than 0.1. Suitable low density filler particles often fall into two categories — microspheres and amorphous particles. The specific gravity of the microspheres can range from 0.1 to 0.7, and they include, for example, polystyrene foam, polyacrylate and polyolefin microspheres, and silica gel microspheres having a particle size in the range from 5 to 100 microns and a specific gravity of 0.25 (Eccospheres ^® ). Other examples include alumina / silica gel microspheres having a particle size in the range of 5 to 300 microns and a specific gravity of 0.7 (Fillite®), aluminum silicate microspheres having a specific gravity of about 0.45 to 0.7 (Z-Light ^®), calcium carbonate coated microspheres polivinilidenovogo copolymer having a specific gravity of 0,13 (Dualite ^® 6001AE), and microspheres coated calcium carbonate acrylonitrile copolymer, such as Dualite ^® E135, having an average particle size of about 40 microns and a density of 0.135 g / cm ³ (Henkel). Suitable fillers for reducing the specific gravity of the composition include, for example, hollow microspheres, such as Expancel ^® microspheres (available from AkzoNobel) or Dualite ^® low density polymer microspheres (available from Henkel). In some embodiments, the compositions described herein contain low-density filler particles that have a thin coating on the outer surface, such as those described in the publication of US Patent Application No. 2010/0041839 in paragraphs [0016] - [0052], the quoted fragment of which is included in this text by reference.

In some embodiments, the implementation, the low density filler is less than 2 weight. % composition, less than 1.5 wt. % less than 1.0 weight. %, less than 0.8 weight. % less than 0.75 weight. % less than 0.7 wt. %, and in some embodiments, the implementation of less than 0.5 weight. % composition, where the weight percent is calculated relative to the total dry weight of the composition.

In some embodiments, the implementation described in the present text of the composition contain at least one filler, which effectively reduces the proportion of the composition. In some embodiments, the implementation, the specific gravity of the composition is from 0.8 to 1, from 0.7 to 0.9, from 0.75 to 0.85, and in some embodiments, the implementation is 0.8. In some embodiments, the implementation, 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 some embodiments less than about 0.55.

In some embodiments, the compositions described herein contain an electrically conductive filler. The electrical conductivity and shielding effectiveness of electromagnetic / radio interference can be imparted to the composition by introducing conductive materials into the polymer. Conductive elements may include, for example, metallic or metal coated particles, fabrics, nets, fibers, and combinations thereof. The metal may be in the form of, for example, filaments, particles, flakes or spheres. Examples of metals include copper, nickel, silver, aluminum, tin and steel. Other conductive materials that can be used to impart a polymeric composition to effective shielding properties from electromagnetic / radio interference include conductive particles or fibers containing carbon or graphite. Conductive polymers such as polythiophenes, polypyrroles, polyaniline, poly (p-phenylene) vinylene, polyphenylene sulfide, polyphenylene, and polyacetylene can also be used. Electrically conductive fillers also include materials with a wide band gap, such as zinc sulfide and inorganic barium compounds.

Other examples of electrically conductive fillers include electrically conductive fillers based on noble metals, such as pure silver; precious metals coated with precious metals, such as silver plated gold; non-noble metals coated with noble metals, such as silver-coated copper, nickel or aluminum, for example silver-coated aluminum particles or platinum-coated copper particles; glass, plastic or ceramic coated with noble metals, such as silver-coated glass microspheres, aluminum-coated with noble metals, or plastic-coated microspheres coated with noble metals; precious metal coated mica; and other similar conductive fillers with noble metals. Non-precious metal materials can also be used, and include, for example, non-precious metal-coated non-precious metals, such as copper-coated iron particles or nickel-coated copper particles; non-noble metals, such as copper, aluminum, nickel, cobalt; non-precious metal coated non-metals, such as nickel-coated graphite and non-metallic materials such as carbon black and graphite. You can also use combinations of electrically conductive fillers to impart target conductivity, shielding effectiveness against electromagnetic / radio interference, hardness, and other properties necessary for a particular application.

The shape and size of the electrically conductive fillers used in the compositions of the present invention can be any, imparting a cured composition of electrical conductivity and / or shielding effectiveness from electromagnetic / radio interference. For example, fillers can be of any shape commonly used in the manufacture of electrically conductive fillers, including spherical, flaky, lamellar, particulate, powder, irregular, fiber, and the like. In some sealant compositions of the present invention, the base of the composition may contain graphite coated with nickel in the form of particles, powder, or flakes. In some embodiments, the implementation, the amount of nickel-coated graphite in the base composition may be in the range of 40 wt. % up to 80 wt. %, and in some embodiments, the implementation may be in the range of 50 weight. % to 70 wt. %, based on the total weight of the base composition. In some embodiments, the implementation, the electrically conductive filler may be a Ni fiber. Ni fiber can have a diameter in the range from 10 μm to 50 μm and a length in the range from 250 μm to 750 μm. The base composition may contain, for example, Ni fiber in an amount of from 2 wt. % to 10 weight. %, and in some embodiments, the implementation of 4 wt. % to 8 wt. %, based on the total weight of the base composition.

Carbon fiber, in particular graphitized carbon fiber, can also be used to impart electrical conductivity to the compositions of the present invention. Carbon fiber obtained by gas-phase pyrolysis and graphitized by heat treatment, which is hollow or solid, with a fiber diameter ranging from 0.1 micron to several microns, has a high conductivity. As described in US Pat. No. 6,184,280, carbon microfibers, nanotubes, or carbon fibers having an outer diameter of less than 0.1 μm to tens of nanometers can be used as electrically conductive fillers. An example of graphitized carbon fiber that can be used in the conductive compositions of the present invention includes ^{Panex ® 3OMF (Zoltek Companies, Inc.} , St. Louis, Mo.), a circular fiber diameter 0.921 microns, having a resistivity 0,00055 Ω-cm.

The average particle size of the electrically conductive filler may be in the range suitable for imparting electrical conductivity to the polymer-based composition. For example, in some embodiments, implementation, the particle size of one or more fillers may be in the range from 0.25 μm to 250 μm, in some embodiments, the implementation can be in the range from 0.25 μm to 75 μm, and in some embodiments, implementation in the range of 0.25 microns to 60 microns. In some embodiments, the composition of the present invention may contain Ketjen Black EC-600 JD (Akzo Nobel, Inc., Chicago, Ill.), Electrically conductive carbon black, characterized by an iodine number of 1000-11500 mg / g (test method J0 / 84-5 ), and a pore volume of 480-510 cm ^3/100 g (DBP adsorption, KTM 81-3504). In some embodiments, the implementation of the electrically conductive particulate filler is Black Pearls 2000 (Cabot Corporation, Boston, Mass.).

In some embodiments, electrically conductive polymers may be used to impart or modify the electrical conductivity of the compositions of the present invention. It is known that polymers having sulfur atoms included in aromatic groups or adjacent to double bonds, as in polyphenylene sulfide and polythiophene, are electrically conductive. Other electrically conductive polymers include, for example, polypyrroles, polyaniline, poly (p-phenylene) vinylene, and polyacetylene. In some embodiments, sulfur-containing polymers that form the base of the composition can be polysulfides and / or polythioethers. As such, sulfur-containing polymers may contain aromatic sulfur-containing groups and sulfur atoms adjacent to conjugated double bonds to enhance the electrical conductivity of the compositions of the present invention.

The compositions of the present invention may contain more than one electrically conductive filler, and these more than one electrically conductive fillers may consist of the same or different materials and / or forms. For example, the sealing composition may contain electrically conductive Ni fibers and electrically conductive nickel-coated graphite in the form of powder, particles, or flakes. The number and type of electrically conductive filler can be selected so as to obtain a sealing composition that, after curing, has a specific surface resistance (four-point resistance) less than 0.50 Ω / cm ² , and, in some embodiments, the specific surface resistance is less than 0.15 Ω / cm ² . The number and type of filler can also be chosen in such a way as to achieve effective shielding of electromagnetic / radio interference in the frequency range from 1 MHz to 18 GHz for the hole sealed using the sealing composition of the present invention.

In some embodiments, the implementation, the electrically conductive base of the composition may contain an amount of non-conductive filler in the range of 2 wt. % to 10 weight. %, based on the total weight of the base composition, and in some embodiments, the implementation is in the range of 3 weight. % to 7 wt. % In some embodiments, the implementation, the composition of the hardener may contain an amount of electroconductive filler less than 6 weight. %, and in some embodiments, implementation. - in the range of 0.5 weight. % to 4 weight. %, based on the total weight of the hardener composition.

Electrochemical corrosion of the differing metal surfaces and conductive compositions of the present invention can be minimized or prevented by adding corrosion inhibitors to the composition and / or selecting suitable conductive fillers. In some embodiments, the implementation of corrosion inhibitors include strontium chromate, calcium chromate, magnesium chromate, and combinations thereof. US Patent No. 5,284,888 and US Patent No. 5,270,364 describe the use of aromatic triazoles to suppress corrosion of aluminum and steel surfaces. In some embodiments, a consumable oxygen scavenger such as Zn can be used as a corrosion inhibitor. In some embodiments, the implementation, the corrosion inhibitor may be less than 10 weight. % of the total weight of the electrically conductive composition. In some embodiments, the implementation, the corrosion inhibitor may be from 2 weight. % to 8 wt. % of the total weight of the electrically conductive composition. Corrosion between different metal surfaces can also be minimized or prevented by selecting the type, amount and properties of conductive fillers that make up the composition.

In some embodiments, the implementation, bis (sulfonyl) alkanol-containing polythioether and / or bis (sulfonyl) alkanol-containing polythioether prepolymer and / or prepolymers containing a ligand for the metal, can be from about 50 weight. % to 90 wt. % composition, from about 60 wt. % to 90 wt. %, from about 70 wt. % to 90 wt. %, and in some embodiments, the implementation of about 80 weight. % to 90 wt. % composition, where the weight percent is calculated relative to the total dry weight of the composition.

The composition may also contain, if desired, any number of additives. Examples of suitable additives include plasticizers, pigments, surfactants, adhesion promoters, thixotropic agents, flame retardants, masking agents and accelerators (such as amines, including 1,4-diaza-bicyclo [2.2.2] octane, DABCO®), and combinations of any of the listed components. In the case of their use, the additives may be present in the composition in an amount of, for example, from about 0% to about 60% by weight. In some embodiments, the additives may be present in the composition in an amount from about 25% to about 60% by weight.

Application

Described in this text, the composition can be applied, for example, in sealants, coatings, encapsulating compositions and sealing compositions. Sealants include compositions that can provide a film that can withstand working conditions, such as humidity and temperature, and at least partially block the penetration of substances such as water, fuel and other liquids and gases. The coating composition is a coating applied to the surface of the substrate, for example, to improve the characteristics of the substrate, such as appearance, adhesion, wettability, corrosion resistance, wear resistance, resistance to fuel and / or resistance to abrasives. The sealing composition includes a material that can be used in electronic components to provide resistance to shock and vibration and to eliminate the effects of moisture and corrosive agents. In some embodiments, the sealant compositions described in this text can be used, for example, as sealants for the aerospace industry and as an internal coating for fuel tanks.

In some embodiments, implementation, compositions, such as sealants, can be produced in the form of multi-component compositions, such as two-component compositions, where one component contains one or more described in this text thiol-terminal polythioether containing a ligand capable of binding to the metal, or prepolymers, containing a thiol terminal ligand capable of binding to the metal, and the second component contains one or more polyfunctional sulfur-containing epoxides described in the present text. Additives and / or other compounds can be added to any of the components as desired and necessary. These two separate components can be combined and mixed before use. In some embodiments, the implementation, the lifetime of one or more of the mixed thiol-terminal polythioethers and epoxides is at least 30 minutes, at least 1 hour, at least 2 hours, and in some embodiments, more than 2 hours, where the period of life is called the time during which the mixed composition remains acceptable for use as a sealant after mixing.

Compositions, including sealants, described in this text, can be applied to any variety of substrates. Examples of substrates on which the composition can be applied include metals, such as titanium, stainless steel, aluminum and their alloys, any of which can be anodized, coated with a primer, an organic coating or a chromate coating; epoxy compounds; urethanes; graphite; fiberglass composites; Kevlar ^® ; acrylic compounds and polycarbonates. In some embodiments, the implementation described in this text, the composition can be applied to the coating on the substrate, such as a polyurethane coating. In some embodiments, implementation, compositions containing bis (sulfonyl) alkanol-containing polythioether or prepolymers containing a ligand for the metal described in the present text, have increased adhesion to aluminum, aluminum oxide, anodized aluminum, titanium, titanium oxide and / or Alodine® surfaces. In particular, compositions containing bis (sulfonyl) alkanol-containing polythioethers or prepolymers containing a metal ligand described in this text have increased adhesion to the bare metal and anodized metal surfaces.

Described in this text, the composition can be applied directly on the surface of the substrate or on top of the primer layer, any suitable methods of coating, known to qualified specialists in this field of technology.

In addition, methods are described for sealing openings using the composition described in the present text. Such methods include, for example, applying a composition as described herein to a surface to seal a hole and curing the composition. In some embodiments, the method of sealing the holes includes (a) applying one or more of the surfaces defining the hole described in this text, and (b) curing the applied sealing composition to form a sealed hole.

In some embodiments, the implementation described hole, sealed with a sealing composition of the present invention.

In some embodiments, the composition can be cured at ambient conditions, where ambient conditions mean a temperature of 20 ° C to 25 ° C and atmospheric humidity. In some embodiments, implementation, the composition can be cured in conditions covering temperatures from 0 ° C to 100 ° C and humidity from 0% relative humidity to 100% relative humidity. In some embodiments, the implementation, the composition can be cured at a higher temperature, such as at least 30 ° C., At least 40 ° C., And in some embodiments, the implementation of at least 50 ° C. In some embodiments, the implementation, the composition can be cured at room temperature, for example 25 ° C. In some embodiments, the implementation, the composition can be cured when exposed to actinic radiation, such as ultraviolet radiation. As will be understood, these methods can be used to seal openings in aerospace ships, including airplanes and spacecraft.

In some embodiments, the composition reaches a tacky hardness in less than about 2 hours, in less than about 4 hours, in less than about 6 hours, in less than about 8 hours, and in some embodiments in less than about 10 hours, temperatures below about 200 ° F.

The time it takes to form a complete hermetic seal using the curable composition of the present invention may depend on several factors, as will be appreciated by those skilled in the art, and as required by accepted standards and specifications. In general, curable compositions of the present invention achieve a sticking force in 24-30 hours, and 90% of the total sticking force is achieved within 2-3 days after mixing and application to the surface. In general, the full strength of adhesion, as well as other properties of the cured composition of the present invention, is fully achieved within 7 days after mixing and applying the curable composition to the surface.

The cured compositions described in this text, such as cured sealants, exhibit properties suitable for use in the aerospace field. In general, it is desirable that the sealants used in the aviation and aerospace industries have the following properties: tensile strength of more than 20 psi. inch (psi) on Aerospace Material Specification (AMS) 3265V substrates, when measured in dry conditions, after being placed in JRF Type I for 7 days and then immersed in 3% NaCl solution, according to the specifications of the AMS 3265 V test ; tensile strength between 300 psi (psi) and 400 psi. inch; peel strength greater than 50 pounds per linear inch (lb / lin. inch); elongation from 250% to 300%; and rigidity greater than 40 by Durometer A. These and other properties of a cured sealant suitable for use in aviation and aerospace are described in AMS 3265B, which is fully incorporated into this text by reference. It is also desirable that, after curing, the compositions of the present invention, used in the field of aviation, have a percentage of volumetric swelling of no more than 25% after one week immersion at 60 ° C (140 ° F) and atmospheric pressure in JRF Type I. Other properties, ranges and / or parameters may be similar to other sealants.

Therefore, in some embodiments, the compositions described herein are resistant to fuels. When used in the present text, the term "fuel resistance" means that a composition, when applied to a substrate and cured, is capable of giving a cured product, such as a sealant, having a swelling percentage of no more than 40%, in some cases no more than 25%, in in some cases no more than 20%, in other cases no more than 10%, after immersion for 1 week at 140 ° F (60 ° C) and ambient air pressure in a Type I Reference Fuel (JRF) according to methods similar to those described in ASTM D792 (American Society for Testing and Materia alam) or AMS 3269 (Aerospace Materials Specification). The Type I JRF Reference Reactive Fuel used to determine fuel resistance has the following composition: toluene: 28% ± 1% by volume; cyclohexane (technical): 34% ± 1% by volume; isooctane: 38% ± 1% by volume; and tert-dibutyl disulfide: 1% ± 0.005% by volume (see AMS 2629, dated July 1, 1989, §3.1.1, etc., available from SAE (Society of Automotive Engineers)).

In some embodiments, the compositions described herein provide a cured product, such as a sealant, that provides an elongation at a strain of at least 100% and a tensile strength of at least 400 psi. inch, when measured in accordance with the procedure described in AMS 3279, §3.3.17.1, test method AS5127 / 1, §7.7.

In some embodiments, the implementation of the composition give a cured product, such as a sealant, which provides the strength of the lap joint with a shear of more than 200 psi. inch, for example at least 220 psi. inch, at least 250 psi. inch, and, in some cases, at least 400 psi. inch, when measured in accordance with the method described in SAE AS5127 / 1 paragraph 7.8.

In some embodiments, the cured sealant containing the composition described in this text meets or exceeds the requirements for aerospace sealants given in AMS 3277.

Holes are also described, including holes in aerospace ships sealed by the compositions described in this text.

In some embodiments, the cured sealant described in this text has the following characteristics after curing for 2 days at room temperature, 1 day at 140 ° F, and 1 day at 200 ° F: dry hardness 49, tensile strength 428 psi inch, and an elongation of 266%; and after 7 days at JRF Type I, hardness 36, tensile strength 312 psi. inch, and an elongation of 247%.

In some embodiments, the compositions described herein have Shore hardness (after 7 days of solidification) greater than 10, greater than 20, greater than 30, and in some embodiments greater than 40; tensile strength greater than 10 psi. inch, more than 100 psi. inch, more than 200 psi. inch, and in some embodiments, the implementation of more than 500 psi. inch; elongation greater than 100%, greater than 200%), greater than 500%), and in some embodiments greater than 1000%; and swelling after treatment in JRF Type I (7 days) is less than 20%).

Cured sealants obtained from the prepolymer described in the present text, containing a ligand capable of binding to a metal, have increased tensile strength and increased adhesion to the surfaces of the metal and / or metal oxide. The ligands capable of binding to the metal included in the main chain of the prepolymer can act as polydentate ligands in metal chelates.

Examples

The embodiments described in the present text are further illustrated by the examples described below, which describe the synthesis, properties and uses of some bis (sulfonyl) alkanol-containing polythioethers and prepolymers containing a ligand for a metal, and compositions containing a bis (sulfonyl) alkanol-containing polythioethers or prepolymers containing a ligand for the metal. Qualified specialists in this field will be obvious that in practice there are numerous modifications, both in terms of materials and methods, not beyond the scope of the present invention.

Example 1

Thiol-terminal polythioether

1,8-Dimercapto-3,6-dioxaoctane (DMDO; 1995.60 g; 10.95 mol) was loaded into a 5-liter 4-necked round bottom flask. The flask was equipped with a gas adapter to introduce nitrogen, a paddle stirrer and a temperature sensor. The flask was purged with nitrogen and the mixture was heated to 60 ° C with stirring. Free radical initiator Vazo ^® -67 (0.41 g) was added to the flask. Divinyl ether (1154.51 g, 7.30 mol) was introduced into the reaction mixture for 6.25 hours, while maintaining the temperature in the range from 60 ° C to 65 ° C. The temperature of the reaction mixture was raised to 77 ° C and two portions of Vazo ^® -67 (0.045 g each) were added at intervals of 3 hours. The reaction mixture was heated at 94 ° C for 2 hours, cooled to 66 ° C and evaporated at 66 ° C - 74 ° C / 15 mm Hg. within 1 hour. The polymer obtained, dithiol, had an equivalent weight of mercaptan 430.

Example 2

Thiol-terminal bis (sulfonyl) alkanol-containing polythioether

The dithiol from 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 gas adapter to introduce nitrogen and a paddle stirrer. The reaction mixture was evaporated at 7 mm Hg. for 30 minutes, and the vacuum was lowered in a nitrogen atmosphere. While stirring, the basic catalyst DBU (1,8-diazabicycloundec-7-ene; 0.013 g) was added, then ethanol (10 g) was added to the flask with a temperature sensor. 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 dropped in for 2 hours at a temperature from 19 ° С to 20 ° С . The water bath was removed and the reagents were stirred at room temperature for another 2 hours. An equivalent weight of mercaptan was used to determine the completion point of the reaction. After removal of the solvents, a liquid difunctional polymer having an equivalent weight of mercaptan of 1166 and a viscosity of 81 poises was obtained.

Example 3

Thiol-terminal bis (sulfonyl) alkanol-containing polythioether prepolymer

The dithiol from Example 2 (62 g; 0.0177 mol) was loaded into a 250 ml 3-necked round bottom flask. With stirring, a solution of triallyl cyanurate (TAS) (0.93 g; 0.0037 mol) and diethylene glycol of divinyl ether (0.22 g; 0.0014 mol) in toluene (1.0 g) were introduced into the reaction mixture, and the mixture was heated to 77 ° C. Seven servings (0.016 g each) of the radical initiator Vazo ^® -67 were added at 1 hour intervals to complete the reaction. Removal of solvents in vacuo gave a polymer having a theoretical thiol functionality of 2.21, an equivalent weight of mercaptan of 1659; and viscosity 195 poise.

Example 4

Bis (sulfonyl) alkanol-containing polythioether sealant

The prepolymer of Example 3 (. 14.93 g; 0.009 eq) and calcium carbonate (Socal ^® N2R; 4,48 g) were charged into the mixer chamber (capacity: 60 g) agitators Hauschild (model: DAC 600 FVZ). The contents were mixed by hand and then mixed in a Hauschild mixer for 30 seconds (speed: 2300 rpm). The contents were mixed again manually and then mixed in a Hauschild mixer for 30 seconds. Added epoxy accelerator S-5304 (available from PPG Aerospace; 3.60 g, 0.009 eq.). The contents were mixed by hand and then mixed in a Hauschild mixer for 30 seconds. A basic DABCO 33-LV catalyst (0.12 g) was added. The contents were mixed by hand and then mixed in a Hauschild mixer for 30 seconds.

Part of the mixture obtained was used to make a back Christmas tree cap for a test of hardness, and the rest was used to make samples for testing adhesion (approximate dimensions: 4 cm × 1.4 cm × 0.3 cm) on seven surfaces: treated with Scotch-Brite® tape naked aluminum; Mil-C-27725; taped Scotch-Brite® Titanium B; Scotch-Brite® Titanium C treated tape; Alodine® 1200; anodized SAA and anodized CAA. All samples were subjected to a curing cycle at room temperature / 20 h; 60 ° C / 27 h. After curing, the hardness was 40 (Shore). The adhesion, as measured by tearing off / cutting off the cured sealant from the metal surface, was very good for six of the seven surfaces (100% cohesive failure); however, the cured sample did not adhere to Alodine® 1200 (0% cohesive failure).

Example 5

Thiol-terminal bis (sulfonyl) alkanol-containing difunctional polythioether

Dithiol from Example 1 (636.40 g; 0.74 mol) was loaded into a 2-liter 4-necked round bottom flask. The flask was equipped with a gas adapter to introduce nitrogen and a paddle stirrer. Content was evaporated at 8 mm Hg. for 1 hour, and lowered the vacuum in a nitrogen atmosphere. Ethanol (116 g) was added with stirring, then a DBU base catalyst (0.145 g), and the flask was equipped with a temperature sensor. While 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 dropped in for about 2 hours at a temperature of 23 °. C to 27 ° C. A mercaptan equivalent was used to control the progress of the reaction. The water bath was removed and the reagents were stirred at room temperature for another 3 hours. Removal of the solvents gave a difunctional polymer having an equivalent weight of mercaptan of 1296 and a viscosity of 107 poises.

Example 6

Thiol-terminal bis (sulfonyl) alkanol-containing polythioether prepolymer

The difunctional polymer from Example 5 (725.29 g; 0.2798 mol) was loaded into a 2-liter 4-necked round bottom flask. The flask was equipped with a gas adapter to introduce nitrogen and a paddle stirrer. The contents were flushed with nitrogen. With stirring, a solution of triallyl cyanurate (10.22 g; 0.041 mol) and diethylene glycol of divinyl ether (0.49 g; 0.0031 mol) in toluene (5.0 ml) were introduced into the reaction mixture, and the mixture was heated to 70 ° C. Fifteen servings (0.084 g each) of the radical initiator Vazo ^® -67 were added at 1 hour intervals to complete the reaction. Removal of solvents in vacuum gave a polymer having a theoretical thiol functionality of 2.21, an equivalent weight of mercaptan of 1657; and a viscosity of 238 poises.

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) were charged into the mixer chamber (capacity: 100 g) Hauschild mixer. The contents were mixed by hand and then mixed in a Hauschild mixer for 30 seconds (speed: 2300 rpm). The mixture was twice subjected to a cycle of manual mixing and further mixing in a Hauschild mixer for 4 minutes. The mixture was cooled to ambient temperature. An epoxy accelerator S-5304 (available from PPG Aerospace; 7.16 g, 0.0197 equiv.) Was added. The mixture was twice subjected to a cycle of manual mixing and further mixing in a Hauschild mixer for 30 seconds. A basic DABCO 33-LV catalyst (0.24 g) was added. The contents were mixed by hand and then mixed in a Hauschild mixer for 30 seconds, and poured into the mill, yielding an effluent (approximate dimensions: length: 6 inches; width: 3.2 inches; thickness: 0.1 inches). A sample of the sealant was subjected to a curing cycle at room temperature / 7 days; then cured at 140 ° F / 24 hours. The cured sealant had a shore hardness of 48, a tensile strength of 373 psi and an elongation of 472%.

Comparative Example 1

Permapol® 3.1E polymer (10 g, thiol-terminal polythioether prepolymer, commercially available from PRC-Desoto International, Sylmar, CA) and calcium carbonate (5.0 g) were mixed in a Hauschild mixer for 30 seconds at 2300 rpm . An accelerator was sequentially added (S-5304, 2.6 g, epoxy paste, commercially available from PRC-Desoto International, Sylmar, CA) and the catalyst (triethylenediamine; 0.08 g) and mixed. Samples were applied to various substrates, including anodized CAA, anodized SAA, Mil C-27725, Alodine® 1200, Titanium C, bare aluminum, and Scotch-Brite® treated bare aluminum, and cured at room temperature for 24 hours, after which cured for 48 hours at 140 ° F. The percentage of cohesive failure was measured by detaching the sample from the substrates. Each sample showed 0% cohesive failure.

Example 8

Calculations using density functional theory

Gibbs free energy for the interaction of various functional groups with the Al ₄ O ₆ cluster (Li et al., "Structural determination of (Al ₂ O ₃ ) _n (n = 1-7)" 2012, 996, 125-131), representing the surface of aluminum oxide of a representative aerospace substrate, was calculated using methods based on density functional theory (DFT). All structures were optimized using Gaussian09 / B3LYP / 6-31g (d), and the vibrational frequency was calculated at the same level of theory to confirm that all structures are at a local minimum. A single-point calculation of energy with a CPCM solvating scheme was used to calculate energy in an aqueous medium. Gibbs free energy for the interaction was calculated under standard pressure and temperature conditions (1 atm and 25 ° C) without adjustment.

Different functional groups were analyzed for their intrinsic properties, including HOMO energy (highest occupied molecular orbital), LUMO (lowest vacant molecular orbital), and the energy difference between HOMO and LUMO. Usually, functional groups with higher HOMO energy are more electron-donor, and groups with lower energy LUMO are more electron-acceptor. Comparing the different functional groups in Table 1, it can be seen that 3-hydroxy-1,2-dimethylpyridin-4 (1H) -one (NORO) has the highest HOMO energy, which indicates that NORO is the most electron-donor group. The bis (sulfonyl) -2-propanol (BSP) functional group, on the other hand, has the lowest energy HOMO, indicating that it is the least electron-donor group.

The calculation of interactions between different functional groups and an aluminum oxide cluster was made. The Gibbs free energy for interaction in the gas phase (ΔG _g ) and in water (ΔG _w ) was calculated, and the results are shown in FIG. 1, together with the contribution of the enthalpy (ΔH) of the reaction. FIG. 1, a more negative ΔG value corresponds to a more stable complex and a stronger interaction between the functional group and aluminum oxide. BSP and NORO have a stronger interaction than acetoacetate with alumina in the gas phase and in a simulated aqueous environment. Acetoacetate binds to Al ₄ O ₆ by coordinating electron-rich carbonyl oxygen (in acetoacetate) with electron-deficient aluminum (in Al ₄ O ₆ ). NORO interacts with Al ₄ O ₆ as a bidentate ligand: i.e. carbonyl oxygen (in NORO) is bound to aluminum (in Al ₄ O ₆ ), and a hydroxyl group (in NORO) is hydrogen bonded to oxygen (in Al ₄ O ₆ ). The tridentate binding of BSP to Al ₄ O ₆ was identified: two sulfonyl groups (in BSP) bind to two aluminum atoms (in Al ₄ O ₆ ) in addition to the hydrogen bond between the hydroxyl group (in BSP) and the oxygen atom (in Al ₄ O ₆ ). Even though the BSP is not very electron donor (as illustrated by the low energy HOMO in table 1), however, strong binding to Al ₄ O ₆ is observed at three coordination sites.

In conclusion, it was shown that the BSP functional group binds to alumina like a tridentate ligand, which leads to a very strong interaction (adhesion). Unlike other strongly binding ligands, such as NORO, BSP is heavily oxidized and is expected to have high stability. Structures with a type of binding similar to BSP can also give strong binding to alumina.

Similar methods can be used to identify other ligands capable of binding to the metal, which are suitable for enhancing adhesion to the surface of a particular metal and can be included in the main chain of the prepolymer and / or act as the terminal group of the prepolymer, as described in the present text.

In conclusion, it should be noted that there are alternative ways of practical implementation of the embodiments described in the present text. Accordingly, the described embodiments are to be regarded as illustrative and non-limiting. In addition, the invention is not limited to the details described in the text, but covers its entire scope and its equivalents.

Claims (191)

1. A prepolymer containing a ligand capable of binding to a metal in which a ligand capable of binding to a metal is included in the main chain of the prepolymer, the ligand capable of binding to the metal including a structure selected from Formula (25a), Formula (25b), Formula (25c), Formulas (25d), Formulas (25e), and combinations of any of the above: −X– (CH ₂ ) _n −CH (−OH) -
−X– (CH ₂ ) _n –CH (–OH) - (CH ₂ ) _n –X–
−CH (−OH) - (CH ₂ ) _n –X– (CH ₂ ) _n –CH (–OH) -
−CH (−OH) −R ⁵ −CH (−OH) -
−C (O) −R ⁵ −C (O) - (25a)
(25b)
(25c)
(25d)
(25e) Where –X– independently represents –C (O) - or –S (O) ₂ -; each n independently represents 1, 2 or 3; and R ⁵ is a C _1-3 alkanediyl. 2. The prepolymer according to claim 1, wherein each X is —C (O) - and each n is 1. 3. The prepolymer according to claim 1, wherein each X is −S (O) ₂ - and each n is 1. 4. A prepolymer containing a ligand capable of binding to a metal in which a ligand capable of binding to a metal is included in the prepolymer main chain, wherein said prepolymer contains a fragment of Formula (26): -AR ^{9 '} -LR ^9' -A- (26) Where each R ^{9 'is} independently a fragment formed by the reaction of R ⁹ metal chelating agent R ⁹ –L – R ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with thiol; and L contains a ligand capable of binding to the metal; each A independently represents a fragment of Formula (12): -SR ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S- (12) Where each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes —O—, —S—, and –NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; and each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ; m is an integer from 0 to 50; n is an integer from 1 to 60; and p is an integer from 2 to 6. 5. The prepolymer according to claim 4, in which the metal chelating agent is selected from bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and a combination of any of the above. 6. A prepolymer containing a ligand capable of binding to a metal in which a ligand capable of binding to a metal is included in the main chain of the prepolymer, where said prepolymer comprises a polythioether of Formula (28a) containing a ligand capable of binding with metal containing a ligand capable of binding to the metal, or a combination of them: R ⁶ -A - [- R ^{9 '} -LR ^9' -A-] _N -R ⁶
{R ⁶ -A - [- R ^{9 '} -LR ^9' -A-] _N -V'-} _z B (28a)
(28b) Where N is an integer from 1 to 10; each R ^{9 'is} independently a fragment formed by the reaction of R ⁹ metal chelating agent R ⁹ –L – R ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with thiol; and L contains a ligand capable of binding to the metal; each A independently represents a fragment of Formula (12): -SR ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S- (12) Where each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen or methyl; each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ; m is an integer from 0 to 50; n is an integer from 1 to 60; and p is an integer from 2 to 6; B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6; each V is a group containing a terminal group capable of reacting with terminal thiol groups; and each -V’- is formed by the reaction of -V with a thiol; and each R ^{6 is} independently selected from a hydrogen atom and a moiety having a terminal reactive group. 7. The prepolymer according to claim 6, in which each R ⁶ represents a hydrogen atom. 8. The prepolymer according to claim 6, in which all R ^{6 are the} same, and the terminal reactive group is selected from –SH, –CH = CH ₂ , –NH ₂ , –OH, epoxy, polyalkoxysilyl group, isocyanate group and acceptor group Michael 9. A thiol-terminal polythioether containing a ligand capable of binding to a metal containing a reaction product of reagents, including: (a) a thiol-terminal polythioether, including a thiol-terminal polythioether of Formula (18a), a thiol-terminal polythioether of Formula (18b), or a combination of them: HS-R ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -SH
{HS-R ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S-V'-} _z B (18a)
(18b) Where each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes —O—, —S-, or –NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given 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; and B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6; each V is a group containing a terminal group capable of reacting with terminal thiol groups; and each -V’- is formed by the reaction of -V with a thiol; and (b) a metal chelating agent R ⁹ -LR ⁹ , where each R ⁹ independently includes a terminal group capable of reacting with a thiol; and –L– contains a ligand capable of binding to the metal. 10. The polythioether of claim 9, wherein the ligand capable of binding to the metal comprises a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e) and combinations of any of listed above: −X– (CH ₂ ) _n −CH (−OH) -
−X– (CH ₂ ) _n –CH (–OH) - (CH ₂ ) _n –X–
−CH (−OH) - (CH ₂ ) _n –X– (CH ₂ ) _n –CH (–OH) -
−CH (−OH) −R ⁵ −CH (−OH) -
−C (O) −R ⁵ −C (O) - (25a)
(25b)
(25c)
(25d)
(25e) Where –X– independently represents –C (O) - or –S (O) ₂ -; each n independently represents 1, 2 or 3; and R ⁵ is a C _1-3 alkanediyl. 11. The polythioether of claim 9, wherein the metal chelating agent comprises a bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, or a combination of any of the above. 12. The polythioether of claim 9, wherein the polythioether of Formula (18a) includes the reaction product of dithiol and divinyl ether. 13. The polythioether of claim 9, wherein the polythioether of Formula (18a) includes the reaction product of 1,8-dimercapto-3,6-dioxoctane and divinyl ether diethylene glycol. 14. The polythioether of claim 9, wherein the polythioether of Formula (18b) comprises the reaction product of dithiol, divinyl ether and polyfunctionalizing agent. 15. The polythioether of claim 9, wherein the polythioether of Formula (18b) comprises the reaction product of 1,8-dimercapto-3,6-dioxoctane, divinyl ether diethylene glycol and triallyl cyanurate. 16. Alkenyl-terminal polythioether prepolymer containing a ligand capable of binding to the metal containing the reaction product of reagents, including: (a) a thiol-terminal polythioether containing a ligand capable of binding to a metal, including a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal , or their combination: HA - [- R ^{9 '} -LR ^9' -A-] _N -H
{HA - [- R ^{9 '} -LR ^9' -A-] _N -V'-} _z B (29a)
(29b) Where N is an integer from 1 to 10; each R ^{9 'is} independently a fragment formed by the reaction of R ⁹ metal chelating agent R ⁹ –L – R ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with thiol; and L is a ligand capable of binding to the metal; each A independently represents a fragment of Formula (12): -SR ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S- (12) Where each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes —O—, —S—, or —NR ⁵ -, where R ^{5 is} selected from hydrogen and methyl; each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ; m is an integer from 0 to 50; n is an integer from 1 to 60; and p is an integer from 2 to 6; B is the core of a z-valent, alkenyl-terminal polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6; and each V is a group containing a terminal alkenyl group; and each -V’- is formed by the reaction of -V with a thiol; and (b) a polyalkenyl compound. 17. The polythioether prepolymer according to claim 16, wherein the ligand capable of binding to the metal comprises a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e) and combinations of any of listed above: −X– (CH ₂ ) _n −CH (−OH) -
−X– (CH ₂ ) _n –CH (–OH) - (CH ₂ ) _n –X–
−CH (−OH) - (CH ₂ ) _n –X– (CH ₂ ) _n –CH (–OH) -
−CH (−OH) −R ⁵ −CH (−OH) -
−C (O) −R ⁵ −C (O) - (25a)
(25b)
(25c)
(25d)
(25e) Where –X– independently represents –C (O) - or –S (O) ₂ -; each n independently represents 1, 2 and 3; and R ⁵ is a C _1-3 alkanediyl. 18. The polythioether prepolymer of claim 16, wherein the polyalkenyl compound includes divinyl ether, an alkenyl terminal polyfunctionalizing agent, or a combination thereof. 19. A method of producing a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal, comprising (N + 1) mol of the thiol-terminal polythioether of Formula (18a) with (N) mol of the metal-chelating agent R ⁹ -LR ⁹ : HA - [- R ^{9 '} -LR ^9' -A-] _N -H
HS-R ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -SH (29a)
(18a) Where N is an integer from 1 to 10; each R ^{9 'is} independently a fragment formed by the reaction of R ⁹ metal chelating agent R ⁹ –L – R ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with thiol; and L contains a ligand capable of binding to the metal; each A independently represents a fragment of Formula (12): -SR ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S- (12) Where each R ¹ independently represents C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes -O-, -S-, or –NR ^5- , where R ⁵ includes a hydrogen atom or methyl; and each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ; m is an integer from 0 to 50; n is an integer from 1 to 60; and p is an integer from 2 to 6. 20. The method of claim 19, wherein the ligand capable of binding to the metal comprises a structure selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and combinations of any of listed above: −X– (CH ₂ ) _n −CH (−OH) -
−X– (CH ₂ ) _n –CH (–OH) - (CH ₂ ) _n –X–
−CH (−OH) - (CH ₂ ) _n –X– (CH ₂ ) _n –CH (–OH) -
−CH (−OH) −R ⁵ −CH (−OH) -
−C (O) −R ⁵ −C (O) - (25a)
(25b)
(25c)
(25d)
(25e) Where –X– independently represents –C (O) - or –S (O) ₂ -; each n independently represents 1, 2 and 3; and R ⁵ is a C _1-3 alkanediyl. 21. The method according to p. 19, in which the metal chelating agent contains: a ligand capable of binding to a metal selected from a bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and / or a combination of any of the above; and at least two terminal groups capable of reacting with thiol groups. 22. A method of producing a thiol-terminal polythioether of Formula (29b) containing a ligand capable of binding to a metal, comprising reacting (z) a mole of a thiol-terminal polythioether of Formula (29a) containing a ligand capable of binding to a metal with one (1) mole polyfunctionalizing agent B {V} _z : {HA - [- R ^{9 '} -LR ^9' -A-] _N -V'-} _z B
HA - [- R ^{9 '} -LR ^9' -A-] _N -H (29b)
(29a) Where N is an integer from 1 to 10; each R ^{9 'is} independently a fragment formed by the reaction of R ⁹ metal chelating agent R ⁹ –L – R ⁹ with a thiol group, where each R ⁹ contains a terminal group capable of reacting with thiol; and L contains a ligand capable of binding to the metal; each A independently represents a fragment of Formula (12): -SR ¹ - [- S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n -S- (12) Where each R ¹ independently includes C _2-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-10 alkancycloalkanediyl, 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 includes a hydrogen atom or methyl; and each X independently includes —O—, —S—, or —NR ⁵ -, where R ⁵ includes a hydrogen atom or methyl; each R ² independently includes C _1-10 alkanediyl, C _6-8 cycloalkanediyl, C _6-14 alkancycloalkanediyl or - [(- CHR ³ -) _{s -} X -] _q - (- CHR ³ -) _r -, where s, q, r, R ³ and X correspond to the definitions given for R ¹ ; m is an integer from 0 to 50; n is an integer from 1 to 60; and p is an integer from 2 to 6; and B is the core of a z-valent polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6; each V is a group containing a terminal group capable of reacting with a terminal thiol group; and each -V'- is formed by the reaction of -V with thiol. 23. The method of claim 22, wherein the ligand capable of binding to the metal comprises a structure selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and combinations of any of listed above: −X– (CH ₂ ) _n −CH (−OH) -
−X– (CH ₂ ) _n –CH (–OH) - (CH ₂ ) _n –X–
−CH (−OH) - (CH ₂ ) _n –X– (CH ₂ ) _n –CH (–OH) -
−CH (−OH) −R ⁵ −CH (−OH) -
−C (O) −R ⁵ −C (O) - (25a)
(25b)
(25c)
(25d)
(25e) Where –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 a C _1-3 alkanediyl. 24. A method according to claim 22, in which the metal chelating agent contains: a ligand capable of binding to a metal selected from bis (sulfonyl) alkanol, hydroxypyridinone, acetylacetonate, and a combination of any of the above; and at least two terminal groups capable of reacting with thiol groups. 25. A composition comprising a prepolymer containing a ligand capable of binding to a metal according to claim 1. 26. A composition according to claim 25, formulated as a sealing composition. 27. The composition of claim 25, comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer is selected from a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, and a combination of any of the above. 28. The composition according to p. 25, containing the hardener. 29. A cured sealant containing composition according to claim 25. 30. A composition comprising a prepolymer containing a ligand capable of binding to a metal according to claim 4. 31. The composition according to claim 30, comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, or a combination of any of the above. 32. The composition according to p. 30, containing a hardener. 33. Cured sealant containing composition according to claim 30. 34. A composition comprising a prepolymer containing a ligand capable of binding to a metal according to claim 6. 35. The composition according to claim 34, comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, or a combination of any of the above. 36. The composition according to p. 34, containing the hardener. 37. Cured sealant containing composition according to claim 34. 38. A composition comprising a prepolymer containing a ligand capable of binding to a metal according to claim 9. 39. The composition according to claim 38, comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, or a combination of any of the above. 40. The composition according to p. 38, containing the hardener. 41. Cured sealant containing composition according to claim 38. 42. A composition comprising a prepolymer containing a ligand capable of binding to a metal according to claim 16. 43. The composition according to claim 42, comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises a polythioether prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, or a combination of any of the above. 44. The composition according to p. 42, containing the hardener. 45. Cured sealant containing composition according to claim 42.