阅读说明：本技术 使用聚醚增效剂控制固化速率 (Control of cure rate using polyether synergist ) 是由 A·L·托里斯 L·赫苏 J·马丁 于 2020-04-06 设计创作，主要内容包括：公开了具有聚醚增效剂的聚硫化物组合物。含有聚醚增效剂的聚硫化物组合物表现出快速开始固化并具有可接受的最终性质。所述聚硫化物组合物可以用作密封剂。(Polysulfide compositions having polyether synergists are disclosed. Polysulfide compositions containing polyether synergists exhibit a fast onset of cure and have acceptable final properties. The polysulfide compositions can be used as sealants.)

1. A composition, comprising:

a polysulfide prepolymer;

a polysulfide cure activator;

a polysulfide curing accelerator;

a porous material; and

a synergist, wherein the synergist comprises a polyether, and

wherein the composition comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is by total weight of the composition.

2. The composition of claim 1, wherein

The polysulfide cure activator comprises a metal oxide; and is

The polysulfide cure accelerator includes an amine-based sulfur donor.

3. The composition of claim 1, wherein the porous material is characterized by:

BET of 5m²G to 700m²/g；

A total pore volume of 0.01mL/g to 10 mL/g;

an average pore diameter of 10nm to 30 nm; or

A combination of any of the foregoing.

4. The composition of claim 1, wherein the porous material comprises silica, alumina, zinc oxide, titania, zirconia, hafnia, yttria, rare earth oxides, boehmite, alkaline earth metal fluoride, calcium phosphate, and hydroxyapatite, or a combination of any of the foregoing.

5. The composition of claim 1, wherein the porous material comprises silica.

6. The composition of claim 1, wherein the composition comprises from 0.1 wt% to 10 wt% of the porous material, wherein wt% is by total weight of the composition.

7. The composition of claim 1, wherein the composition comprises a filler.

8. The composition of claim 7, wherein the composition comprises from 5 wt% to 70 wt% filler, wherein wt% is by total weight of the composition.

9. The composition of claim 1, wherein the polyether comprises polyethylene glycol, polypropylene glycol, poly (tetramethylene ether) glycol, a block copolymer of any of the foregoing, a crown ether, or a combination of any of the foregoing.

10. The composition of claim 1, wherein the polyether comprises a terminal hydroxyl group, a terminal alkyl group, a terminal substituted phenyl group, a terminal (meth) acryloyl group, or a combination of any of the foregoing.

11. The composition of claim 1, wherein the polyether comprises a polyether having a structure of formula (7), a structure of formula (8), or a combination thereof:

wherein

n is an integer of 1 to 6;

p is an integer from 2 to 50;

z is an integer from 3 to 6;

each R¹Independently selected from hydrogen, C_1-10Alkyl, (meth) acryloyl, and substituted aryl;

each R²Independently selected from hydrogen and C_1-3An alkyl group; and is

B is a multifunctional moiety.

12. The composition of claim 1, wherein the polyether has a number average molecular weight of less than 5,000Da, wherein molecular weight is determined by gel permeation chromatography.

13. The composition of claim 1, wherein the composition comprises:

20 to 70 wt% of the polysulfide prepolymer, wherein wt% is by total weight of the composition;

less than 10 wt% of said polysulfide cure activator, wherein wt% is by total weight of said composition;

less than 2 wt% of said polysulfide cure accelerator; and

1 to 6 wt% of the synergist, wherein wt% is based on the total weight of the composition.

14. A cured composition prepared from the composition of claim 1.

15. A part comprising the cured composition of claim 14.

16. A method of sealing a component, the method comprising:

applying the composition of claim 1 to a surface of a part; and

curing the applied composition to seal the part.

17. A component sealed using the method of claim 16.

18. A sealant system, comprising:

(a) a first component, wherein the first component comprises a polysulfide prepolymer; and

(b) a second component, wherein the second component comprises a polysulfide cure activator;

wherein at least one of the first component and the second component independently comprises a synergist comprising a polyether, a porous material, a polysulfide cure accelerator, or a combination of any of the foregoing, and

wherein the sealant system comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is based on the total weight of the first component and the second component.

19. A cured sealant prepared from the sealant system of claim 18.

20. A part comprising the cured sealant of claim 19.

21. A method of sealing a component, the method comprising:

combining the first component and the second component of the sealant system of claim 18 to provide a curable sealant composition;

applying the curable sealant composition to a surface of a part; and

curing the applied sealant composition to seal the part.

22. A component sealed using the method of claim 21.

Technical Field

Polysulfide compositions containing polyether synergists are disclosed. Polysulfide compositions containing polyether synergists exhibit a fast onset of cure and have acceptable cure properties. The polysulfide compositions can be used as sealants.

Background

Polysulfide compositions typically include a polysulfide cure activator and a polysulfide cure accelerator to control the rate of cure. To obtain acceptable properties, such as tensile strength and elongation, large amounts of fillers, including porous materials, are typically added to the polysulfide composition. While fillers can improve the physical properties of the cured polysulfide composition, fillers can also reduce the rate of cure. Porous materials such as silica have been observed to reduce the cure rate of polysulfide sealants. Although the silica content can be reduced, silica is unique in its ability to impart enhanced physical properties to the cured polysulfide composition.

Polysulfide formulations containing porous materials such as silica and exhibiting fast cure rates and acceptable cure properties are desired.

Disclosure of Invention

According to the invention, the composition comprises: a polysulfide prepolymer; a polysulfide cure activator; a polysulfide curing accelerator; a porous material; and a synergist, wherein the synergist comprises a polyether, and wherein the composition comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is by total weight of the composition.

According to the invention, the sealant system comprises: (a) a first component, wherein the first component comprises a polysulfide prepolymer; and (b) a second component, wherein the second component comprises a polysulfide cure activator; wherein at least one of the first component and the second component independently comprises: a synergist, wherein the synergist comprises a polyether; a porous material; a polysulfide curing accelerator; or a combination of any of the foregoing, and wherein the sealant system comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is based on the total weight of the first component and the second component.

Drawings

The drawings described herein are for illustration purposes only. The drawings are not intended to limit the scope of the present disclosure.

Figure 1 shows the shore a hardness during curing of polysulfide sealants containing different amounts and different types of polyethers.

Figure 2 shows the shore a hardness during curing of polysulfide sealants containing different amounts and different types of polyethers.

Figure 3 shows the shore a hardness during curing of polysulfide sealants containing different amounts and different types of polyethers.

Figure 4 shows the shore a hardness during curing of polysulfide sealants containing different amounts and different types of polyethers and polysulfide sealants containing water.

Fig. 5 shows the% swelling of polysulfide sealants containing different types of polyethers after 7 days immersion in 3% NaCl or JRF type I at 60 ℃.

Figure 6 shows the shore a hardness during curing of polysulfide sealants containing different polyethers.

Figure 7 shows the shore a hardness during curing of polysulfide sealants containing different polyethers.

Figure 8 shows the shore a hardness during curing of polysulfide sealants containing varying amounts of hydrophobic silica.

FIG. 9 shows the results when different amounts of TiO are included₂And varying amounts of polysulfide cure accelerator.

Figure 10 shows the shore a hardness during curing of polysulfide sealants containing hydrophilic silica with and without polyether.

Figure 11 shows the shore a hardness during curing of polysulfide sealants containing different types of silica with and without polyether synergists.

Detailed Description

For the purposes of the following detailed description, it is to be understood that the embodiments provided by the present disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

It should also be understood that all numerical ranges recited herein are intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

A dash ("-") that is not between two letters or symbols is used to indicate a substituent or a point of bonding between two atoms. For example, -CONH₂Attached through a carbon atom.

"Alkanediyl" means having, for example, 1 to 18 carbon atoms (C)_1-18)1 to 14 carbon atoms (C)_1-14)1 to 6 carbon atoms (C)_1-6)1 to 4 carbon atoms (C)_1-4) Or 1 to 3 hydrocarbon atoms (C)_1-3) A saturated or unsaturated, branched or straight chain acyclic hydrocarbon radical of (a). It is understood that a branched alkanediyl group has at least three carbon atoms. Alkanediyl may be C_2-14Alkanediyl, C_2-10Alkanediyl, C_2-8Alkanediyl, C_2-6Alkanediyl, C_2-4Alkanediyl or C_2-3An alkanediyl group. Examples of alkanediyl include methane-diyl (-CH)₂-), ethane-1, 2-diyl (-CH)₂CH₂-), propane-1, 3-diyl, and isopropane-1, 2-diyl (e.g., -CH₂CH₂CH₂-and-CH (CH)₃)CH₂-), butane-1, 4-diyl (-CH)₂CH₂CH₂CH₂-) pentane-1, 5-diyl (-CH)₂CH₂CH₂CH₂CH₂-), hexane-1, 6-diyl (-CH)₂CH₂CH₂CH₂CH₂CH₂-), heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl and dodecane-1, 12-diyl.

"alkyl" refers to a single radical of a saturated or unsaturated, branched or straight chain acyclic hydrocarbon group having, for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. It is understood that branched alkyl groups have at least three carbon atoms. The alkyl group may be C_1-6Alkyl radical, C_1-4Alkyl or C_1-3An alkyl group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl and tetradecyl. Alkyl is C_1-6Alkyl radical, C_1-4Alkyl and C_1-3An alkyl group.

"Aryldiyl" refers to a diradical monocyclic or polycyclic aromatic group. Examples of aryldiyl groups include phenyldiyl and naphthalenediyl. The aryldiyl group may be C_6-12Aryl diyl, C_6-10Aryl diyl, C_6-9Aryldiyl or benzenediyl.

E.g. branched C_2-10"branched" groups such as alkanediyl refer to a non-linear C wherein at least one carbon atom is bonded to at least three carbon atoms_2-10An alkanediyl group. For example, part-CH₂–CH₂–CH₂–CH₂Is linear C₄Alkanediyl, and moiety-CH₂–CH(–CH₃)–CH₂–CH₂-is a branch C₄Examples of alkanediyl.

"BET surface area" is determined in accordance with DIN EN ISO 9277/DIN 66132.

"Total pore volume" is determined according to ASTM D-3663-78 using N₂Desorption isotherm determination.

"average pore diameter"is the use of N according to ASTM D-3663-78₂Desorption isotherm determination.

"composition" is intended to encompass a product comprising the specified components in the specified amounts, as well as any product which results, directly or indirectly, from combination of the specified components in the specified amounts.

A "polysulfide cure activator" is an oxidizing agent that provides a source of oxygen for the oxidation of the terminal thiol groups of the polysulfide.

"polysulfide cure accelerators" such as organic bases can increase the rate of oxidation of thiol groups.

As used herein, the term "cure" or "cured" as used in connection with a composition, e.g., "composition as cured" or "cured composition" means that any curable or crosslinkable component of the composition is at least partially reacted or crosslinked.

"curable composition" refers to a composition comprising at least two reactants capable of reacting to form a cured composition. For example, the curable composition can include an isocyanate-terminated chain extended polythioether prepolymer and a polyamine that can react to form a cured polymer. The curable composition may contain a catalyst for the curing reaction and other components such as fillers, pigments and adhesion promoters. The curable composition may be curable at room temperature or may require exposure to elevated temperatures, such as temperatures above room temperature, or other conditions to initiate and/or accelerate the curing reaction. The curable composition may initially be provided in the form of a two-component composition comprising, for example, a separate base component and accelerator component. The base composition may contain one of the reactants involved in the curing reaction, such as an isocyanate-terminated chain-extended polythioether prepolymer, and the accelerator component may contain another reactant, such as a polyamine. The two components may be mixed shortly before use to provide a curable composition. The curable composition may exhibit a viscosity suitable for the particular application method. For example, a class a sealant composition suitable for brush-on application (brush-on application) can be characterized by a viscosity of 1 poise to 500 poise (0.1 pascal-seconds to 50 pascal-seconds). Class B sealant compositions suitable for fillet seal application can be characterized by a viscosity of 4,500 poise to 20,000 poise (450 pa-sec to 2,000 pa-sec). A class C sealant composition suitable for joint sealing applications may be characterized by a viscosity of 500 poise to 4,500 poise (50 pa-sec to 450 pa-sec). The viscosity of the composition was measured as described herein. After the two components of the sealant system are combined and mixed, the curing reaction can proceed and the viscosity of the curable composition can increase and at some point will no longer be useful, as described herein. The duration of time between when the two components are mixed to form the curable composition and when the curable composition can no longer be reasonably or practically applied to a surface for its intended purpose may be referred to as the working time. It will be appreciated that the working time may depend on a number of factors including, for example, the curing chemistry, the catalyst used, the application method and the temperature. Once the curable composition is applied to the surface (and during application), a curing reaction can proceed to provide a cured composition. The cured composition forms a tack-free surface, cures, and then fully cures over a period of time. For a type B sealant or a type C sealant, the curable composition may be considered cured when the surface hardness is at least shore 30A. After the sealant cures to a shore 30A hardness, the curable composition may take several days to several weeks to fully cure. When the hardness no longer increased, the composition was considered to be fully cured. Depending on the formulation, the fully cured sealant may exhibit a hardness of, for example, shore 40A to shore 70A, as determined according to ISO 868. For coating applications, the viscosity of the curable composition can be, for example, from 200cps to 800cps 0.2 (pascal-seconds to 0.8 pascal-seconds). For sprayable coating and sealant compositions, the viscosity of the curable composition can be, for example, from 15cps to 100cps (0.015 pa-sec to 0.1 pa-sec), such as from 20cps to 80cps (0.02 pa-sec to 0.0.8 pa-sec).

"JRF type I" (jet reference fluid type I) was used to determine solvent resistance and had the following composition: toluene: 28 plus or minus 1 volume percent; cyclohexane (technical): 34 +/-1 volume percent; isooctane: 38 + -1 vol%; and tert-dibutyl disulfide: 1 + -0.005 vol% (see AMS 2629, published in 1989, 7/1/3.1.1, available from SAE (Society of Automotive Engineers)). JRF type I Testing was performed according to the method described in ASTM D792 (American Society for Testing and Materials) or AMS 3269 (Aerospace Material Specification).

"(meth) acryloyl" means-O-C (═ O) -CH ═ CH₂and-O-C (═ O) -C (-CH)₃)＝CH₂A group.

"molecular weight" refers to a theoretical molecular weight estimated from the chemical structure of a compound such as a monomer compound, or a number average molecular weight suitable for a prepolymer, as determined by gel permeation chromatography using polystyrene standards, for example.

The "particle size" is determined according to ISO 13320 from the median value obtained from laser diffraction measurements.

"polyether" refers to a compound containing two or more ether groups-O. The polyether may be a monomer such as a crown ether and/or a prepolymer such as polyethylene glycol.

"polyether synergist" refers to a polyether that when added to a curable composition such as a manganese dioxide-cured polysulfide composition, can accelerate the cure rate of the curable composition. Polyether synergists are used to reinforce other cure accelerators that may be present in the curable composition.

"multifunctional moiety" refers to a moiety that contains three or more moieties bonded to a common moiety. For example, the common moiety may be derived from an atom such as a carbon atom, a cycloalkane, a heterocycloalkane, an arene, a heteroarene, an alkane, or a heteroalkane hydrocarbon group. The polyfunctional moiety may be, for example, C_2-20Alkane-triyl, C_2-20Heteroalkane-triyl, C_5-10Cycloalkane-triyl, C_5-10Heterocyclane-triyl, C_6-20Alkane cycloalkane-triyl, C_6-20Heteroalkanecycloalkane-triyl substituted C_2-20Alkane-triyl, substituted C_2-20Heteroalkane-triyl, substituted C_5-10Cycloalkanetriyl, substituted C_5-10Heterocyclane-triyl, substituted C_6-20Alkanoalkycloalkanetriyl or substituted C_6-20Heteroalkane cycloalkane-triyl. The polyfunctional moiety may be, for example, C_2-8Alkane-tetrayl, C_2-8Heteroalkane-tetrayl, C_5-10Cycloalkane-tetrayl, C_5-10Heterocyclane-tetrayl, C_6-10Arene-tetrayl, C₄Heteroarene-tetrayl, substituted C_2-8Alkane-tetrayl, substituted C_2-8Heteroalkane-tetrayl, substituted C_5-10Cyclo-cyclo-alka-tetra-yl, substituted C_5-10Heterocyclane-tetrayl, substituted C_6-10Arene-tetrayl and substituted C_4-10A heteroarene-diyl group.

"polysulfide" means a prepolymer having one or more polysulfide linkages (i.e., -S) in the main chain of the prepolymer_x-a bond), wherein x is 2 to 4. The polysulfide prepolymer may have two or more sulfur-sulfur bonds. Suitable thiol-terminated polysulfide prepolymers are available, for example, from Akzo Nobel and Toray Industries, Inc., Japan, under the trade namesAndare commercially available.

"porous material" refers to a material that includes voids or pores, wherein the size of the pores may be widely distributed in the nanometer to micrometer range. The porous material may comprise a porous inorganic material, a porous organic material, or a combination thereof. The porous material may be a filler, rheology control agent, extender, flame retardant, corrosion inhibitor, or a combination of any of the foregoing. The porous material may be characterized, for example, by: BET of 5m²G to 700m²(ii)/g; a total pore volume of 0.01mL/g to 10 mL/g; an average pore diameter of 5nm to 30 nm; or a combination of any of the foregoing. The porous material may be characterized, for example, by: BET of more than 5m²(ii)/g; the total pore volume is more than 0.01 mL/g; an average pore diameter greater than 5; or a combination of any of the foregoing.

"prepolymer" refers to oligomers, homopolymers and copolymers. The prepolymer comprises repeating units in the backbone of the prepolymer. Homopolymer refers to a prepolymer having the same repeating units. Copolymer refers to a prepolymer comprising alternating copolymers, random copolymers, and block copolymers. The prepolymer may have a number average molecular weight of, for example, greater than 1,000Da, greater than 2,000Da, or greater than 3,000 Da. For thiol-terminated prepolymers, the molecular weight is the number average molecular weight "Mn" as determined by end group analysis using iodine titration. For example, the SH content of the thiol-terminated prepolymer can be determined using iodometric titration. For non-thiol-terminated prepolymers, the number average molecular weight is determined by gel permeation chromatography using polystyrene standards. The prepolymer includes reactive groups that can react with another compound, such as a curing agent or a crosslinking agent, to form a cured polymer. Prepolymers, such as the chain-extended polythioether prepolymers provided by the present disclosure, can be combined with a curing agent to provide a curable composition that can be cured to provide a cured polymer network. The prepolymer was liquid at room temperature (25 ℃ C.) and pressure (760 torr; 101 kPa). The prepolymer is reacted with another compound to provide a cured polymer network. The prepolymer comprises a plurality of repeating subunits bonded to each other, which subunits may be the same or different. The plurality of repeating subunits comprise the backbone of the prepolymer.

Shore A hardness was measured according to ASTM D2240 using a type A durometer.

"silica" means SiO₂And may be in particulate form. Silica includes, for example, ionic silica, nonionic silica, hydrophobic silica, hydrophilic silica, untreated silica, treated silica, fumed silica, precipitated silica, and combinations of any of the foregoing.

The specific weight and density of the composition and sealant were determined according to ISO 2781.

"thiol-terminated" refers to-SH end groups, such as the end groups of a prepolymer.

When referring to a chemical group, for example, defined by a number of carbon atoms, the chemical group is intended to encompass all subranges of carbon atoms as well as a specific number of carbon atoms. E.g. C_2-10Alkanediyl comprises_2-4Alkanediyl, C_5-7Alkanediyl and other subranges,C₂Alkanediyl, C₆Alkanediyl and alkanediyl having other specified numbers of carbon atoms from 2 to 10.

Reference is now made to certain compounds, compositions and methods of the present invention. The disclosed compounds, compositions, and methods are not intended to limit the claims. On the contrary, the claims are intended to cover all alternatives, modifications, and equivalents.

The addition of small amounts of polyether to the polysulfide composition can increase the cure rate without reducing the performance attributes of the cured polysulfide composition.

The polysulfide composition provided by the present disclosure comprises a polysulfide prepolymer, a polysulfide cure activator, a polysulfide cure accelerator, a porous material, and a synergist, wherein the synergist comprises a polyether. The polysulfide composition may optionally comprise, for example, fillers, adhesion promoters, thixotropic agents, plasticizers, flame retardants, corrosion inhibitors, colorants, moisture control additives, extenders, solvents, and combinations of any of the foregoing.

The polysulfide prepolymer may comprise a single polysulfide prepolymer or a combination of polysulfide prepolymers. The polysulfide prepolymer may comprise a thiol-terminated polysulfide prepolymer.

Examples of suitable polysulfide prepolymers are disclosed in, for example, U.S. patent nos. 4,623,711 and 7,009,032.

The polysulfide prepolymer may be a blend of difunctional and trifunctional molecules, where the difunctional polysulfide prepolymer may include a structure of formula (1a) or may include a moiety of formula (1):

-(-R-S-S-)_n-R- (1)

HS-(-R-S-S-)_n-R-SH (1a)

and the trifunctional polysulfide prepolymer may have the structure of formula (2a) or may include moieties of formula (2):

-(-R-S-S-)_a-CH₂-CH{-CH₂-(-S-S-R-)_b-}{-(-S-S-R-)_c-} (2)

HS-(-R-S-S-)_a-CH₂-CH{-CH₂-(-S-S-R-)_b-SH}{-(-S-S-R-)_c-SH} (2a)

wherein each R is- (CH)₂)₂-O-CH₂-O-(CH₂)₂And n ═ a + b + c, where the value of n may be from 7 to 38, depending on the amount of trifunctional crosslinking reagent (1,2, 3-trichloropropane; TCP) used during the synthesis of the polysulfide prepolymer. Suitable polysulfide prepolymers may have a number average molecular weight of less than 1,000Da to 6,500Da, an SH (thiol) content of 1% to more than 5.5%, and a crosslink density of 0% to 2.0%.

Examples of suitable thiol-terminated polysulfide prepolymers having a moiety of formula (2) or a structure of formula (2a) include Thioplast^TMG polysulphides, e.g. Thioplast^TM G1、Thioplast^TM G4、Thioplast^TM G10、Thioplast^TM G12、Thioplast^TM G21、Thioplast^TM G22、Thioplast^TM G44、Thioplast^TMG122 and Thioplast^TMG131, commercially available from aksunobel corporation.

Polysulfide prepolymers may include, for example, Thioplast^TMG1 and Thioplast^TM112.

The polysulfide prepolymer may have a number average molecular weight of 1,000Da to 7,500Da, an SH (thiol) content of 0.8% to 7.7%, and a crosslinking density of 0% to 2%. The polysulfide prepolymer may have the general structure of formula (3a) or may include moieties of formula (3):

-[(CH₂)₂-O-CH₂-O-(CH₂)₂-S-S-]_n-(CH₂)₂-O-CH₂-O-(CH₂)₂- (3)

HS-[(CH₂)₂-O-CH₂-O-(CH₂)₂-S-S-]_n-(CH₂)₂-O-CH₂-O-(CH₂)₂-SH (3a)

wherein n may be selected such that the number average molecular weight is from 1,000Da to 7,500Da, for example n is an integer from 8 to 80.

Suitable thiol-terminated poly(s) having a moiety of formula (3) or a structure of formula (3a)Examples of the sulfide prepolymer further include Thiokol commercially available from Toray corporation of Japan^TMLP polysulfides, e.g. Thiokol^TM LP2、Thiokol^TM LP3、Thiokol^TM LP12、Thiokol^TM LP23、Thiokol^TMLP33 and Thiokol^TM LP55。

The thiol-terminated sulfur-containing prepolymer can include Thiokol-LP^TMPolysulphide, Thioplast^TMG polysulfide, or a combination thereof.

The thiol-terminated polysulfide prepolymer may comprise a thiol-terminated polysulfide prepolymer of formula (4a) or may comprise moieties of formula (4):

-R-(S_y-R)_t- (4)

HS-R-(S_y-R)_t-SH (4a)

wherein

t may be an integer from 1 to 60;

q may be an integer from 1 to 8;

p may be an integer from 1 to 10;

r may be an integer from 1 to 10;

the average value of y may be in the range of 1.0 to 1.5; and is

Each R may be independently selected from the group consisting of branched alkanediyl, branched aryldiyl, and a compound having the structure- (CH)₂)_p–O–(CH₂)_q–O–(CH₂)_r-part (a).

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), t may be, for example, an integer from 2 to 60, from 1 to 40, or from 1 to 20.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), q may be, for example, an integer of 1 to 6 or an integer of 1 to 4. For example, q may be 1,2,3, 4,5, or 6.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), each p may be, for example, an integer from 1 to 6 or from 1 to 4. For example, each p can be 1,2,3, 4,5, 6, 7, 8,9, or 10.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), each r may be, for example, an integer of 1 to 6 or 1 to 4. For example, each p can be 1,2,3, 4,5, 6, 7, 8,9, or 10.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), each value of y may independently be 1,2,3, 4,5, or 6.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), the average value of y may be, for example, 1, such as 1.05 to 2, 1.1 to 1.8, or 1.1 to 1.5.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), R may be- (CH)₂)_p–O–(CH₂)_q–O–(CH₂)_r–。

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), R may be- (CH)₂)_p–O–(CH₂)_q–O–(CH₂)_r-, each q may be 1,2,3 or 4, and each p and r may be 1 or 2.

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), 0% to 20% of the R groups may comprise branched alkanediyl or branched aryldiyl, and 80% to 100% of the R groups may be- (CH)₂)_p–O–(CH₂)_q–O–(CH₂)_r–。

In the thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4), the branched alkanediyl or branched aryldiyl group may be-R¹(–A)_n-, wherein R¹Is a hydrocarbyl group, n is 1 or 2, and A is a branch point. The branched alkanediyl may have the structure-CH₂(–CH(–CH₂–)–。

The thiol-terminated polysulfide prepolymer of formula (4a) and the moiety of formula (4) may be prepared by reacting an alpha, omega-dihalo-organic compound, a metal hydrosulfide, a metal hydroxide and optionally a polyfunctionalizing agent. An example of a suitable α, ω -dihalogenated organic compound comprises bis (2-chloroethyl) formal. Examples of suitable metal hydrosulfides and metal hydroxides include sodium hydrosulfide and sodium hydroxide. Examples of suitable polyfunctionalizing agents include 1,2, 3-trichloropropane, 1,1, 1-tris (chloromethyl) propane, 1,1, 1-tris (chloromethyl) ethane and 1,3, 5-tris (chloromethyl) benzene.

Examples of thiol-terminated polysulfide prepolymers of formula (4a) and moieties of formula (4) are disclosed in, for example, U.S. application publication No. 2016/0152775, U.S. patent No. 9,079,833, and U.S. patent No. 9,663,619.

The thiol-terminated polysulfide prepolymer may comprise a thiol-terminated polysulfide prepolymer of formula (5a) or may comprise moieties of formula (5):

-(R-O-CH₂-O-R-S_m)_n-1-R-O-CH₂-O-R- (5)

HS-(R-O-CH₂-O-R-S_m)_n-1-R-O-CH₂-O-R-SH (5a)

wherein R may be C_2-4Alkanediyl, m may be an integer of 1 to 8, and n may be an integer of 2 to 370.

In the thiol-terminated polysulfide prepolymer of formula (5a) and the fraction of formula (5), the average value of m may for example be greater than 1, such as from 1.05 to 2 or from 1.1 to 1.8.

In the thiol-terminated polysulfide prepolymer of formula (5a) and the moiety of formula (5), m may be, for example, an integer from 1 to 6 and an integer from 1 to 4, or an integer of 1,2,3, 4,5, 6, 7, or 8.

In the thiol-terminated polysulfide prepolymer of formula (5a) and the moiety of formula (5), n may be, for example, an integer from 2 to 200 or an integer from 2 to 100.

In the thiol-terminated polysulfide prepolymer of formula (5a) and the moiety of formula (5), each R may be independently selected from the group consisting of ethylene glycol, 1, 3-propanediyl, 1-propanediyl, 1, 2-propanediyl, 1, 4-butanediyl, 1-butanediyl, 1, 2-butanediyl, and 1, 3-butanediyl.

Examples of thiol-terminated polysulfide prepolymers of formula (5a) and moieties of formula (5) are disclosed in, for example, JP 62-53354.

The thiol-terminated polysulfide prepolymer may be liquid at room temperature. The thiol-terminated monosulfide prepolymer has a viscosity of less than 1,500 poise (150 Pa-sec), such as from 40 poise to 500 poise (4 Pa-sec to 50 Pa-sec), as measured at a temperature of about 25 ℃ and a pressure of 760mm Hg (101kPa) using a Brookfield CAP 2000 viscometer according to ASTM D-2849 § 79-90.

The number average molecular weight of the thiol-terminated polysulfide prepolymer may be, for example, from 300Da to 10,000Da, such as from 1,000Da to 8,000Da, where the molecular weight is determined by gel permeation chromatography using polystyrene standards. Glass transition temperature T of thiol-terminated polysulfide prepolymers_gMay be at a temperature of less than-40 deg.C, less than-55 deg.C or less than-60 deg.C. Glass transition temperature T_gIs determined by Dynamic Mass Analysis (DMA) using a TA instruments Q800 apparatus at a frequency of 1Hz, an amplitude of 20 microns and a temperature ramp of-80 ℃ to 25 ℃, wherein T_gIdentified as the peak of the tan delta curve.

The compositions provided by the present disclosure can include, for example, 30 wt% to 70 wt%, 35 wt% to 65 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of the polysulfide prepolymer or combination of polysulfide prepolymers, where the wt% is by total weight of the composition. For example, the composition can include greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, or greater than 70 wt% of the polysulfide prepolymer or combination of polysulfide prepolymers, where the wt% are by total weight of the composition.

The compositions provided by the present disclosure may include a polysulfide cure activator or a combination of polysulfide cure activators.

The polysulfide cure activator may include an oxidizing agent capable of oxidizing the terminal thiol groups to form disulfide bonds. Examples of suitable oxidizing agents include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, and dichromate.

The polysulfide cure activator may comprise an inorganic activator, an organic activator, or a combination thereof.

Examples of suitable inorganic activators include metal oxides. Examples of suitable metal oxide activators include zinc oxide (ZnO), lead oxide (PbO), lead peroxide (PbO)₃) Manganese dioxide (MnO)₂) Sodium perborate (NaBO)₃·H₂O), potassium permanganate (KMnO)₄) Calcium peroxide (CaCO)₃) Barium peroxide (BaO)₃) Cumene hydroperoxide, and combinations of any of the foregoing. The polysulfide cure activator may be MnO₂。

The metal oxide may be complexed with fatty acids such as stearic acid, lauric acid, palmitic acid, oleic acid, and naphthenic acid in the form of fatty acid esters. Fatty acids can be used to facilitate dispersion of the polysulfide cure activator and can be used as solubilizers for metal oxides.

The compositions provided by the present disclosure can include, for example, from 1 wt% to 10 wt% of a polysulfide cure activator or combination of polysulfide cure activators, where the wt% are by total weight of the composition. For example, the composition can include from 1 wt% to 9 wt%, from 2 wt% to 8 wt%, from 3 wt% to 7 wt%, or from 4 wt% to 6 wt% of an activator or combination of polysulfide cure activators, where the wt% is by total weight of the composition. For example, the composition can include greater than 1 wt% of a polysulfide cure activator or combination of polysulfide cure activators, greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, or greater than 6 wt% of a polysulfide cure activator or combination of polysulfide cure activators, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may comprise a polysulfide cure accelerator or a combination of polysulfide cure accelerators.

The polysulfide cure accelerator may act as a sulfur donor to generate active sulfur fragments capable of reacting with the terminal thiol groups of the thiol-terminated polysulfide prepolymer.

Examples of suitable polysulfide cure accelerators include thiazoles, thiurams (thiuram), sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldamines, and combinations of any of the foregoing.

The polysulfide cure accelerator may be a thiuram polysulfide, a thiuram disulfide, or a combination thereof.

Examples of suitable thiazoles include bis (2-benzothiazole) disulfide (MBTS), 2-Mercaptobenzothiazole (MBT), and the zinc salt of mercaptobenzothiazole (ZMBT).

Examples of suitable thiurams include: tetramethylthiuram monosulfide; tetramethylthiuram Disulfide (TMTD); tetraethylthiuram disulfide; tetrabutylthiuram disulfide; dipentamethylenethiuram hexasulfide; dicyclohexamethylenethiuram disulfide; diisopropyl thiuram disulfide; bis (morpholinothiocarbonyl) sulfide; tetramethylthiuram Monosulfide (TMTM); dipentamethylenethiuram tetrasulfide (DPTT); and has the structure (R)₂N–C(＝S)–S_x–C(＝S)–N(R)₂Wherein each R may be C_1-6Alkyl, and x is an integer from 1 to 4; and combinations of any of the foregoing.

Examples of suitable sulfenamides include N-cyclohexyl-2-benzothiazolesulfenamide, t-butyl-2-benzothiazolesulfenamide (TBBS), dicyclohexyl-2-benzothiazolesulfenamide (DCBS), and combinations of any of the foregoing.

Examples of suitable guanidines include: diphenylguanidine (DPG); n, N' -di-o-tolylguanidine (DOTG); a compound having the structure R-NH-C (═ NH) -NH-R, wherein each R is selected from C_1-6Alkyl, phenyl and toluyl; and combinations of any of the foregoing.

Examples of suitable dithiocarbamates include: zinc dialkyldithiocarbamates, such as dimethyl dithiocarbamate (ZDMC), diethyl dithiocarbamate (ZDEC) and dibutyl dithiocarbamate (ZDBC); other metal or ammonium salts of dithiocarbamic acids; having the structure Zn (-S-C (═ S) -N (R)₂) Wherein each R is selected from C_1-6Alkyl, phenyl and toluyl; and combinations of any of the foregoing.

Examples of suitable xanthates include zinc salts of xanthates.

Examples of suitable thioureas include: ethylene Thiourea (ETU); dipentamethylenethiourea (DPTU); dibutylthiourea (DBTU); and compounds having the structure R-NH-C (═ S) -NH-R, where each R is selected from C_1-6Alkyl, phenyl and toluyl; and combinations of any of the foregoing.

Examples of suitable aldamines include condensation products of aldehydes and amines, such as aniline, shellac or derivatives thereof, and butyraldehyde, crotonaldehyde, or formaldehyde, such as butyraldehyde aniline and crotyl tetramine, and combinations of any of the foregoing.

Examples of other suitable polysulfide cure accelerators also include metal and amine salts of triazines and sulfides or dialkyldithiophosphoric acids and dithiophosphoric acids, such as metal and amine salts of triazines and sulfides or dialkyldithiophosphoric acids and combinations of any of the foregoing. For example, the polysulfide cure accelerator may be one having the structure Zn (-S-C (═ S) - (OR)₂) The dithiophosphoric acid of (1).

Examples of the sulfur-free polysulfide cure accelerator include Tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water, and a base.

The compositions provided by the present disclosure can include, for example, 0.01 wt% to 2 wt% of a polysulfide cure accelerator or combination of polysulfide cure accelerators, 0.05 wt% to 1.8 wt%, 0.1 wt% to 1.6 wt%, or 0.5 wt% to 1.5 wt% of a polysulfide cure accelerator or combination of polysulfide cure accelerators, where the wt% are based on the total weight of the composition.

The compositions provided by the present disclosure can include, for example, less than 2 wt%, less than 1.8 wt%, less than 1.6 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or less than 0.05 wt% of a polysulfide cure accelerator or a combination of polysulfide cure accelerators, where the wt% are based on the total weight of the composition.

The compositions provided by the present disclosure may include a synergist or combination of synergists. Synergists are used to increase the activity of polysulfide cure activators and polysulfide cure accelerators. Synergists can be particularly effective in accelerating the cure rate of a composition containing a porous material.

Examples of suitable synergists include polyethers terminated with hydroxyl, alkyl, alkoxy, (meth) acryloyl, substituted phenyl, or substituted aryloxy groups. The synergist may comprise a polyether terminated with hydroxyl or alkoxy groups.

The polyether backbone may be a prepolymer, such as a homopolymer or a copolymer. The prepolymer comprises repeating units in the backbone of the prepolymer. Homopolymer refers to a prepolymer having the same repeating units. Copolymer refers to a prepolymer comprising alternating copolymers, random copolymers, and block copolymers.

The functionality of the polyether synergist may be, for example, 1 to 6, such as 1 to 4, 1 to 3, 1 to 2. The functionality of the polyether synergist may be 1,2,3, 4,5 or 6. For combinations of polyethers, the average functionality may be, for example, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2.

The molecular weight of the polyether synergist may be, for example, 100Da to 4,000Da, 100Da to 3,000Da, 100Da to 2,000Da, 200Da to 1,750Da, 250Da to 1,500Da, 500Da to 1,250Da, or 500Da to 1,000 Da.

The molecular weight of the polyether synergist may for example be less than 4,000Da, less than 3,000Da, less than 2,000Da, less than 1,500Da, less than 1,000Da, less than 750Da, less than 500Da or less than 250 Da.

The polyether synergist may be a liquid at a temperature of 25 ℃ and a pressure of 760 torr (101 kPa).

Examples of suitable polyether synergists include polyethylene glycol, polypropylene glycol, methoxypolyethylene glycol, polytetrahydrofuran, or a combination of any of the foregoing. The combination may comprise homopolymers having different chemical structures or may be a copolymer in which segments of the copolymer have different chemical structures.

Polyether synergists include homopolymer polyethers and copolymer polyethers.

Suitable polyethylene glycols and methoxypolyethylene glycols are available from Dow Chemical under the trade name Carbowax^TMAnd (4) obtaining.

The polyether synergist may have a chemical structure of formulae (6a) - (6 k):

CH₃–CH–C{–CH₂–(–O–CH₂–CH₂–)_x–O–C(＝O)–CH₂＝CH₂}₃ (6c)

HC[(–O(–CH₂–CH(–CH₃)–O–)_y–H][–CH₂-O–(–CH₂–CH(–CH₃)–O–)_x–H]_x (6k)

wherein each n, x, y and z may be selected from an integer from 1 to 20, such as 1 to 15, 1 to 10, 5 to 20, 5 to 15, or 5 to 10; and R may be C_1-10An alkyl group.

The polyether may include Carbowax^TM 200、Carbowax^TM 300、Carbowax^TM 400、Carbowax^TM 540、Carbowax^TM 600、Carbowax^TM 1000、Carbowax^TM 1450、Carbowax^TM 350、Carbowax^TM 550、Carbowax^TM750, or a combination of any of the foregoing, which is commercially available from the dow chemical company.

The polyether synergist may include (methoxypolyethylene glycol methacrylate), such asMPEG350MA、DEGDMA、EP100DMA、EP150DMA、MPEG550MA、PEG200DMA、PEM63P、PPA6、PPM5、S 10W、S20W, or a combination of any of the foregoing, commercially available from GEO Specialty Chemicals.

The polyether synergist may include, for example, CD553(MPEG 550), CD730, SR230(DEGDA), SR231(DEGDMA), SR203(THFMA), SR259(PEG2000DA), SR268(TTEGDA), SR272, SR306F (TPGDA), SR344(PEG400DA), SR508(DPGDA), SR550(MPEG350MA), SR551(MPEG550MA), SR603OP (PEG400DMA), SR610(PEG600DA), SR611, SR644(PPGDMA400), SR499(EO6TMPTA), SR501(PO6TMPTA), SR502(EO9TMPTA), SR9035(EO35TMPTA), or a combination of any of the foregoing, which is commercially available from Sartomer America (Sartomer America).

The polyether may include octylphenyl ethoxylate, such asX-100、X-102、X-14、X-15、X-165、X-305、X-25 andx-405 or a combination of any of the foregoing, commercially available from the Dow chemical company.

The polyether synergist may include polyether diols, such asPTMEG 250、PTMEG 650、PTMEG 1000、PTMEG 1400、PTMEG 1800、PTMEG 2000, or a combination of any of the foregoing, commercially available from inflatada (Invista).

The polyether synergist may include a glycol block copolymer, such as ethylene oxide capped with propylene oxide. Examples includeBlock copolymers, e.g.17R4, which is commercially available from BASF (BASF).17R4 is a poly (ethylene glycol) -block poly (propylene glycol) -block-poly (ethylene glycol) copolymer.

The polyether synergist may include polypropylene glycol, such as220-056、220-056N、220-094、220-110N、220-260、220-530、222-.

Polyether synergists may include, for example, polyethylene glycol, polyethylene oxide, poly (ethylene glycol) diacrylate, poly (ethylene glycol) diglycidyl ether, poly (ethylene glycol) dimethacrylate, poly (ethylene glycol) monomethyl ether monomethacrylate, aliphatic block polyethylene glycol, or a combination of any of the foregoing, which are commercially available from, for example, Polysciences, Inc.

Suitable polyether synergists may include two or more consecutive ethylene oxide or phenylene ether units.

The polyether synergist may comprise a sulfur-free diol or derivative thereof. The sulfur-free diol does not contain a sulfur atom.

The hydroxyl functionality of the polyether synergist may be, for example, 1 to 6, such as 1 to 5, 1 to 4, 1 to 3, or 1 to 2. The hydroxyl functionality of the diol may be, for example, 1,2,3, 4,5, or 6.

The polyether synergist may be an ethoxylated or methoxylated derivative of the corresponding polyether. For example, the polyether may comprise a terminal acryloyl group or a terminal methacryloyl group.

Suitable polyethers include cyclic polyethers, such as crown ethers. Examples of suitable crown ethers include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, diaza-18-crown-6, and combinations of any of the foregoing. Suitable crown ethers are commercially available from Parchem.

The polyether synergist can include a polyether having a structure of formula (7), a structure of formula (8), or a combination thereof:

wherein

n is an integer of 1 to 6;

p is an integer from 2 to 50;

z is an integer from 3 to 6;

each R¹Independently selected from hydrogen, C_1-10Alkyl, (meth) acrylate, and substituted aryl;

each R²Independently selected from hydrogen and C_1-3An alkyl group; and is

B is a multifunctional moiety.

In the polyethers of formula (7) and formula (8), each n may be independently selected from an integer of 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2.

In the polyethers of formula (7) and formula (8), each n may be independently selected from 1,2,3, 4,5 or 6.

In the polyethers of formula (7) and formula (8), p may be an integer from 2 to 50, 2 to 40, 2 to 30, 2 to 20, 2 to 10 or 2 to 5.

In the polyethers of formula (7) and formula (8), each z may be independently selected from an integer of 3 to 6,3 to 5, or 3 to 4.

In the polyethers of formula (7) and formula (8), each z may be independently selected from 3,4, 5 or 6.

In the polyethers of the formulae (7) and (8), each R¹Can be independently selected from hydrogen and C_1-10Alkyl, (meth) acryloyl, and substituted aryl.

In the polyethers of the formulae (7) and (8), each R¹May be hydrogen.

In the polyethers of the formulae (7) and (8), each R¹May be independently selected from hydrogen and C_1-3Alkyl groups such as methyl, ethyl, propyl or isopropyl.

In the polyethers of the formulae (7) and (8), each R¹May be a (meth) acryloyl group.

In the polyethers of the formulae (7) and (8), each R¹May be a substituted phenyl group wherein the substituents are selected from C_1-12An alkyl group.

In the polyethers of the formulae (7) and (8), each R¹May be para-substituted phenyl, wherein the substituents are selected from C_1-12Alkyl radicals, e.g. C_1-10Alkyl radical, C_1-8Alkyl radical, C_1-6Alkyl radical, C_1-4Alkyl, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl and isobutyl.

In the polyethers of the formulae (7) and (8), each R¹May be substituted phenyl, e.g. para-substituted phenyl, wherein the substituents are selected from C_1-10An alkyl group.

In the polyethers of the formulae (7) and (8), each R²May be independently selected from hydrogen, methyl, ethyl, propyl and isopropyl.

In the polyethers of the formulae (7) and (8), B may be a polyfunctional core having a functionality z of, for example, 3 to 6,3 to 5 or 3 to 4. z may be, for example, 3,4, 5 or 6.

In the polyethers of the formulae (7) and (8), B may be C_2-20Alkane-triyl, C_2-20Heteroalkane-triyl, C_2-20Alkane-tetrayl or C_2-20A heteroalkan-tetrayl.

In the polyethers of the formulae (7) and (8), B may be CH₃-CH₂-C(-CH₂-)₃。

The polyether can be an ionic polyether, a nonionic polyether, or a combination thereof.

The compositions provided by the present disclosure may include a filler or a combination of fillers.

The compositions provided by the present disclosure can include, for example, from 5 wt% to 95 wt%, from 10 wt% to 60 wt% of a filler or combination of fillers, from 15 wt% to 55 wt%, from 20 wt% to 50 wt%, from 25 wt% to 45 wt%, or from 30 wt% to 40 wt% of a filler or combination of fillers, where the wt% is by total weight of the composition. The compositions provided by the present disclosure can include, for example, greater than 5 wt% of a filler or combination of fillers, greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, or greater than 60 wt% of a filler or combination of fillers, where the wt% is by total weight of the composition. The compositions provided by the present disclosure can include, for example, less than 10 wt% of a filler or combination of fillers, less than 20 wt%, less than 30 wt%, less than 40 wt%, less than 50 wt%, less than 60 wt%, or less than 70 wt% of a filler or combination of fillers, where the wt% is by total weight of the composition. The filler may comprise a combination of non-porous and porous fillers.

For example, 1 wt% to 10 wt% of the filler in the composition can be porous filler and 90 wt% to 99 wt% can be non-porous filler.

The filler may comprise a porous material and/or a non-porous material. The filler comprising the porous material and the non-porous material may comprise an inorganic filler, an organic filler, a low density filler, or a combination of any of the foregoing.

The filler may comprise a porous material or a combination of porous materials.

For example, the porous material may have a BET surface area of 5m²G to 700m²In terms of/g, e.g. 10m²G to 600m²/g、50m²G to 500m²In g or 100m²G to 400m²(ii) in terms of/g. The porous material may have a BET surface area of greater than 5m²A ratio of the total of the carbon atoms to the carbon atoms of greater than 50m²A ratio of/g to more than 100m²A ratio of the total of the carbon atoms to the carbon atoms of more than 200m²A ratio of the total amount of the carbon atoms to the total amount of the carbon atoms is more than 400m²A/g or more than 600m²(ii) in terms of/g. The BET surface area is measured in accordance with DIN EN ISO 9277/DIN 66132.

The pore volume of the porous material may be, for example0.01mL/g to 10mL/g, such as 0.05mL/g to 8mL/g, 0.1mL/g to 6mL/g, or 1mL/g to 5 mL/g. The pore volume of the porous material can be, for example, greater than 0.01mL/g, greater than 0.05mL/g, greater than 0.1mL/g, greater than 0.5mL/g, greater than 1mL/g, greater than 2mL/g, greater than 4mL/g, greater than 6mL/g, or greater than 8 mL/g. Pore volume was determined according to ASTM D-3663-78 using N₂Desorption isotherms.

The average pore size of the porous material may be, for example, 1nm to 100nm, 2nm to 80nm, 3nm to 60nm, 5nm to 40nm, or 10nm to 30 nm. The average pore size of the porous material may be, for example, greater than 1nm, greater than 5nm, greater than 10nm, greater than 30nm, greater than 40nm, greater than 60nm, or greater than 80 nm. The mean pore diameter is determined according to ASTM D-3663-78 using N₂Desorption isotherms.

The average diameter (d50) of the porous material may be 0.1 μm to 40 μm, such as 0.5 μm to 30 μm, 1 μm to 20 μm, or 2 μm to 10 μm. The porous material may have an average (d50) diameter of, for example, greater than 0.1 μm, greater than 0.5 μm, greater than 1 μm, greater than 5 μm, greater than 10 μm, greater than 20 μm, greater than 30 μm, or greater than 40 μm. The average diameter can be determined using laser diffraction.

The porous material may have any suitable shape, for example, the porous material may be in the form of particles having a substantially spherical shape, for example having an aspect ratio of less than 2: 1.

Examples of porous materials include silica, alumina, zinc oxide, titania, zirconia, hafnia, yttria, rare earth oxides, boehmite, alkaline earth metal fluorides, calcium phosphate, and hydroxyapatite, and combinations of any of the foregoing.

The porous material may comprise silica.

The silica may comprise fumed silica, hydrophobic silica, hydrophilic silica, precipitated silica, untreated silica, treated silica, or a combination of any of the foregoing.

Examples of suitable hydrophilic silicas include200 (win)Chuang company (Evonik Corporation)) and Hi-sil^TMT700(PPG Industries, Inc.)).

Examples of suitable hydrophobic silicas include Lo-vel^TM2018(PPG industries, Ltd.), Lo-vel^TM8100(PPG industries Co.) andd13 (winning company).

Examples of suitable fumed silicas include those available from winning companies200。

Examples of precipitated silicas include Hi-sil available from PPG industries, Inc^TMWB10 and Hi-sil^TMT700。

Examples of modified silicas include Inhibisil available from PPG industries, Inc^TM73 and Inhibisil^TM75。

Suitable silica particles are commercially available, for example, from winning companies, Cabot Corporation (Cabot Corporation), Wacker chemistry (Wacker Chemie), Dow Corning (Dow Corning), PPG industries, and heili (Heraeus).

The compositions provided by the present disclosure can include, for example, 0.1 wt% to 10 wt% of a porous material such as silica, 0.1 wt% to 6 wt% of a porous material, 0.1 wt% to 5 wt% of a porous material, 0.5 wt% to 4 wt% of a porous material, 0.5 wt% to 3 wt%, 0.5 wt% to 2 wt%, 1 wt% to 10 wt%, 1 wt% to 6 wt%, or 1 wt% to 4 wt% of a porous material, where the wt% is based on the total weight of the composition.

The compositions provided by the present disclosure can include, for example, less than 10 wt% of a porous material such as silica, less than 8 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% of a porous material, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may include a non-porous material or a combination of non-porous materials.

The porous material may comprise, for example, a porous inorganic filler, a porous organic filler, a porous low density filler, a porous conductive filler, or a combination of any of the foregoing.

The non-porous material may include, for example, a non-porous inorganic filler, a non-porous organic filler, a non-porous low density filler, a non-porous conductive filler, or a combination of any of the foregoing.

Non-porous materials such as non-porous fillers may be characterized, for example, by: BET surface area of less than 1m²(ii)/g; the total pore volume is less than 0.01 mL/g; the average pore diameter is less than 1 nm; or a combination of any of the foregoing.

The compositions provided by the present disclosure may include an inorganic filler or a combination of inorganic fillers. Inorganic fillers may be included to provide mechanical reinforcement and control the rheological properties of the composition. Inorganic fillers may be added to the composition to impart desired physical properties, for example, for improving impact strength, for controlling viscosity, or for altering the electrical properties of the cured composition. Inorganic substance

Inorganic fillers useful in the compositions provided by the present disclosure and useful in sealant applications, such as aerospace sealant applications, include carbon black, calcium carbonate, precipitated calcium carbonate, calcium hydroxide, hydrated alumina (aluminum hydroxide), talc, mica, titanium dioxide, aluminum silicate, carbonate, chalk, silicates, glass, metal oxides, graphite, and combinations of any of the foregoing.

Inorganic fillers may include, for example, calcium carbonate, talc, and titanium dioxide.

Examples of suitable calcium carbonate fillers include products available from Solvay specialty Chemicals, such as Suwei specialty Chemicals31、312、U1S1、UaS2、N2R、SPM andand (4) SPT. The calcium carbonate filler may comprise a combination of precipitated calcium carbonates.

The inorganic filler may be surface treated to provide a hydrophobic or hydrophilic surface that may facilitate dispersion and compatibility of the inorganic filler with other components of the co-reactive composition. The inorganic filler may comprise surface-modified particles, such as surface-modified silica. The surface of the silica particles may be modified, for example, to tailor the hydrophobicity or hydrophilicity of the silica particle surface. Surface modification can affect the dispensability, viscosity, cure rate, and/or adhesion of the particles.

The filler may comprise from 70 wt% to 99 wt% calcium carbonate, such as from 75 wt% to 95 wt% or from 80 wt% to 90 wt% calcium carbonate, where wt% is based on the total weight of the filler. The filler can include 4 wt% to 14 wt% titanium dioxide, such as 6 wt% to 12 wt% or 8 wt% to 10 wt% titanium dioxide, where wt% is based on the total weight of the filler.

The compositions provided by the present disclosure can include, for example, 15 wt% to 55 wt% inorganic filler, 20 wt% to 50 wt% inorganic filler, 25 wt% to 45 wt% inorganic filler, or 30 wt% to 40 wt% inorganic filler, where the wt% is by total weight of the composition.

The compositions and sealants provided by the present disclosure may include an organic filler or a combination of organic fillers. The organic filler may be selected to have low specific gravity and to be resistant to solvents such as JRF type I. Suitable organic fillers may also have acceptable adhesion to the sulfur-containing polymer matrix. The organic filler may comprise solid powders or particles, hollow powders or particles, or a combination thereof.

The specific gravity of the organic filler may be, for example, less than 1.15, less than 1.1, less than 1.05, less than 1, less than 0.95, less than 0.9, less than 0.8, or less than 0.7. The specific gravity of the organic filler may be, for example, in the range of 0.85 to 1.15, in the range of 0.9 to 1.1, in the range of 0.9 to 1.05, or in the range of 0.85 to 1.05.

The organic filler may comprise a thermoplastic, a thermoset, or a combination thereof. Examples of suitable thermoplastics and thermosets include epoxies, epoxyamides, ethylene tetrafluoroethylene copolymers, nylons, polyethylenes, polypropylenes, polyethylene oxides, polypropylene oxides, polyvinylidene chlorides, polyvinyl fluorides, tetrafluoroethylene, polyamides, polyimides, ethylene propylene, perfluorocarbons, vinyl fluorides, polycarbonates, polyether ether ketones, polyether ketones, polyphenylene oxides, polyphenylene sulfides, polystyrenes, polyvinyl chlorides, melamines, polyesters, phenolics, epichlorohydrin, fluorinated hydrocarbons, polycyclic compounds, polybutadienes, polychloroprenes, polyisoprenes, polysulfides, polyurethanes, isobutylene isoprene, silicones, styrene butadiene, liquid crystal polymers, and combinations of any of the foregoing.

Examples of suitable organic fillers include polyamides, polyimides, polyethylenes, polyphenylene sulfides, and combinations of any of the foregoing, which can be particulate and/or powder.

Examples of suitable polyamide 6 and polyamide 12 particles are available from Toray Plastics, Inc. (Toray Plastics) as grades SP-500, SP-10, TR-1 and TR-2. Suitable polyamide powders are also available from the echoma Group (Arkema Group) under the trade nameAnd from the winning Industries (Evonik Industries) under the trade nameAnd (4) obtaining.

Examples of suitable polyimide powders are available from the winning industry under the trade nameAnd (4) obtaining.

The organic filler may comprise a polyethylene powder, such as an oxidized polyethylene powder. Suitable polyethylene powders are available under the trade name HONEYWELL INTERNATIONAL INC from HONEYWELL INTERNATIONALObtained under the trade name of Intel corporation of Enlisha (INEOS)Obtained under the trade name Mipelon from Mitsui Chemicals America, Inc^TMAnd (4) obtaining.

The use of organic fillers such as polyphenylene sulfide in aerospace sealants is disclosed in U.S. patent No. 9,422,451. Polyphenylene sulfide is a thermoplastic engineering resin that exhibits dimensional stability, chemical resistance, and corrosion and high temperature environments. Polyphenylene sulfide engineering resins can be used, for example, under the trade name(Chevron) to,(Quadrant)、(Celanese) and(Toray) was obtained commercially. Polyphenylene sulfide resins are generally characterized by a specific gravity of from about 1.3 to about 1.4.

The organic filler may have any suitable shape. For example, the organic filler may comprise a fraction of comminuted polymer that has been filtered to select a desired size range. The organic filler may comprise substantially spherical particles. The particles may be solid or may be porous.

The average particle size of the organic filler may be, for example, in the range of 1 μm to 100 μm, 2 μm to 40 μm, 2 μm to 30 μm, 4 μm to 25 μm, 4 μm to 20 μm, 2 μm to 12 μm, or 5 μm to 15 μm. The average particle size of the organic filler may be, for example, less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm or less than 20 μm. The particle size distribution can be determined using a Fischer Sub-Sieve Sizer (Fischer Sub-Sieve Sizer) or by optical inspection.

The organic filler may comprise low density (e.g. modified), expanded thermoplastic microcapsules. Suitable modified expanded thermoplastic microcapsules may comprise an outer coating of melamine resin, melamine/formaldehyde resin or urea/formaldehyde resin.

The compositions provided by the present disclosure may include low density microcapsules. The low density microcapsules may comprise thermally expandable microcapsules.

Thermally expandable microcapsules refer to hollow shells comprising a volatile material that expands at a predetermined temperature. The average primary particle size of the thermally expandable thermoplastic microcapsules may be from 5 μm to 70 μm, in some cases from 10 μm to 24 μm or from 10 μm to 17 μm. The term "average primary particle size" refers to the average particle size (the numerically weighted average of the particle size distribution) of the microcapsules prior to any expansion. The particle size distribution can be determined using a heschel subsieve sizer or by optical inspection.

The thermally expandable thermoplastic microcapsules may include a volatile hydrocarbon within the wall of the thermoplastic resin. Examples of hydrocarbons suitable for use in such microcapsules include methyl chloride, methyl bromide, trichloroethane, dichloroethane, n-butane, n-heptane, n-propane, n-hexane, n-pentane, isobutane, isopentane, isooctane, neopentane, petroleum ethers, and ethers such as Freon^TMAnd the like, fluorine-containing aliphatic hydrocarbons, and combinations of any of the foregoing.

Examples of materials suitable for forming the walls of the thermally expandable microcapsules include polymers of vinylidene chloride, acrylonitrile, styrene, polycarbonate, methyl methacrylate, ethyl acrylate, and vinyl acetate, copolymers of these monomers, and combinations of polymers and copolymers. The cross-linking agent may be contained in the material forming the wall of the thermally expandable microcapsules.

Examples of suitable thermoplastic microcapsulesComprises Expancel^TMMicrocapsules, such as Expancel available from akksonobel^TMDE microspheres. Suitable Expancel^TMExamples of DE microspheres include Expancel^TM920DE 40 and Expancel^TM920DE 80. Suitable low density microcapsules are also available from wuyu Corporation (Kureha Corporation).

The average diameter (D0.5) of suitable low-density fillers, such as low-density microcapsules, may be, for example, from 1 μm to 100 μm, from 10 μm to 80 μm, or from 10 μm to 50 μm, as determined according to ASTM D1475.

Low density fillers such as low density microcapsules may be characterized by a specific gravity within the following range: 0.01 to 0.09, 0.04 to 0.08, 0.01 to 0.07, 0.02 to 0.06, 0.03 to 0.05, 0.05 to 0.09, 0.06 to 0.09, or 0.07 to 0.09, wherein the specific gravity is determined according to ASTM D1475. The low density filler, such as a low density microcapsule, may be characterized by a specific gravity of less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, less than 0.05, less than 0.04, less than 0.03, or less than 0.02, wherein the specific gravity is determined according to ASTM D1475.

The low density filler, such as a low micro capsule, may be characterized by an average particle size of 1 μm to 100 μm and may have a substantially spherical shape. The low density filler, such as a low density microcapsule, may be characterized, for example, by an average particle size of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm, as determined according to ASTM D1475.

The low density filler may include uncoated microcapsules, coated microcapsules, or a combination thereof.

The low density filler, such as low density microcapsules, may comprise expanded microcapsules or microspheres having a coating of an aminoplast resin, such as a melamine resin. Aminoplast resin coated particles are described, for example, in U.S. patent No. 8,993,691. Such microcapsules may be formed by heating microcapsules comprising a blowing agent surrounded by a thermoplastic shell. The uncoated, low density microcapsules may be reacted with an aminoplast resin such as a urea/formaldehyde resin to provide a coating of thermosetting resin on the outer surface of the particles.

The low density filler, such as a low density microcapsule, may comprise thermally expandable thermoplastic microcapsules having an outer coating of an aminoplast resin, such as a melamine resin. The coated low density microcapsules may have an outer coating of melamine resin, wherein the coating may have a thickness of, for example, less than 2 μm, less than 1 μm, or less than 0.5 μm. The melamine coating on the low density microcapsules is believed to render the microcapsules reactive with thiol-terminated polythioether prepolymers and/or polyepoxide curing agents, which enhances fuel resistance and renders the microcapsules pressure resistant.

The thin coating of aminoplast resin may have a film thickness of less than 25 μm, less than 20 μm, less than 15 μm, or less than 5 μm. The thin coating of aminoplast resin may have a film thickness of at least 0.1 nanometers, such as at least 10 nanometers, or at least 100 nanometers, or in some cases at least 500 nanometers.

Aminoplast resins may be based on condensation products of formaldehyde with substances bearing amino or amide groups. The condensation products can be obtained from the reaction of alcohols and formaldehyde with melamine, urea or benzoguanamine. Condensation products of other amines and amides may also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines, and alkyl-substituted and aryl-substituted derivatives of such compounds including alkyl-substituted and aryl-substituted ureas and alkyl-substituted and aryl-substituted melamines. Examples of such compounds include N, N' -dimethylurea, phenylurea (benzourea), dicyandiamide, formylguanamine (formalguanamine), acetoguanamine (acetoguanamine), glycoluril, ammeline, 2-chloro-4, 6-diamino-1, 3, 5-triazine, 6-methyl-2, 4-diamino-1, 3, 5-triazine, 3, 5-diaminotriazole, triaminopyrimidine, 2-mercapto-4, 6-diaminopyrimidine, and 3,4, 6-tris (ethylamino) -1,3, 5-triazine. Suitable aminoplast resins may also be based on condensation products of other aldehydes, such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, and glyoxal.

The aminoplast resin may comprise a highly alkylated, low imino aminoplast resin having a degree of polymerization of less than 3.75, such as less than 3.0 or less than 2.0. The number average degree of polymerization can be defined as the average number of structural units per polymer chain. For example, a degree of polymerization of 1.0 represents the triazine structure of the complete monomer, while a degree of polymerization of 2.0 represents two triazine rings connected by a methylene or methylene-oxygen bridge. The degree of polymerization represents the average degree of polymerization as determined by gel permeation chromatography using polystyrene standards.

The aminoplast resin may contain methylol or other hydroxyalkyl groups, and at least a portion of the hydroxyalkyl groups may be etherified by reaction with an alcohol. Examples of suitable monohydric alcohols include alcohols such as: methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, benzyl alcohol, other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of glycols, and halogen-substituted or otherwise substituted alcohols such as 3-chloropropanol and butoxyethanol. The aminoplast resin may be substantially alkylated with methanol or butanol.

The aminoplast resin may comprise a melamine resin. Examples of suitable melamine resins include methylated melamine resins (hexamethoxymethylmelamine), mixed ether melamine resins, butylated melamine resins, urea resins, butylated urea resins, benzoguanamine and glycoluril resins, and formaldehyde-free resins. For example, such resins are available from the highly new Group (Allnex Group) and the vaseliness (Hexion). Examples of suitable melamine resins include methylated melamine resins, such as Cymel^TM 300、Cymel^TM 301、Cymel^TM 303LF、Cymel^TM 303ULF、Cymel^TM 304、Cymel^TM350、Cymel 3745、Cymel^TM XW-3106、Cymel^TM MM-100、Cymel^TM 370、Cymel^TM 373、Cymel^TM380、ASTRO MEL^TM 601、ASTRO MEL^TM 601ULF、ASTRO MEL^TM 400、ASTRO MEL^TM NVV-3A、Aricel PC-6A、ASTRO MEL^TMCR-1 and ASTRO SET^TM 90。

Suitable aminoplast resins may include urea-formaldehyde resins. Suitable aminoplast resins may include melamine-formaldehyde resins.

The aminoplast resin-coated particles are different from the uncoated particles that are incorporated only into the polymer network, as is the case when the uncoated, low-density particles are dispersed in a film-forming binder. For aminoplast resin coated particles, a thin film is deposited on the outer surface of individual discrete particles, such as thermally expandable microcapsules. These aminoplast resin-coated particles may then be dispersed in a film-forming binder, thereby dispersing the coated particles throughout the polymer network. For example, the thin coating of aminoplast resin may cover 70% to 100%, 80% to 100%, or 90% to 100% of the outer surface of the low-density particles, such as the thermally-expansible microcapsules. The coating of aminoplast resin may form a substantially continuous coating on the outer surface of the low-density particles.

Low density microcapsules can be prepared by any suitable technique, including, for example, the techniques described in U.S. patent nos. 8,816,023 and 8,993,691. For example, coated low density microcapsules can be obtained by preparing an aqueous dispersion of the microcapsules in water with melamine resin under stirring. The catalyst may then be added and the dispersion heated to a temperature of, for example, 50 ℃ to 80 ℃. Low density microcapsules such as thermally expandable microcapsules with a polyacrylonitrile shell, deionized water and aminoplast resins such as melamine resins can be combined and mixed. A10% w/w solution of p-toluenesulfonic acid in distilled water may then be added and the mixture reacted at 60 ℃ for about 2 hours. Saturated sodium bicarbonate can then be added and the mixture stirred for 10 minutes. The solid can be filtered, washed with distilled water, and dried overnight at room temperature. The resulting aminoplast resin-coated microcapsule powder may then be screened through a 250 μm sieve to remove and separate the agglomerates.

Prior to application of the aminoplast resin coating, the thermally expanded thermoplastic microcapsules may be characterized by a specific gravity, for example, in the range of 0.01 to 0.05, in the range of 0.015 to 0.045, in the range of 0.02 to 0.04, or in the range of 0.025 to 0.035, wherein the specific gravity is determined according to ASTM D1475. For example, Expancel^TM920DE 40 and Expancel^TM920DE 80 may be characterized by a specific gravity of about 0.03, wherein the specific gravity is determined according to ASTM D1475.

After coating with the aminoplast resin, the aminoplast-coated microcapsules may be characterized by a specific gravity, for example, in the range of 0.02 to 0.08, in the range of 0.02 to 0.07, in the range of 0.02 to 0.06, in the range of 0.03 to 0.07, in the range of 0.03 to 0.065, in the range of 0.04 to 0.065, in the range of 0.045 to 0.06, or in the range of 0.05 to 0.06, wherein the specific gravity is determined according to ASTM D1475.

The compositions provided by the present disclosure may include a micronized oxidized polyethylene homopolymer. The organic filler may comprise polyethylene, such as polyethylene oxide powder. Suitable polyethylenes are available under the trade name HONEYWELL INTERNATIONAL CORPORATIONObtained from the Enlishi group under the trade nameObtained and sold under the name Mipelon from mitsui chemical america corporation^TMAnd (4) obtaining.

The compositions provided by the present disclosure can include, for example, 5 wt% to 65 wt% filler, 10 wt% to 60 wt%, 15 wt% to 55 wt%, 20 wt% to 50 wt%, 25 wt% to 45 wt%, or 30 wt% to 40 wt% filler, where the wt% is by total weight of the composition.

The composition can include greater than 5 wt% filler, greater than 15 wt%, greater than 25 wt%, greater than 35 wt%, greater than 45 wt%, greater than 55 wt%, or greater than 65 wt% filler, where the wt% is based on the total weight of the composition.

The co-reactive conductive compositions provided by the present disclosure may include a conductive filler or a combination of conductive fillers. The conductive filler may comprise an electrically conductive filler, a semiconductive filler, a thermally conductive filler, a magnetic filler, an EMI/RFI shielding filler, a static dissipative filler, an electrically active filler, or a combination of any of the foregoing.

To render the component electrically conductive, the concentration of the electrically conductive filler may be above the electro-percolation threshold, at which a conductive network of electrically conductive particles is formed. Once the electroosmotic filtration threshold is reached, the increase in conductivity with filler loading can be modeled by a simple power law expression:

whereinIs the volume fraction of the filler,is the percolation threshold, σ_fIs the electrical conductivity of the filler material,is the composite conductivity and t is the scaling component. The filler does not need to be in direct contact because current flow and conduction can occur by tunneling between the thin layer of binder surrounding the conductive filler particles, and this tunneling resistance can be a limiting factor for the conductivity of the conductive composite.

The compositions provided by the present disclosure may include a conductive filler or a combination of conductive fillers.

The conductive filler may have any suitable shape and/or size. For example, the conductive filler may be in the form of: particles, powders, flakes, platelets, filaments, fibers, crystals, or a combination of any of the foregoing.

The conductive fillers may include combinations of conductive fillers having different shapes, different sizes, different properties, such as different thermal conductivities, electrical conductivities, magneto-dielectric constants, electromagnetic properties, or combinations of any of the foregoing.

The conductive filler may be solid or may be in the form of a substrate, such as a particle having a coating of conductive material. For example, the conductive filler may be a low density microcapsule with an outer conductive coating.

Examples of suitable conductive fillers, such as conductive fillers, include metals, metal alloys, conductive oxides, semiconductors, carbon, and combinations of any of the foregoing.

Other examples of conductive fillers include: conductive noble metal-based fillers such as pure silver; noble metal-plated noble metals, such as silver-plated gold; noble metal-plated non-noble metals, such as silver-plated copper, nickel or aluminum, e.g., silver-plated aluminum core particles or platinum-plated copper particles; noble metal-plated glass, plastic or ceramic, such as silver-plated glass microspheres, noble metal-plated aluminum or noble metal-plated plastic microspheres; mica plated with a noble metal; and other such noble metal conductive fillers. Non-noble metal based materials may also be used, and include: for example, non-noble metal plated non-noble metals, such as copper-coated iron particles or nickel-plated copper; non-noble metals, such as copper, aluminum, nickel, cobalt; non-noble metal-plated non-metals, such as nickel-plated graphite and non-metallic materials, such as carbon black and graphite. Combinations of conductive fillers and shapes of conductive fillers may be used to achieve desired electrical conductivity, EMI/RFI shielding effectiveness, stiffness, and other properties suitable for a particular application.

Carbon fibers, such as graphitized carbon fibers, may also be used to impart electrical conductivity to the compositions of the present disclosure. The carbon fiber formed by the vapor phase pyrolysis method and graphitized by the heat treatment is hollow or solid, has a fiber diameter in the range of 0.1 to several micrometers, and has high electrical conductivity. Carbon microfibers such as nanotubes or carbon fibrils having an outer diameter of less than 0.1 μm to several tens of nanometers may be used as the conductive filler. Examples of graphitized carbon fibers suitable for use in the electrically conductive compositions of the present disclosure include3OMF (Zoltek company, Inc., St. Louis, Mo.) which is a 0.921 μm diameter round fiber with a resistivity of 0.00055 Ω -cm.

The average particle size of the conductive filler can be within a range useful for imparting conductivity to the polymer-based composition. For example, the particle size of the one or more fillers may be at 0.In the range of 25 μm to 250 μm, may be in the range of 0.25 μm to 75 μm, or may be in the range of 0.25 μm to 60 μm. The compositions provided by the present disclosure may include a conductive carbon black, which may be characterized by: iodine absorption of 1,000mg/g to 11,500mg/g (J0/84-5 test method) and pore volume of 480cm³100g to 510cm³100g (DBP absorption, KTM 81-3504). Examples are commercially available from Akzo Nobel, IncEC-600 JD. The conductive carbon Black filler is Black, commercially available from Cabot corporation2000。

The conductive compositions provided by the present disclosure may include more than one conductive filler and the more than one conductive filler may be the same or different materials and/or shapes. For example, the composition may include conductive Ni fibers and Ni-coated conductive graphite in the form of powder, granules, or flakes. The amount and type of conductive filler can be selected to produce a conductive filler that, when cured, exhibits less than 0.50 Ω/cm²Sheet resistance (four-point resistance) or less than 0.15. omega./cm²The sheet resistance of (a). The amount and type of filler can also be selected to provide effective EMI/RFI shielding of apertures sealed using the sealant composition of the present disclosure in the frequency range of 1MHz to 18 GHz.

The organic, inorganic and low density fillers may be coated with a metal to provide a conductive filler.

The conductive filler may include graphene.

Graphene comprises a close-packed honeycomb lattice of carbon atoms with a thickness equal to the atomic size of one carbon atom, i.e. sp arranged in a two-dimensional lattice²A monolayer of hybridized carbon atoms.

The graphene may include graphene carbon particles. Grapheme carbon particles are meant to have sp comprising one or more layers of a single atom thickness²Carbon particles of structure bonded to planar sheets of carbon atomsThe carbon atoms are closely packed in a honeycomb lattice. The average number of stacked layers may be less than 100, for example less than 50. The average number of stacked layers may be 30 or less, such as 20 or less, 10 or less, or 5 or less. The grapheme carbon particles may be substantially planar, however, at least a portion of the planar sheet may be substantially curved, curled, wrinkled or buckled. The grapheme carbon particles generally do not have a spheroidal or equiaxed morphology.

The thickness of the grapheme carbon particles, measured in a direction perpendicular to the carbon atom layers, may, for example, be no more than 10nm, no more than 5nm, or no more than 4nm or 3nm or 2nm or 1nm, such as no more than 3.6 nm. The grapheme carbon particles may be from 1 atomic layer up to 3,6, 9, 12, 20, or 30 atomic layers thick or thicker. The grapheme carbon particles may have a width and length, measured in a direction parallel to the carbon atom layers, of at least 50nm, such as greater than 100nm, greater than 100nm up to 500nm, or greater than 100nm up to 200 nm. The grapheme carbon particles may be provided in the form of ultra-thin flakes, platelets, or sheets having a relatively high aspect ratio, wherein the aspect ratio is the ratio of the longest dimension of the particle to the shortest dimension of the particle, the ratio being greater than 3:1, such as greater than 10: 1.

The grapheme carbon particles may have a relatively low oxygen content. For example, the grapheme carbon particles may have an oxygen content of no more than 2 atomic weight percent, such as no more than 1.5 or 1 atomic weight percent, or no more than 0.6 atomic weight percent, such as about 0.5 atomic weight percent, even at thicknesses of no more than 5nm or no more than 2 nm. The oxygen content of the grapheme carbon particles may be determined using X-ray photoelectron spectroscopy.

The BET specific surface area of the grapheme carbon particles is at least 50m²G, e.g. 70m²G to 1000m²A/g, or in some cases, 200m²G to 1000m²(ii)/g or 200m²G to 400m²/g。

The grapheme carbon particles may have a raman spectroscopy 2D/G peak ratio of at least 1:1, such as at least 1.2:1 or 1.3: 1. The 2D/G peak ratio is 2692cm^-1Intensity of 2D peak and 1,580cm^-1The ratio of the G peak intensities at (a).

The grapheme carbon particles may have a relatively low bulk density. For example, the grapheme carbon particles are characterized as having less than 0.2g/cm³E.g. not more than 0.1g/cm³Bulk density (tap density). The bulk density of the grapheme carbon particles is determined by placing 0.4 grams of the grapheme carbon particles in a glass measuring cylinder having a readable scale. The cylinder was raised approximately one inch and tapped 100 times by impacting the bottom of the cylinder onto a hard surface to cause the grapheme carbon particles to settle within the cylinder. The volume of the particles was then measured and the bulk density was calculated by dividing 0.4g by the measured volume, where the bulk density is in g/cm³And (4) showing.

The compressed density and percent density of the grapheme carbon particles may be less than the compressed density and percent density of graphite powders and certain types of substantially planar grapheme carbon particles, such as grapheme carbon particles formed from exfoliated graphite. It is currently believed that lower compressed densities and lower density percentages each contribute to better dispersion and/or rheological properties than graphenic carbon particles exhibiting higher compressed densities and higher density percentages. The compressed density of the grapheme carbon particles is 0.9 or less, such as less than 0.8, less than 0.7, such as from 0.6 to 0.7. The grapheme carbon particles have a percent density of less than 40 percent, such as less than 30 percent, such as from 25 percent to 30 percent.

The compressed density of the grapheme carbon particles may be calculated from the measured thickness of a given mass of the particles after compression. For example, the measured thickness can be determined by cold pressing 0.1g of grapheme carbon particles in a 1.3cm mold at a force of 15,000 pounds for 45 minutes, with a contact pressure of 500 MPa. The compressed density of the grapheme carbon particles may then be calculated from the measured thickness according to the following equation: compressed density (gm/cm)³)＝0.1gm×3.14×(1.3cm^-2)²X (measured thickness in cm). The calculated compressed density of the grapheme carbon particles may then be compared to the density of the graphite of 2.2g/cm³The percent densification of the grapheme carbon particles is determined as a ratio of (a).

The graphene is mixed immediately and at a later point in time, such as at 10 minutes or 20 minutes or 30 minutes or 40 minutesThe clock may have a measured bulk liquid conductivity of at least 100 μ S (microsiemens), such as at least 120 μ S, such as at least 140 μ S. The bulk liquid conductivity of graphene can be determined using the following procedure. Comprising graphene in butylA sample of the 0.5% solution in (a) may be sonicated with a bath sonicator for 30 minutes. Immediately after sonication, the samples were placed in a standard calibrated electrolytic conductivity cell (K ═ 1). A Fisher Scientific AB 30 conductivity meter may be introduced to the sample to measure the conductivity of the sample. The conductivity can be plotted over the course of about 40 minutes.

Suitable graphene may be manufactured, for example, by a thermal process. For example, graphene may be produced from a carbon-containing precursor material that is heated to an elevated temperature in a hot zone. For example, graphene can be produced by the systems and methods disclosed in U.S. patent No. 8,486,363 and its corresponding patents.

The grapheme carbon particles may comprise exfoliated graphite and have different characteristics compared to thermally produced grapheme carbon particles, such as having different size distributions, thicknesses, aspect ratios, structural morphologies, oxygen content, and basal/edge chemical functionalities.

The grapheme carbon particles may be functionalized. Functionalized grapheme carbon particles refer to grapheme carbon particles having covalently bonded organic groups. Grapheme carbon particles may be functionalized through the formation of covalent bonds between carbon atoms of the particles and other chemical moieties such as carboxylic acid groups, sulfonic acid groups, hydroxyl groups, halogen atoms, nitro groups, amine groups, aliphatic hydrocarbon groups, phenyl groups, and the like. For example, functionalization with carbonaceous materials can result in the formation of carboxylic acid groups on the grapheme carbon particles. The grapheme carbon particles may also be functionalized by other reactions such as diels-alder addition reactions, 1, 3-dipolar cycloaddition reactions, free radical addition reactions, and diazo addition reactions. The hydrocarbyl and phenyl groups may be further functionalized. For grapheme carbon particles having hydroxyl functionality, the hydroxyl functionality may be modified and extended by reacting these groups with, for example, organic isocyanates.

Different types of grapheme carbon particles may be used in the composition. For example, when thermally produced grapheme carbon particles are combined with commercially available grapheme carbon particles, a bimodal, trimodal, or other distribution of grapheme carbon particle characteristics and/or properties may be obtained. The graphenic carbon particles contained in the composition may have a multimodal particle size distribution, aspect ratio distribution, structural morphology, edge functionality differences, oxygen content, and combinations of any of the foregoing. When thermally produced grapheme carbon particles and commercially available grapheme carbon particles (e.g., from exfoliated graphite) are used to produce a bimodal graphene particle size distribution, the relative amounts of the different types of grapheme carbon particles are controlled to produce the desired conductivity properties of the coating. For example, thermally produced graphene particles may comprise 1 wt% to 50 wt%, and commercially available graphene carbon particles may comprise 50 wt% to 99 wt%, based on the total weight of the graphene carbon particles.

The composition can include, for example, 2 wt% to 50 wt%, 4 wt% to 40 wt%, 6 wt% to 35 wt%, or 10 wt% to 30 wt% of the thermally produced grapheme carbon particles, based on the total wt% of the composition. The compositions may include thermally produced grapheme carbon nanoparticles as well as grapheme carbon particles produced by other methods, and also include other forms of carbon or graphite.

Fillers for imparting electrical conductivity and EMI/RFI shielding effectiveness may be used in combination with the graphene. Examples of the conductive filler used in combination with graphene include conductive noble metal-based fillers; a noble metal plated with a noble metal; a noble metal-plated non-noble metal; noble metal-plated glass, plastic or ceramic; mica plated with a noble metal; and other noble metal conductive fillers. Non-noble metal based materials may also be used, and include: for example, non-noble metal plated non-noble metals; a non-noble metal; non-noble metal plated non-metals. Examples of suitable materials and combinations are disclosed, for example, in U.S. application publication No. 2004/0220327a 1.

Conductive non-metallic fillers such as carbon nanotubes, carbon fibers such as graphitized carbon fibers, and conductive carbon black may also be combined with grapheneCombinations are used in the co-reactive compositions. An example of a suitable graphitized carbon fiber is PANEX 3OMF (Tourette's Corp.), a 0.921- μm diameter round fiber with an electrical resistivity of 0.00055 Ω -cm. Examples of suitable conductive carbon blacks include:EC-600JD (akysonobel), a conductive carbon black characterized by: iodine uptake was in the range of 1,000mg/g to 11,500mg/g (J0/84-5 test method) and a pore volume of 480-³100gm (DBP absorption, KTM 81-3504); and2000 and660R (Kabert Corporation, Boston, Mass.)). The composition may include carbon nanotubes having a length dimension of, for example, 5 μm to 30 μm and a diameter of 10nm to 30 nm. The size of the carbon nanotubes may be, for example, 11nm × 10 μm.

The conductive filler may include a magnetic filler or a combination of magnetic fillers.

The magnetic filler may comprise a soft magnetic metal. This can increase the magnetic permeability of the magnetic molding resin. At least one magnetic material selected from the group consisting of Fe, Fe-Co, Fe-Ni, Fe-Al, and Fe-Si may be used as a main component of the soft magnetic metal. The magnetic filler may be a soft magnetic metal having a high bulk permeability (bulk permeability). At least one magnetic material selected from Fe, FeCo, FeNi, FeAl, and FeSi may be used as the soft magnetic metal. Specific examples include permalloy (permalloy) (FeNi alloy), super permalloy (FeNiMo alloy), sendust (FeSiAl alloy), FeSi alloy, FeCo alloy, FeCr alloy, FeCrSi alloy, FeNiCo alloy, and Fe. Other examples of the magnetic filler include iron-based powder, iron-nickel-based powder, iron powder, ferrite powder, Alnico (Alnico) powder, Sm₂Co₁₇Powder, Nd-B-Fe powder, barium ferrite BaFe₂O₄Bismuth ferrite BiFeO₃Chromium dioxide CrO₂SmFeN, NdFeB and SmCo.

The surface of the magnetic filler may be insulation-coated or may have an insulation coating layer with a film thickness equal to or greater than 10 nm.

The surface of the magnetic filler may be insulation-coated with metal oxides such as Si, Al, Ti, Mg, or organic materials to enhance fluidity, adhesion, and insulation properties.

Examples of suitable metal fillers include, for example, silver, copper, aluminum, platinum, palladium, nickel, chromium, gold, bronze, and colloidal metals. Examples of suitable metal oxides include antimony tin oxide and indium tin oxide, as well as materials such as fillers coated with metal oxides. Suitable metal and metal oxide coated materials include metal coated carbon and graphite fibers, metal coated glass beads, metal coated ceramic materials such as ceramic beads. These materials may be coated with a variety of metals, including nickel.

Examples of conductive materials include: metals such as silver, copper, gold, platinum, palladium, tungsten and iron; nanomaterials, such as nanoparticles, nanorods, nanowires, nanotubes, and nanoplatelets; conductive oxides such as indium tin oxide, antimony oxide, and zinc oxide; conductive polymers such as poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), polyacetylene, polythiophene, and other conjugated polymers; carbonaceous nanomaterials such as graphene (single or multilayer), carbon nanotubes (CNT, single or multi-walled), graphene nanoribbons and fullerenes; and reactive metal systems, such as metal oxide nanoparticles. Carbonaceous nanomaterials and metallic materials are stable at very high temperatures and can therefore be used in high temperature components.

Examples of carbonaceous materials used as conductive fillers, in addition to graphene and graphite, include, for example, graphitized carbon blacks, carbon fibers and fibrils, vapor grown carbon nanofibers, metal coated carbon fibers, carbon nanotubes including single-walled and multi-walled nanotubes, fullerenes, activated carbon, carbon fibers, expanded graphite, expandable graphite, graphite oxide, hollow carbon spheres, and carbon foams.

The conductive filler may comprise a semiconductor or a combination of semiconductors.

Examples of suitable semiconductor materials include: semiconductor nanomaterials such as nanoparticles, nanorods, nanowires, nanotubes, and nanosheets; semiconductive metal oxides such as tin oxide, antimony oxide, and indium oxide; semiconducting polymers such as PEDOT PSS, polythiophene, poly (p-phenylene sulfide), polyaniline, poly (pyrrole), poly (acetylene), poly (p-phenylene vinylene), any other conjugated polymer; and, for example, semiconducting small molecules having a number average molecular weight of less than 5,000Da, such as rubrene, pentacene, anthracene, and aromatic hydrocarbons. Examples of semiconductor nanomaterials include quantum dots, III-V or II-VI semiconductors, Si, Ge, e.g. WS₂、WSe₂And MoSe_sIsotransition metal dichalcogenides, graphene nanoribbons, semiconducting carbon nanotubes, and fullerenes and fullerene derivatives.

Examples of suitable metal fibers include steel, titanium, aluminum, gold, silver, and alloys of any of the foregoing.

Examples of suitable ceramic fibers include metal oxides, such as alumina fibers, aluminosilicate fibers, boron nitride fibers, silicon carbide fibers, and combinations of any of the foregoing.

Examples of suitable inorganic fibers include carbon, alumina, basalt, calcium silicate, and rock wool.

The fibers may be glass fibers such as S-glass fibers, E-glass fibers, soda-lime-silica fibers, basalt fibers or quartz fibers. The glass fibers may be in the form of woven and/or interwoven glass fibers or non-woven glass fibers.

The fibers may comprise carbon, such as graphite fibers, glass fibers, ceramic fibers, silicon carbide fibers, polyimide fibers, polyamide fibers, or polyethylene fibers. The continuous fibers may comprise titanium, tungsten, boron, shape memory alloys, graphite, silicon carbide, boron, aramid, poly (p-phenylene-2, 6-benzobisoxazole), and combinations of any of the foregoing.

The fiber capable of withstanding high temperature includes, for example, carbon fiber, high-strength glass (SiO)₂) Fibres, oxide fibres, oxygenAlumina fibers, ceramic fibers, metal fibers, and high temperature thermoplastics and thermoset fibers.

The filler may comprise carbon nanotubes, fullerenes, or combinations thereof.

The filler may comprise graphene or other flat polycyclic aromatic hydrocarbons. Graphene may be used to impart thermal conductivity, electrical conductivity, EMI/RFI shielding capability, and/or antistatic properties to the cured composition.

The carbon particles may be graphene or carbon nanotubes.

Suitable carbon nanotubes may be characterized by a length of, for example, 1nm to 5,000 nm.

Suitable carbon nanotubes may be cylindrical in shape and structurally related to fullerenes. Suitable carbon nanotubes may be open or closed at their ends. Suitable carbon nanotubes may include, for example, more than 90 wt%, more than 95 wt%, more than 99 wt%, or more than 99.9 wt% carbon, where wt% is based on the total weight of the carbon nanotube.

Suitable carbon nanotubes may be prepared by any suitable method known in the art. For example, carbon nanotubes can be prepared by catalytic decomposition of hydrocarbons such as Catalytic Carbon Vapor Deposition (CCVD). Other processes for preparing carbon nanotubes include arc discharge processes, plasma decomposition of hydrocarbons, and pyrolysis of selected polyolefins under selected oxidation conditions. The starting hydrocarbon may be acetylene, ethylene, butane, propane, ethane, methane or any other gaseous or volatile carbon-containing compound. The catalyst, if present, may be used in pure or supported form. Purification can remove undesirable by-products and impurities.

Nanotubes may be present in the form of single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs), for example in the form of nanotubes having one single wall and nanotubes having more than one wall, respectively. In single-walled nanotubes, an atomic sheet that is one atom thick, for example, a graphite sheet that is one atom thick, graphene, is seamlessly rolled up to form a cylinder. Multi-walled nanotubes consist of a plurality of such cylinders arranged concentrically.

The multi-walled nanotubes may have, for example, an average of 5 to 15 walls.

Nanotubes, whether they are single-walled or multi-walled, can be characterized by their outer diameter or their length or both.

Single-walled nanotubes may be characterized by a diameter of, for example, at least 0.5nm, such as at least 1nm, or at least 2 nm.

The diameter of the single-walled nanotubes may be, for example, less than 50nm, such as less than 30nm or less than 10 nm. The diameter of the single-walled nanotubes may be, for example, from 0.2nm to 50, such as from 1nm to 30 nm. The length of the single-walled nanotubes may be, for example, at least 0.05 μm, at least 0.1 μm, or at least 1 μm. The length of the single-walled nanotubes may be, for example, less than 50mm, such as less than 25 mm. The length of the single-walled nanotubes may be, for example, 0.05 μm to 50mm, 0.1 μm to 10mm, or 1 μm to 1 mm.

The multi-walled nanotubes may be characterized by an outer diameter of at least 1nm, such as at least 2nm, 4nm, 6nm, 8nm, or at least 9 nm. The outer diameter may be less than 100nm, less than 80nm, 60nm, 40nm, or less than 20 nm. The outer diameter may be 9nm to 20 nm. The length of the multi-walled nanotubes may be less than 50nm, less than 75nm, or less than 100 nm. The length may be less than 500 μm or less than 100 μm. The length may be 100nm to 10 μm. The multi-walled carbon nanotubes may have an average outer diameter of 9nm to 20nm and/or an average length of 100nm to 10 μm.

The BET surface area of the carbon nanotubes may be, for example, 200m²G to 400m²/g。

The average number of walls of the carbon nanotubes is 5 to 15.

The composition may include an antioxidant or a combination of antioxidants. Examples of suitable antioxidants include phenolic antioxidants, such as pentaerythritol tetrakis [3- (3',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate](referred to herein as1010) Tris (2, 4-di-tert-butylphenyl) phosphite (referred to herein as168) 3 DL-alpha-tocopherol, 2, 6-di-tert-butyl-4-methylphenol, dibutyl hydroxy phenyl propionic acid stearate, 3, 5-di-tert-butyl-4-hydroxy hydrogenationCinnamic acid, 2' -methylenebis (6-tert-butyl-4-methyl-phenol), hexamethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]Phenylacrylamide, N' -1, 6-adipoylbis [3, 5-bis (1, 1-dimethylethyl) -4-hydroxy]Diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium bis [ monoethyl (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphonate]Triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 6 '-di-tert-butyl-4, 4' -butylidenedim-cresol, 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy-1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro [5.5]Undecane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, (2,4, 6-trioxa-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -triyl) trivinyltris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]Tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, ethylenebis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate]And 2, 6-bis [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] group]Octahydro-4, 7-methylene-1H-indenyl]-4-methyl-phenol.

Suitable antioxidants also include, for example, phenolic antioxidants with bifunctional groups, such as 4,4 '-thio-bis (6-tert-butyl-m-methylphenol), 2,2' -sulfanyldiylbis (6-tert-butyl-4-methylphenol), 2-methyl-4, 6-bis (octylsulfanylmethyl) phenol, thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-4- (4, 6-bis (octylthio) -1,3, 5-triazin-2-ylamino) phenol, N- (4-hydroxyphenyl) stearamide, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] butylmalonate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate and 2- (1, 1-dimethylethyl) -6- [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] -methyl ] -4-methylphenyl acrylate. Suitable antioxidants also comprise, for example, aminic antioxidants, such as N-phenyl-2-naphthylamine, poly (1, 2-dihydro-2, 2, 4-trimethyl-quinoline), N-isopropyl-N' -phenyl-p-phenylenediamine, N-phenyl-1-naphthylamine and 4, 4-bis (α, α -dimethylbenzyl) diphenylamine.

The compositions provided by the present disclosure may include a thermally conductive filler or a combination of thermally conductive fillers.

The conductive filler may also be thermally conductive.

The thermally conductive filler may comprise, for example, a metal nitride such as boron nitride, silicon nitride, aluminum nitride, boron arsenide, a carbon compound such as diamond, graphite, carbon black, carbon fiber, graphene, and grapheme carbon particles, a metal oxide such as alumina, magnesium oxide, beryllium oxide, silica, titanium oxide, nickel oxide, zinc oxide, copper oxide, tin oxide, a metal hydroxide such as aluminum hydroxide or magnesium hydroxide, a carbide such as silicon carbide, a mineral such as agate and silicon carbide, a ceramic such as ceramic microspheres, mullite, silica, silicon carbide, carbonyl iron, cerium (III) molybdate, copper, zinc, or a combination of any of the foregoing.

The compositions provided by the present disclosure can have greater than 50 wt% conductive filler, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, greater than 90 wt%, or greater than 95 wt% conductive filler, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include less than 50 wt% conductive filler, less than 60 wt%, less than 70 wt%, less than 80 wt%, less than 90 wt%, or less than 95 wt% conductive filler, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can have 50 wt% to 95 wt% conductive filler, 60 wt% to 95 wt%, 70 wt% to 95 wt%, or 80 wt% to 95 wt% conductive filler, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can have greater than 50 vol% conductive filler, greater than 60 vol%, greater than 70 vol%, greater than 80 vol%, greater than 90 vol%, or greater than 95 vol% conductive filler, where vol% is by total volume of the composition.

The compositions provided by the present disclosure can include less than 50 vol% conductive filler, less than 60 vol%, less than 70 vol%, less than 80 vol%, less than 90 vol%, or less than 95 vol% conductive filler, where vol% is by total volume of the composition.

The compositions provided by the present disclosure can have 50 vol% to 95 vol% conductive filler, 60 vol% to 95 vol%, 70 vol% to 95 vol%, or 80 vol% to 95 vol% conductive filler, where vol% is by total volume of the composition.

The compositions provided by the present disclosure may comprise one or more additional ingredients, such as adhesion promoters, solvents, plasticizers, reactive diluents, rheology modifiers, polysulfide cure retarders, colorants, corrosion inhibitors, flame retardants, or a combination of any of the foregoing.

The compositions provided by the present disclosure may include an adhesion promoter or a combination of adhesion promoters. The adhesion promoter may comprise a phenolic adhesion promoter, a combination of phenolic adhesion promoters, an organofunctional silane, a combination of organofunctional silanes, or a combination of any of the foregoing. The organosilane may be an amine functional silane.

The use of aminosilane adhesion promoters may be used to control the acidity of the sealant composition.

The compositions and sealants provided by the present disclosure may include phenolic adhesion promoters, organosilanes, or combinations thereof. The phenolic adhesion promoter may comprise a cured phenolic resin, an uncured phenolic resin, or a combination thereof. Examples of suitable adhesion promoters include: phenolic resins, e.g.A phenolic resin; and organosilanes, e.g. epoxy-functional silanes, mercapto-functional silanes or amine-functional silanes, e.g.An organosilane.

Phenolic adhesion promoters may comprise the reaction product of a condensation reaction of a phenolic resin with one or more thiol-terminated polysulfides and are known as phenolic resoles. The phenolic adhesion promoter may be thiol-terminated.

Examples of phenolic resins include 2- (hydroxymethyl) phenol, (4-hydroxy-1, 3-phenylene) dimethanol, (2-hydroxybenzene-1, 3, 4-triyl) trimethanol, 2-benzyl-6- (hydroxymethyl) phenol, (4-hydroxy-5- ((2-hydroxy-5- (hydroxymethyl) cyclohex-2, 4-dien-1-yl) methyl) -1, 3-phenylene) dimethanol, (4-hydroxy-5- ((2-hydroxy-3, 5-bis (hydroxymethyl) cyclohex-2, 4-dien-1-yl) methyl) -1, 3-phenylene) dimethanol, and combinations of any of the foregoing.

Suitable phenolic resins can be synthesized by the base-catalyzed reaction of phenol with formaldehyde.

Phenolic adhesion promoters may include those available from Durez CorporationResin, a,Resin orResins and polymers such asA reaction product of a condensation reaction of a thiol-terminated polysulfide such as a resin.

Examples of the resin include75108 (allyl ethers of hydroxymethylphenol, see U.S. Pat. No. 3,517,082) and75202。

examples of the resin include29101、29108、29112、29116、29008、29202、29401、29159、29181、92600、94635、94879 and94917。

examples of the resins are34071。

The compositions provided by the present disclosure may include an organofunctional adhesion promoter, such as an organofunctional alkoxysilane. The organofunctional alkoxysilane may include a silane bonded to a silicon atomA hydrolyzable group and at least one organic functional group. The organofunctional alkoxysilane may have the structure R¹³-(CH₂)_n-Si(-OR)_3-nR_nWherein R is¹³Is an organic functional group, n is 0,1 or 2, and R is an alkyl group, such as methyl or ethyl. Examples of organic functional groups include epoxy, amino, methacryloxy, or sulfide groups. The organofunctional alkoxysilane may be a dipodal alkoxysilane having two or more alkoxysilane groups, a functional dipodal alkoxysilane, a non-functional dipodal alkoxysilane, or a combination of any of the foregoing. The organofunctional alkoxysilane may be a combination of a monoalkoxysilane and a bipedal alkoxysilane. For amino-functional alkoxysilanes, R¹³May be-NH₂。

The amine functional alkoxysilane may include a primary amine functional alkoxysilane, a secondary amine functional alkoxysilane, or a combination thereof. Primary amine functional alkoxysilanes refer to alkoxysilanes having a primary amino group. Secondary amine functional alkoxysilanes refer to alkoxysilanes having secondary amine groups. The amine functional alkoxysilane can include, for example, 40 to 60 wt% of a primary amine functional alkoxysilane and 40 to 60 wt% of a secondary amine functional alkoxysilane; 45 to 55 weight percent of a primary amine functional alkoxysilane and 45 to 55 weight percent of a secondary amine functional alkoxysilane; or 47 to 53 weight percent of a primary amine functional alkoxysilane and 47 to 53 weight percent of a secondary amine functional alkoxysilane; wherein the weight percent is based on the total weight of amine functional alkoxysilane in the composition.

The secondary amine functional alkoxysilane may be a sterically hindered amine functional alkoxysilane. In sterically hindered amine functional alkoxysilanes, the secondary amine can be adjacent to a bulky group or moiety that limits or constrains the degree of freedom of the secondary amine, as compared to the degree of freedom of a non-sterically hindered secondary amine. For example, in the sterically hindered secondary amine, the secondary amine may be adjacent to a phenyl group, a cyclohexyl group, or a branched alkyl group.

The amine functional alkoxysilane may be a monomeric amine functional alkoxysilane having a molecular weight of, for example, 100Da to 1000Da, 100Da to 800Da, 100Da to 600Da, or 200Da to 500 Da.

Examples of suitable primary amine functional alkoxysilanes include 4-aminobutyltriethoxysilane, 4-amino-3, 3-dimethylbutyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 11-aminoundecyltriethoxysilane, 2- (4-pyridylethyl) triethoxysilane, 2- (2-pyridylethyltrimethoxysilane, N- (3-trimethoxysilylpropyl) pyrrole, 3-aminopropylsilanetriol, 4-amino-3, 3-dimethylbutylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 1-amino-2- (dimethylethoxysilyl) propane, 3-aminopropyldiisopropyleneoxysilane and 3-aminopropyldimethylethoxysilane.

Examples of suitable diamine-functional alkoxysilanes include aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (beta-aminoethyl) gamma-aminopropyltrimethoxysilane.

Examples of suitable secondary amine-functional silanes include 3- (N-allylamino) propyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, t-butylaminopropyltrimethoxysilane, (N, N-cyclohexylaminomethyl) methyldiethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-cyclohexylaminopropyl) trimethoxysilane, (3- (N-ethylamino) isobutyl) methyldiethoxysilane, (3- (N-ethylamino) isobutyl) trimethoxysilane, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, (phenylaminomethyl) methyldimethoxysilane, N-phenylaminomethyltriethoxysilane and N-phenylaminopropyltrimethoxysilane.

The name of the commodity isExamples of suitable amino-functional alkoxysilanes of includeA-1100 (gamma-aminopropyltriethoxysilane),A-1108 (gamma-aminopropyl silsesquioxane),A-1110 (gamma-aminopropyltrimethoxysilane),1120 (N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane),1128 (benzyl amino silane),A-1130 (triaminofunctional silane),Y-11699 (bis- (gamma-triethoxysilylpropyl) amine),A-1170 (bis- (gamma-trimethoxysilylpropyl) amine),A-1387 (Polyazaamides),Y-19139 (Polyazanamide based on ethoxy) anda-2120 (N-. beta. - (aminoethyl) - γ -aminopropylmethyldimethoxysilane).

Suitable amine-functional alkoxysilanes are commercially available from, for example, Gelest Inc (Gelest Inc), Dow Corning Corporation (Dow Corning Corporation), and meyer Corporation (Momentive).

The organofunctional alkoxysilane may be a mercapto-functional alkoxysilane including, for example, 3-mercaptopropyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and combinations of any of the foregoing.

The compositions provided by the present disclosure can include, for example, 1 wt% to 16 wt% adhesion promoter, 3 wt% to 14 wt%, 5 wt% to 12 wt%, or 7 wt% to 10 wt% adhesion promoter or a combination of adhesion promoters, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include less than 16 wt% adhesion promoter, less than 14 wt%, less than 12 wt%, less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt% adhesion promoter, or a combination of adhesion promoters.

The compositions provided by the present disclosure may contain a solvent or combination of solvents. Solvents may be included to adjust the viscosity of the composition and facilitate application.

Examples of suitable solvents include organic solvents such as toluene, methyl ethyl ketone, benzene, n-hexane, and combinations of any of the foregoing.

The compositions provided by the present disclosure can include 1 wt% to 10 wt% solvent, 2 wt% to 9 wt%, 3 wt% to 8 wt%, or 4 wt% to 7 wt% solvent or combination of solvents, where wt% is by total weight of the composition.

The compositions provided by the present disclosure can include less than 10 wt% solvent, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt% solvent or combination of solvents, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may contain a plasticizer or a combination of plasticizers. Plasticizers may be included to adjust the viscosity of the composition and facilitate application.

Examples of suitable plasticizers include combinations of: phthalate, terephthalic acid, isophthalic acid, hydrogenated terphenyl, quaterphenyl and higher benzenes or polyphenyls, phthalate, chlorinated paraffins, modified polyphenyls, tung oil, benzoate, dibenzoate, thermoplastic polyurethane plasticizers, phthalate, naphthalenesulfonate, trimellitate, adipate, sebacate, maleate, sulfonamide, organophosphate, polybutene, and combinations of any of the foregoing.

The compositions provided by the present disclosure can include 0.5 wt% to 7 wt% of a plasticizer or combination of plasticizers, 1 wt% to 6 wt%, 2 wt% to 5 wt%, or 2 wt% to 4 wt% of a plasticizer or combination of plasticizers, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include less than 8 wt% plasticizer, less than 6 wt%, less than 4 wt%, or less than 2 wt% plasticizer or combination of plasticizers, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may contain an extender or a combination of extenders. Extenders may be included to adjust the viscosity of the composition and facilitate application.

Examples of suitable extenders include talc, silica, clay, calcium sulfate, calcium carbonate, glass fibers, glass beads, carbon black, alumina trihydrate, wollastonite, and combinations of any of the foregoing.

The compositions provided by the present disclosure can include from 0.1 wt% to 3 wt% of a bulking agent or combination of bulking agents, from 0.2 wt% to 2 wt%, from 0.5 wt% to 1.5 wt%, or from 0.5 wt% to 1 wt% of a bulking agent or combination of bulking agents, wherein the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include less than 3 wt% of an extender, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% of an extender or combination of extenders, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may include a polysulfide cure retarder or a combination of polysulfide cure retarders.

Polysulfide cure retarders may include acids, such as fatty acids, organic or inorganic acids, or fatty acid salts. Examples of suitable polysulfide cure retarders include phenylphosphonic acid and itaconic acid. The cure retarder may improve the stability of polysulfide cure activators and polysulfide cure accelerators.

The compositions provided by the present disclosure can include less than 5 wt% polysulfide cure retarder, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% polysulfide cure retarder, or a combination of polysulfide cure retarders, where the wt% are by total weight of the composition.

The compositions provided by the present disclosure may include a flame retardant or a combination of flame retardants.

The flame retardant may comprise an inorganic flame retardant, an organic flame retardant, or a combination thereof.

Examples of suitable inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, antimony oxide, hydromagnesite, Aluminum Trihydroxide (ATH), calcium phosphate, titanium oxide, zinc oxide, magnesium carbonate, barium sulfate, barium borate, kaolinite, silica, antimony oxide, and combinations of any of the foregoing.

Examples of suitable organic flame retardants include halogenated hydrocarbons, halogenated esters, halogenated ethers, chlorinated and/or brominated flame retardants, halogen-free compounds such as organic phosphorus compounds, organic nitrogen compounds, and combinations of any of the foregoing.

The composition may comprise, for example, from 1 wt% to 30 wt%, such as from 1 wt% to 20 wt% or from 1 wt% to 10 wt%, of the flame retardant or combination of flame retardants, based on the total weight of the composition. For example, the composition can include less than 30 wt%, less than 20 wt%, less than 10 wt%, less than 5 wt%, or less than 2 wt% of a flame retardant or combination of flame retardants, based on the total weight of the composition.

The compositions provided by the present disclosure may include a corrosion inhibitor or a combination of corrosion inhibitors.

Examples of suitable corrosion inhibitors include, for example, zinc phosphate based corrosion inhibitors, e.g., micronized commercially available from HaloxSZP-391、430 calcium phosphate,Zinc phosphate ZP,SW-111 strontium phosphosilicate,720 mixed metal phosphor-carbonates and550 and 650 proprietary organic corrosion inhibitors. Other suitable corrosion inhibitors include those commercially available from Heucotech Inc. (Heucotech Ltd)ZPA zinc aluminium phosphate andZMP zinc molybdenum phosphate.

The corrosion inhibitor may include lithium silicate, such as lithium orthosilicate (Li)₄SiO₄) And lithium metasilicate (Li)₂SiO₃) MgO, oxazole, or a combination of any of the foregoing. The corrosion inhibiting component (2) may further include at least one of magnesium oxide (MgO) and oxazole.

The corrosion inhibitor may include a monomeric amino acid, a dimeric amino acid, an oligomeric amino acid, or a combination of any of the foregoing. Examples of suitable amino acids include histidine, arginine, lysine, cysteine, cystine, tryptophan, methionine, phenylalanine, tyrosine, and combinations of any of the foregoing.

The corrosion inhibitor may include a nitrogen-containing heterocyclic compound. Examples of such compounds include oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, indolizines and triazines, tetrazoles, tolyltriazoles, and combinations of any of the foregoing.

Examples of suitable triazoles include 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, derivatives thereof, and combinations of any of the foregoing. Derivatives of 1,2, 3-triazole include 1-methyl-1, 2, 3-triazole, 1-phenyl-1, 2, 3-triazole, 4-methyl-2-phenyl-1, 2, 3-triazole, 1-benzyl-1, 2, 3-triazole, 4-hydroxy-1, 2, 3-triazole, 1-amino-1, 2, 3-triazole, 1-benzamido-4-methyl-1, 2, 3-triazole, 1-amino-4, 5-diphenyl-1, 2, 3-triazole, 1,2, 3-triazolaldehyde, 2-methyl-1, 2, 3-triazole-4-carboxylic acid and 4-cyano-1, 2, 3-triazole, or a combination thereof. Derivatives of 1,2, 4-triazole include 1-methyl-1, 2, 4-triazole, 1, 3-diphenyl-1, 2, 4-triazole, 5-amino-3-methyl-1, 2, 4-triazole, 3-mercapto-1, 2, 4-triazole, 1,2, 4-triazole-3-carboxylic acid, 1-phenyl-1, 2, 4-triazol-5-one, 1-phenylurazole, and combinations of any of the foregoing. Examples of diazoles include 2, 5-dimercapto-1, 3, 4-thiadiazole.

The corrosion inhibitor may comprise an azole or a combination of azoles. Oxazoles are 5-membered N-heterocyclic compounds containing two double bonds in the heterocyclic ring, one to three carbon atoms and optionally a sulfur or oxygen atom. Examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, tolyltriazole, 2, 5-dimercapto-1, 3, 4-thiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-amino-5-mercapto-1, 3, 4-thiadiazole, 2-mercapto-1-methylimidazole, 2-amino-5-ethyl-1, 3, 4-thiadiazole, 2-amino-5-ethylthio-1, 3, 4-thiadiazole, 5-phenyltetrazole, 7H-imidazo (4,5-d) pyrimidine, and 2-aminothiazole. Any of the foregoing salts, such as sodium and/or zinc salts, may also be used as effective corrosion inhibitors. Other suitable oxazoles include 2-hydroxybenzothiazole, benzothiazole, 1-phenyl-4-methylimidazole, and 1- (p-tolyl) -4-methylimidazole.

The compositions provided by the present disclosure may include corrosion resistant particles, such as inorganic oxide particles, including, for example, zinc oxide (ZnO), magnesium oxide (MgO), cerium oxide (CeO)₂) Molybdenum oxide (MoO)₃) Silicon dioxide (SiO)₂) And combinations of any of the foregoing. The inorganic oxide may include the following oxides: zinc, cerium, yttrium, manganese, magnesium, molybdenum, lithium, aluminum, magnesium, tin, calcium, boron, phosphorus, silicon, zirconium, iron, titanium, or a combination of any of the foregoing. In certain embodiments, the particles comprise an oxide of magnesium, zinc, cerium, or calcium.

The compositions provided by the present disclosure can include less than 5 wt% of a corrosion inhibitor or combination of corrosion inhibitors, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% of a corrosion inhibitor or combination of corrosion inhibitors, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may include a moisture control additive or a combination of moisture control additives.

Examples of suitable moisture control additives include synthetic zeolites, activated alumina, silica gel, calcium oxide, magnesium oxide, molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, and combinations of any of the foregoing.

Examples of alkoxysilane compounds that may be used as moisture control agents include n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicates, ethylsilicates, γ -mercaptopropylmethyldimethoxysilane, γ -mercaptopropylmethyldiethoxysilane, γ -glycidoxypropyltrimethoxysilane, and combinations of any of the foregoing.

An example of an oxazolidine compound useful as a moisture control agent is 3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine.

Examples of other suitable moisture control agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-trimethoxysilylmethyl-O-methylcarbamate, N-dimethoxy (methyl) silylmethyl-O-methylcarbamate, N-methyl [3- (trimethoxysilyl) propyl ] carbamate, vinyldimethoxymethylsilane, vinyltris (2-methoxyethoxy) silane, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate, oligomeric vinylsilanes, and combinations of any of the foregoing.

The compositions provided by the present disclosure can include less than 5 wt% of a moisture control agent or combination of moisture control agents, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% of a moisture control agent or combination of moisture control agents, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure may include a polysulfide or combination of polysulfides, an activator or combination of activators, a polysulfide cure promoter or combination of polysulfide cure promoters, and a porous material or combination of porous materials.

The composition can further include, for example, a non-porous material, a plasticizer, a solvent, a flame retardant, a corrosion inhibitor, a polysulfide cure retarder, an adhesion promoter, an extender, a colorant, a moisture control agent, or a combination of any of the foregoing.

The compositions provided by the present disclosure can include 20 wt% to 70 wt% of the polysulfide prepolymer, such as 25 wt% to 65 wt%, 30 wt% to 60 wt%, 35 wt% to 55 wt%, or 40 wt% to 50 wt%, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include greater than 20 wt% polysulfide prepolymer, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, or greater than 60 wt% polysulfide prepolymer, and include less than 95 wt% polysulfide prepolymer, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include from 0.5 wt% to 10 wt% of a polysulfide cure activator or combination of polysulfide cure activators such as from 1 wt% to 9 wt%, from 2 wt% to 8 wt%, from 3 wt% to 7 wt%, or from 4 wt% to 6 wt% of a polysulfide cure activator or combination of polysulfide cure activators, where the wt% are by total weight of the composition. The compositions provided by the present disclosure can include less than 10 wt% polysulfide cure activator or combination of polysulfide cure activators, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt%; and greater than 1 wt% of a polysulfide cure activator or combination of polysulfide cure activators, wherein the wt% are by total weight of the composition.

The compositions provided by the present disclosure can include from 0.01 wt% to 2 wt% of a polysulfide cure accelerator or combination of polysulfide cure accelerators, such as from 0.02 wt% to 1.5 wt%, from 0.05 wt% to 1.25 wt%, from 0.075 wt% to 1 wt%, or from 0.1 wt% to 0.75 wt% of a polysulfide cure accelerator or combination of polysulfide cure accelerators, where the wt% is by total weight of the composition. The compositions provided by the present disclosure can include, for example, less than 2 wt% polysulfide cure accelerator or combination of polysulfide cure accelerators, less than 1.5 wt%, less than 1.25 wt%, less than 1 wt%, less than 0.75 wt%, less than 0.5 wt%, less than 0.25 wt%, or less than 0.2 wt%; and greater than 0.01 wt% of a polysulfide cure accelerator or combination of polysulfide cure accelerators, wherein the wt% are by total weight of the composition.

The compositions provided by the present disclosure can include, for example, 0.1 wt% to 10 wt% of a potentiator or combination of potentiators, such as 0.1 wt% to 9 wt%, 0.5 wt% to 8 wt%, 1 wt% to 6 wt%, or 2 wt% to 4 wt% of a potentiator or combination of potentiators, where the wt% are by total weight of the composition. The composition may comprise, for example, greater than 0.1 wt% of a synergist or combination of synergists and comprise less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt% of a synergist or combination of synergists, where the wt% is by total weight of the composition.

The synergist can include a polyether or a combination of polyethers, and the compositions provided by the present disclosure can include, for example, 0.1 wt% to 10 wt% of a polyether or a combination of polyethers, such as 0.1 wt% to 9 wt%, 0.5 wt% to 8 wt%, 1 wt% to 6 wt%, or 2 wt% to 4 wt% of a polyether or a combination of polyethers, where the wt% is by total weight of the composition. The composition can include, for example, greater than 0.1 wt% of a polyether or combination of polyethers and include less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt% of a polyether or combination of polyethers, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include, for example, 0.1 wt% to 15 wt% of a porous material such as silica, 0.1 wt% to 10 wt%, 0.5 wt% to 5 wt% of a porous material, 0.75 wt% to 3 wt%, or 1 wt% to 2 wt% of a porous material, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include, for example, less than 15 wt% of a porous material such as silica, less than 10 wt%, less than 7.5 wt%, less than 5 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt% of a porous material; and comprises more than at least 0.1 wt% of a porous material, wherein wt% is by total weight of the composition.

The compositions provided by the present disclosure can include, for example, 15 wt% to 55 wt% total filler, such as 20 wt% to 50 wt%, 25 wt% to 45 wt%, or 30 wt% to 40 wt% total filler, where the wt% is by total weight of the composition. The compositions provided by the present disclosure can include, for example, less than 55 wt% filler, less than 45 wt%, less than 35 wt%, or less than 25 wt% filler; and comprises greater than 15 wt% total filler, wherein wt% is by total weight of the composition.

The compositions provided by the present disclosure can include, for example, 20 wt% to 70 wt% polysulfide prepolymer, 10 wt% to 60 wt% non-porous inorganic filler, 0.1 wt% to 10 wt% porous material, 0.1 wt% to 10 wt% polysulfide cure activator, 0.01 wt% to 5 wt% polysulfide cure accelerator, and 2 wt% to 30 wt% of one or more additional ingredients, where the wt% is by total weight of the composition.

The compositions provided by the present disclosure can include, for example, 30 wt% to 60 wt% polysulfide prepolymer, 20 wt% to 50 wt% non-porous inorganic filler, 0.5 wt% to 5 wt% porous material, 1 wt% to 8 wt% polysulfide cure activator, 0.1 wt% to 3 wt% polysulfide cure accelerator, and 5 wt% to 25 wt% of one or more additional ingredients, where the wt% are based on the total weight of the composition.

The compositions provided by the present disclosure can include, for example, 40 wt% to 50 wt% polysulfide prepolymer, 30 wt% to 40 wt% non-porous inorganic filler, 0.5 wt% to 3 wt% porous material, 5 wt% to 7 wt% polysulfide cure activator, 0.3 wt% to 2 wt% polysulfide cure accelerator, and 10 wt% to 20 wt% of one or more additional ingredients, where the wt% are based on the total weight of the composition.

The one or more additional ingredients may include adhesion promoters, solvents, plasticizers, other additives, or a combination of any of the foregoing.

The uncured sealants provided by the present disclosure may be provided in the form of a two-component system including a first component and a second component that may be separately prepared and stored and combined and mixed at the time of use.

The first component of the sealant system can include, for example, a polysulfide prepolymer.

The second component of the sealant system can include a polysulfide cure activator.

At least one of the first component and the second component may include a synergist, a porous material, or a polysulfide cure activator.

Each of the first component and the second component may independently comprise a synergist, a porous material, a polysulfide cure accelerator, or a combination of any of the foregoing.

When the first component and the second component are combined to form the curable composition, the curable composition may include a polysulfide prepolymer, a polysulfide cure activator, a polysulfide cure accelerator, a synergist, and a porous material.

To promote uniform mixing, it may be desirable for the viscosities of the first and second components to be similar.

The curable compositions provided by the present disclosure may be used as sealants or coatings, such as vehicle and aerospace sealants and coatings, and in particular, as sealants or coatings requiring resistance to hydraulic fluids. By sealant is meant a curable composition that, when cured, is capable of withstanding atmospheric conditions, such as moisture and temperature, and at least partially blocking the transmission of materials such as water, water vapor, fuel, solvents, and/or liquids and gases.

The compositions provided by the present disclosure may be applied directly onto the surface of a substrate or over an underlying layer such as a primer by any suitable coating process.

Further, methods for sealing an aperture using the compositions provided by the present disclosure are provided. These methods include, for example: applying a curable composition to at least one surface of the part; and curing the applied composition to provide a sealed part.

The sealant-containing compositions provided by the present disclosure can be applied to any of a variety of substrates. Examples of substrates to which the composition may be applied include: metals, such as titanium, stainless steel, steel alloys, aluminum and aluminum alloys,any of the metals may be anodized, primed, organically coated, or chromate coated; epoxy resin, polyurethane, graphite, glass fiber composite material,Acrylic resins and polycarbonates. The compositions provided by the present disclosure may be applied to a substrate such as aluminum or an aluminum alloy.

The sealant compositions provided by the present disclosure can be formulated as class a, class B, or class C sealants. Class a sealants refer to brushable sealants having viscosities of 1 to 500 poise (0.1 to 50 pascal-seconds) and are designed for brushing. Class B sealants refer to extrudable sealants having viscosities of 4,500 poise to 20,000 poise (450 pa-sec to 2,000 pa-sec) and are designed for application by extrusion via a pneumatic gun. Class B sealants can be used to form fillets and can be used to seal on vertical surfaces or edges where low slump/slag is desired. Class C sealants have viscosities of 500 poise to 4,500 poise (50 pa-sec to 450 pa-sec) and are designed for application by roll or comb coaters. A class C sealant may be used to join the surface seals. Viscosity can be measured according to SAE space Standard AS5127/1C, section 5.3, published by the SAE International Group.

The compositions provided by the present disclosure can be cured at ambient conditions, where ambient conditions refer to a temperature of 20 ℃ to 25 ℃ and atmospheric humidity. The composition can be cured under conditions that encompass a temperature of 0 ℃ to 100 ℃ and a humidity of 0% relative humidity to 100% relative humidity. The composition may be cured at higher temperatures, such as at least 30 ℃, at least 40 ℃, or at least 50 ℃. The composition may be cured at room temperature, for example 25 ℃. The method may be used to seal holes on aerospace vehicles, including aircraft and aerospace vehicles.

Curing the applied composition encompasses subjecting the composition to ambient conditions such as 25 ℃ and 50% RH and exposing the applied coating to an elevated temperature, such as a temperature greater than 30 ℃, for a period of time.

Also disclosed are holes, surfaces, joints, fillets, joining surfaces, including holes, surfaces, fillets, joints and joining surfaces of an aerospace vehicle, sealed with the compositions provided by the present disclosure. Compositions and sealants may also be used to seal the fasteners.

As will be appreciated by those skilled in the art and as defined by the requirements of applicable standards and specifications, the time to form a viable seal using the curable compositions of the present disclosure may depend on several factors. Generally, the curable compositions of the present disclosure develop adhesive strength in about 3 days to about 7 days after mixing and application to a surface. Generally, the full bond strength and other properties of the cured compositions of the present disclosure become fully developed up to 7 days after the curable composition is mixed and applied to a surface. A viable seal is one that meets the requirements of the intended use.

The thickness of the cured composition can be, for example, 5 mils to 25 mils (127 μm to 635 μm), such as 10 mils to 20 mils (254 μm to 508 μm).

Cured compositions, such as cured sealants, provided by the present disclosure may exhibit properties that are acceptable for use in vehicle and aerospace sealant applications. In general, sealants used in aerospace applications are expected to exhibit the following properties: peel strength greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS)3265B substrates, as determined under dry conditions after immersion for 7 days in JRF I form and after immersion in a solution of 3% NaCl according to AMS 3265B test specification; a tensile strength of between 300 pounds per square inch (psi) and 400psi (2.75 MPa); tear strength greater than 50 pounds per linear inch (pli) (8.75N/mm); elongation between 250% and 300%; and a hardness greater than 40 durometer A (Durometer A). These and other cured sealant properties suitable for aerospace applications are disclosed in AMS 3265B. It is also desirable that the compositions of the present disclosure for aerospace and aircraft applications exhibit a percent volume swell no greater than 25% after one week immersion in Jet Reference Fluid (JRF) type 1 at 60 ℃ (140 ° f) and ambient pressure when cured. Other properties, ranges, and/or thresholds may be suitable for other sealant applications.

The cured compositions provided by the present disclosure can be fuel resistant. The term "fuel resistance" means that the composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that exhibits a percent volume swell no greater than 40%, in some cases no greater than 25%, in some cases no greater than 20%, and in other cases no greater than 10% after immersion in JRF form I at 140 ° f (60 ℃) and ambient pressure for one week, according to a method similar to that described in ASTM D792 (american society for testing and materials) or AMS 3269 (aerospace material specifications). JRF form I as used to determine fuel resistance has the following composition: toluene: 28 plus or minus 1 volume percent; cyclohexane (technical): 34 +/-1 volume percent; isooctane: 38 + -1 vol%; and tert-dibutyl disulfide: 1 + -0.005 vol% (see AMS 2629, published in 1989, 7/1/3.1.1 et al, available from SAE (Society of Automotive Engineers)).

The compositions provided by the present disclosure provide cured products, such AS sealants, that exhibit tensile elongation of at least 200% and tensile strength of at least 200psi when measured according to the procedures described in AMS 3279 § 3.3.17.1, test procedure AS5127/1 § 7.7. Generally, there is no tensile and elongation requirement for class a sealants. For class B sealants, as a general requirement, the tensile strength is equal to or greater than 200psi (1.38MPa) and the elongation is equal to or greater than 200%. Acceptable elongation and tensile strength may vary depending on the application.

The composition provides a cured product, such AS a sealant, that exhibits a lap shear strength greater than 200psi (1.38MPa), such AS a lap shear strength of at least 220psi (1.52MPa), at least 250psi (1.72MPa), and in some cases at least 400psi (2.76MPa), when measured according to the procedure described in SAE AS5127/1 paragraph 7.8.

The cured sealant prepared from the compositions provided by the present disclosure may meet or exceed aerospace sealant requirements as set forth in AMS 3277.

Also disclosed are holes, surfaces, joints, fillets, joining surfaces, including holes, surfaces, fillets, joints and joining surfaces of an aerospace vehicle, sealed with the compositions provided by the present disclosure.

The compositions provided by the present disclosure may be used to seal components comprising surfaces of vehicles.

The term "vehicle" is used in its broadest sense and encompasses all types of aircraft, spacecraft, watercraft and land vehicles. For example, the vehicle may include aircraft, such as airplanes, including private aircraft, as well as small, medium, or large commercial passenger aircraft, cargo aircraft, and military aircraft; helicopters, including private, commercial, and military helicopters; space vehicles, including rockets and other spacecraft. The vehicle may comprise a land vehicle such as a trailer, automobile, truck, bus, van, construction vehicle, golf cart, motorcycle, bicycle, train, and rail vehicle. The vehicle may also comprise a watercraft such as a ship, a boat, and a hovercraft.

The compositions provided by the present disclosure may be used to: F/A-18 jet or related aircraft, such as F/A-18E Rheum palmatum and F/A-18F; boeing 787 fantasy airliners, 737, 747, 717 jet passenger aircraft, related aircraft (manufactured by Boeing Commercial airlines); v-22Osprey type inclined rotor wing aircraft (V-22 Osprey); VH-92, S-92 and related aircraft (produced by the U.S. naval aviation systems department of command (NAVAIR) and Sekorsky aircraft corporation (Sikorsky)); g650, G600, G550, G500, G450 and related aircraft (produced by Gulfstream); and a350, a320, a330 and related aircraft (manufactured by air bus). The compositions provided by the present disclosure may be used in any suitable commercial, military, or general aviation aircraft, such as those produced by pombodi corporation (bombodier Inc.) and/or pombodi Aerospace corporation (bombodier Aerospace), such as canadian Regional aircraft (CRJ) and related aircraft; aircraft produced by Rockheed Martin, Inc. (locked Martin), such as F-22 bird warplane (F-22Raptor), F-35Lightning fighter (F-35Lightning) and related aircraft; aircraft produced by Northrop Grumman, Inc. (Northrop Grumman), such as B-2 ghost strategic bombers (B-2Spirit) and related aircraft; aircraft manufactured by piranus aircrafts Ltd (Pilatus Aircraft Ltd.); aircraft manufactured by Eclipse Aviation Corporation; or Aircraft produced by Eclipse aeronautics (Kestrel Aircraft).

The compositions provided by the present disclosure may be used to seal parts and surfaces of vehicles, such as fuel tank surfaces and other surfaces exposed to or potentially exposed to aerospace solvents, aerospace hydraulic fluids, and aerospace fuels.

The present invention encompasses components sealed with compositions provided by the present disclosure as well as assemblies and devices comprising components sealed with compositions provided by the present disclosure.

The present invention encompasses a vehicle comprising a component such as a surface sealed with a composition provided by the present disclosure. For example, aircraft that include fuel tanks or portions of fuel tanks sealed with the sealants provided by the present disclosure are encompassed within the scope of the present invention.

Aspects of the invention

Embodiments of the present disclosure are further defined by the following aspects of the invention.

Aspect 1a composition comprising: a polysulfide prepolymer; a polysulfide cure activator; a polysulfide curing accelerator; a filler, wherein the filler comprises a porous material; and a synergist, wherein the synergist comprises a polyether, and wherein the composition comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is by total weight of the composition.

Aspect 2. the composition of aspect 1, wherein the polysulfide prepolymer comprises a polysulfide prepolymer comprising moieties of formula (1) or a polysulfide prepolymer having the structure of formula (1 a):

-(-R-S-S-)_n-R- (1)

HS-(-R-S-S-)_n-R-SH (1a)

wherein each R is- (CH)₂)₂-O-CH₂-O-(CH₂)₂-; and isn is an integer from 7 to 38.

Aspect 3. the composition of any one of aspects 1-2, wherein the polysulfide prepolymer comprises a polysulfide prepolymer comprising moieties of formula (2) or a polysulfide prepolymer having the structure of formula (2 a):

-(-R-S-S-)_a-CH₂-CH{-CH₂-(-S-S-R-)_b-}{-(-S-S-R-)_c-} (2)

HS-(-R-S-S-)_a-CH₂-CH{-CH₂-(-S-S-R-)_b-SH}{-(-S-S-R-)_c-SH} (2a)

wherein

Each R is- (CH)₂)₂-O-CH₂-O-(CH₂)₂-；

n is the sum of a, b and c; and is

n is an integer from 7 to 38.

Aspect 4. the composition of aspect 3, wherein the polysulfide prepolymer has a number average molecular weight of 1,000Da to 6,500Da, an SH content of 1% to 6%, and a crosslink density of 0% to 2%.

Aspect 5. the composition of any one of aspects 1 to 4, wherein the polysulfide prepolymer comprises a polysulfide prepolymer comprising moieties of formula (3) or a polysulfide prepolymer having the structure of formula (3 a):

-[(CH₂)₂-O-CH₂-O-(CH₂)₂-S-S-]_n-(CH₂)₂-O-CH₂-O-(CH₂)₂- (3)

HS-[(CH₂)₂-O-CH₂-O-(CH₂)₂-S-S-]_n-(CH₂)₂-O-CH₂-O-(CH₂)₂-SH (3a)

wherein n is an integer from 8 to 80.

Aspect 6. the composition of any one of aspects 1 to 5, wherein the polysulfide prepolymer comprises a polysulfide prepolymer comprising moieties of formula (4) or a polysulfide prepolymer having the structure of formula (4 a):

-R-(S_y-R)_t- (4)

HS-R-(S_y-R)_t-SH (4a)

wherein

t is an integer of 1 to 60;

q is an integer of 1 to 8;

p is an integer from 1 to 10;

r is an integer from 1 to 10;

the average value of y is in the range of 1.0 to 1.5; and is

Each R is independently selected from branched C_1-10Alkanediyl, branched C_6-12Aryl diyl and having the structure- (CH)₂)_p–O–(CH₂)_q–O–(CH₂)_r-part (a).

Aspect 7. the composition of any one of aspects 1 to 6, wherein the polysulfide prepolymer comprises a polysulfide prepolymer comprising moieties of formula (5) or a polysulfide prepolymer having the structure of formula (5 a):

-(R-O-CH₂-O-R-S_m-)_n-1-R-O-CH₂-O-R- (5)

HS-(R-O-CH₂-O-R-S_m-)_n-1-R-O-CH₂-O-R-SH (5a)

wherein

Each R is independently C_2-4An alkanediyl group;

m is an integer of 1 to 8; and is

n is an integer from 2 to 370.

Aspect 8 the composition of any one of aspects 1 to 7, wherein the polysulfide prepolymer comprises a thiol-terminated polysulfide prepolymer.

Aspect 9. the composition of any one of aspects 1 to 8, wherein the polysulfide prepolymer has an average functionality of from 2.1 to 2.9.

Aspect 10 the composition of any one of aspects 1 to 9, wherein the polysulfide cure activator comprises a metal oxide.

The composition of any of aspects 1-9, wherein the polysulfide cure activator comprises manganese dioxide.

Aspect 12 the composition of any one of aspects 1 to 11, wherein the polysulfide cure accelerator comprises an amine-based sulfur donor.

The composition of aspect 12, wherein the polysulfide cure accelerator comprises a polythiuram sulfide.

Aspect 14 the composition of any one of aspects 12-13, wherein the polysulfide cure accelerator comprises a thiuram disulfide.

Aspect 15 the composition of any one of aspects 1 to 14, wherein the porous material is characterized by: BET of 5m²G to 700m²(ii)/g; a total pore volume of 0.01mL/g to 10 mL/g; an average pore diameter of 10nm to 30 nm; or a combination of any of the foregoing.

The composition of aspect 16. the composition of any one of aspects 1 to 15, wherein the porous material comprises silica, alumina, zinc oxide, titania, zirconia, hafnia, yttria, rare earth oxides, boehmite, alkaline earth metal fluorides, calcium phosphate, and hydroxyapatite, or a combination of any of the foregoing.

The composition of any one of aspects 1-16, wherein the porous material comprises silica.

The composition of any one of aspects 1-17, wherein the porous material comprises untreated silica.

The composition of any one of aspects 1-17, wherein the porous material comprises treated silica.

Aspect 20 the composition of any one of aspects 1-19, wherein the porous material comprises fumed silica, precipitated silica, or a combination thereof.

The composition of aspect 20, wherein the fumed silica comprises hydrophobic silica, hydrophilic silica, or a combination thereof.

Aspect 22. the composition of any one of aspects 1 to 21, wherein the porous material has an average diameter (d50) of 1 μ ι η to 20 μ ι η.

Aspect 23. the composition of any one of aspects 1 to 21, wherein the porous material has an average diameter (d50) of less than 20 μ ι η.

Aspect 24. the composition of any one of aspects 1 to 23, wherein the porous material has a BET surface area of 5m²G to 700m²(iv)/g, wherein the BET surface area is determined according to DIN EN ISO 9277/DIN 66132.

Aspect 25. the composition of any of aspects 1-23, wherein the porous material has a BET surface area of greater than 5m²(iv)/g, wherein the BET surface area is determined according to DIN EN ISO 9277/DIN 66132.

The composition of any of aspects 1-25, wherein the composition comprises from 0.1 wt% to 10 wt% of the porous material, wherein wt% is by total weight of the composition.

The composition of any one of aspects 1-26, wherein the composition comprises less than 10 wt% of the porous material, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-27, wherein the composition comprises a filler.

Aspect 29. the composition of aspect 28, wherein the composition comprises from 5 wt% to 70 wt% filler, wherein wt% is by total weight of the composition.

Aspect 30. the composition of any of aspects 28-29, wherein the filler comprises a porous material.

The composition of aspect 30, wherein the porous material comprises hydrophobic silica, hydrophilic silica, or a combination thereof.

The composition of any of aspects 1-31, wherein the filler comprises an inorganic filler, an organic filler, a low density filler, a conductive filler, or a combination of any of the foregoing.

The composition of aspect 33. the composition of any of aspects 1-32, wherein the filler further comprises aluminum silicate, calcium carbonate, talc, titanium dioxide, or a combination of any of the foregoing.

Aspect 34. the composition of any of aspects 1-33, wherein the filler comprises 70 wt% to 99 wt% calcium carbonate, wherein wt% is by total weight of the filler.

The composition of any of aspects 1-34, wherein the filler comprises from 4 wt% to 14 wt% titanium dioxide, wherein wt% is by total weight of the filler.

Aspect 36. the composition of any one of aspects 1 to 35, wherein the polyether comprises a polyether that is liquid at 25 ℃.

Aspect 37 the composition of any one of aspects 1-36, wherein the polyether comprises polyethylene glycol, polypropylene glycol, poly (tetramethylene ether) glycol, a block copolymer of any of the foregoing, a crown ether, or a combination of any of the foregoing.

The composition of aspect 38, wherein the polyether comprises a terminal hydroxyl group, a terminal alkyl group, a terminal substituted phenyl group, a terminal (meth) acryloyl group, or a combination of any of the foregoing.

The composition of any one of aspects 1-38, wherein the polyether comprises a polyether having a structure of formula (7), a structure of formula (8), or a combination thereof:

wherein

n is an integer of 1 to 6;

p is an integer from 2 to 50;

z is an integer from 3 to 6;

each R¹Independently selected from hydrogen, C_1-10Alkyl, (meth) acryloyl, and substituted aryl;

each R²Independently selected from hydrogen and C_1-3An alkyl group; and is

B is a multifunctional moiety.

Aspect 40. the composition of aspect 39, wherein B is selected from C_2-20Alkane-triyl, C_2-20Heteroalkanetriyl, C_2-20Alkane-tetrayl and C_2-20A heteroalkane tetrayl group.

The composition of any of aspects 1-40, wherein the polyether comprises an ionic polyether.

Aspect 42 the composition of any one of aspects 1 to 36, wherein the polyether comprises a nonionic polyether.

The composition of any one of aspects 1-42, wherein the polyether has a number average molecular weight of 100Da to 5,000Da, wherein molecular weight is determined by gel permeation chromatography.

The composition of any one of aspects 1-42, wherein the polyether has a number average molecular weight of less than 5,000Da, wherein molecular weight is determined by gel permeation chromatography.

Aspect 45 the composition of any one of aspects 1 to 44, wherein the composition comprises from 20 wt% to 70 wt% of the polysulfide prepolymer, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-44, wherein the composition comprises greater than 20 wt% of the polysulfide prepolymer, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-46, wherein the composition comprises from 1 wt% to 10 wt% of the polysulfide cure activator, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-46, wherein the composition comprises less than 10 wt% of the polysulfide cure activator, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-48, wherein the composition comprises from 0.01 wt% to 2 wt% of the polysulfide cure accelerator, wherein wt% is by total weight of the composition.

Aspect 50 the composition of any one of aspects 1 to 48, wherein the composition comprises less than 2 wt% of the polysulfide cure accelerator.

The composition of any of aspects 1-45, wherein the composition comprises from 1 wt% to 10 wt% of the potentiator, wherein wt% is by total weight of the composition.

The composition of any of aspects 1-45, wherein the composition comprises from 2 wt% to 6 wt% of the potentiator, wherein wt% is by total weight of the composition.

The composition of any one of aspects 1-48, wherein the composition comprises one or more additives.

The composition of aspect 54, wherein the one or more additives comprise a polysulfide cure retarder, an adhesion promoter, a solvent, an extender, a plasticizer, a flame retardant, a corrosion inhibitor, a colorant, or a combination of any of the foregoing.

The composition of any of aspects 1-52, wherein the composition comprises a polysulfide cure retarder.

The composition of aspect 56. the composition of aspect 55, wherein the polysulfide cure retarder comprises a fatty acid, an inorganic acid, a zeolite, or a combination of any of the foregoing.

Aspect 57 the composition of any one of aspects 55 to 56, wherein the composition comprises from 0.1 wt% to 2 wt% of the polysulfide cure retarder, wherein wt% is by total weight of the composition.

Aspect 58. the composition of any one of aspects 1 to 58, wherein the composition comprises an adhesion promoter.

Aspect 59. the composition of aspect 58, wherein the adhesion promoter comprises a phenolic resin, an organofunctional polyalkoxysilane, or a combination thereof.

Aspect 60 the composition of any one of aspects 1 to 59, wherein the composition further comprises a solvent.

Aspect 61 the composition of aspect 60, wherein the solvent comprises an organic solvent.

Aspect 62. the composition of aspect 61, wherein the organic solvent comprises toluene, methyl ethyl ketone, xylene, light aromatic naphtha, or a combination of any of the foregoing.

The composition of any of aspects 60-62, wherein the composition comprises from 0.1 wt% to 8 wt% of the solvent, wherein wt% is by total weight of the composition.

The composition of any one of aspects 1 to 63, wherein the composition further comprises a bulking agent.

The composition of aspect 65. the composition of aspect 64, wherein the bulking agent comprises calcium sulfonate.

The composition of any of aspects 64-65, wherein the composition comprises from 0.1 wt% to 3 wt% of the bulking agent, wherein wt% is by total weight of the composition.

Aspect 67. the composition of any one of aspects 1 to 66, wherein the composition further comprises a plasticizer.

Aspect 68. the composition of aspect 67, wherein the plasticizer comprises a modified polyphenyl.

Aspect 69 the composition of any one of aspects 67 to 68, wherein the composition comprises from 0.1 wt% to 8 wt% of the plasticizer, wherein wt% is by total weight of the composition.

Aspect 70 the composition of any one of aspects 1 to 69, wherein the composition further comprises a corrosion inhibitor.

The composition of aspect 71. the composition of aspect 70, wherein the corrosion inhibitor comprises a zinc phosphate-based corrosion inhibitor.

Aspect 72. the composition of any of aspects 70-71, wherein the composition comprises from 0.1 wt% to 10 wt% of the corrosion inhibitor, wherein wt% is by total weight of the composition.

Aspect 73. the composition of any one of aspects 1 to 72, wherein the composition further comprises a flame retardant.

Aspect 74. the composition of aspect 73, wherein the flame retardant comprises aluminum hydroxide, magnesium hydroxide, zinc borate, antimony oxide, hydromagnesite, Aluminum Trihydroxide (ATH), calcium phosphate, titanium oxide, zinc oxide, magnesium carbonate, barium sulfate, barium borate, kaolinite, silica, antimony oxide, halogenated hydrocarbons, halogenated esters, halogenated ethers, chlorinated and/or brominated flame retardants, organophosphorus compounds, organonitrogen compounds, or a combination of any of the foregoing.

The composition of any of aspects 74-75, wherein the composition comprises from 0.1 wt% to 10 wt% of the flame retardant, wherein wt% is by total weight of the composition.

Aspect 76. a cured composition prepared from the composition of any one of aspects 1-73.

Aspect 77. a component comprising the cured composition of aspect 76.

Aspect 78 a vehicle comprising the cured composition of aspect 76 or the part of aspect 77.

Aspect 79 the vehicle of aspect 78, wherein the vehicle comprises an aerospace vehicle.

Aspect 80. a method of sealing a component, the method comprising: applying a composition according to any one of aspects 1 to 73 to a surface of a part; and curing the applied composition to seal the part.

Aspect 81. a component sealed using the method of aspect 80.

Aspect 82 a sealant system, comprising: (a) a first component, wherein the first component comprises a polysulfide prepolymer; and (b) a second component, wherein the second component comprises a polysulfide cure activator; wherein at least one of the first component and the second component independently comprises: a synergist comprising a polyether; a porous material; a polysulfide curing accelerator; or a combination of any of the foregoing, and wherein the sealant system comprises from 0.1 wt% to 10 wt% of the synergist, wherein wt% is based on the total weight of the first component and the second component.

Aspect 83. the sealant system of aspect 82, wherein the porous material comprises silica.

Aspect 84. a cured sealant prepared from the sealant system of any one of aspects 80-81.

Aspect 85. a component comprising the cured sealant of aspect 84.

Aspect 86. a vehicle comprising the cured sealant of any one of aspects 84 or the component of aspect 85.

The vehicle of aspect 86, wherein the vehicle comprises an aerospace vehicle.

Aspect 88. a method of sealing a component, the method comprising: combining the first component and the second component of the sealant system according to any one of aspects 82 and 83 to provide a curable sealant composition; applying the curable sealant composition to a surface of a part; and curing the applied sealant composition to seal the part.

Aspect 89. a component sealed using the method of aspect 88.

Aspect 90 a vehicle comprising the sealed component of aspect 89.

Aspect 91 the vehicle of aspect 90, wherein the vehicle comprises an aerospace vehicle.

Examples of the invention

The examples provided in this disclosure are further illustrated by reference to the following examples, which describe the compositions and uses provided in this disclosure. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the present disclosure.

Example 1

Sealant composition

A manganese dioxide cured polysulfide sealant similar to that described in U.S. patent No. 4,623,711 was used. The sealant consists of two components; the two components are a base component and an accelerator component.

The compositions of the base component and the accelerator component of the sealant are shown in tables 1 and 2, respectively.

Table 1 base components.

Base component	Amount (wt%)
		Polysulfide prepolymers	49
Filler material	34
		Phenolic resin	8
TiO2	3.5
		Polysulfide curing accelerator	0.46
Additive/solvent	5

TABLE 2 Accelerator component.

The polyether is combined with a base component and the base component is combined and mixed with an accelerator component in a 10:1 wt% ratio to provide a curable polysulfide sealant. The composition of the curable polysulfide sealant is shown in table 2.

TABLE 3 curable sealant composition.

Components	Amount (wt%)
		Polysulfide prepolymers1	45
Non-porous inorganic filler2	34
		Porous hydrophobic silica	1
Phenolic resin	7
		Solvent and hydrogenated terphenyl plasticizer	7
Polysulfide curing activators	5
		Polysulfide curing accelerator MnO2	0.7
Additive agent	1

¹Polysulfide resins, U.S. patent No. 4,623,711.

²TiO₂(3 wt% of the composition), calcium carbonate (30 wt% of the composition) and talc (0.7 wt% of the composition).

The curable sealant composition contained about 1 wt% porous hydrophobic silica.

To evaluate the effect of various polyether synergists shown in table 4 on the cure rate of polysulfide sealants, the polyether synergist was added to the base component of the sealant and the base component and accelerator component were combined. Unless otherwise stated, the samples were cured in a controlled humidity chamber at 25 ℃ at 50% relative humidity until a constant final hardness was achieved.

TABLE 4 polyether.

¹ 350, methoxypolyethylene glycol having an average molecular weight of 335Da to 365Da and an average hydroxyl number (mg KOH/g) of 154 to 167, available from Dow Chemical Co.

² MPEG350, average molecular weight 430Da andand hydroxyl numbers of 127 to 140mg KOH/g (determined according to ISO 3657; 19-09) of methoxypolyethylene glycol methacrylate, available from GEO specialty Chemicals.

³ SR 415, ethoxylated trimethylolpropane triacrylate of molecular weight 428Da, available from echoma (Arkema).

⁴ X-35, a nonionic octylphenol ethoxylate, available from the Dow chemical company.

⁵ X-100, a nonionic octylphenol ethoxylate, available from the Dow chemical company.

⁶ X-405, a nonionic octylphenol ethoxylate, available from the Dow chemical company.

⁷Propylene glycol 725 having a molecular weight of 760Da and a hydroxyl number of 141.9 to 151.9mg KOH/g, available from Covestro.

⁸ 650, polytetramethylene ether glycol having an average molecular weight of 230Da to 270Da and a hydroxyl number of 415.6 to 487.8mg KOH/gm, available from Lycra (The Lycra Company).

⁹ 17R4, poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (A)Propylene glycol) having a number average molecular weight of 2,700 and a polyethylene glycol content of 40%, available from basf.

¹⁰Voranol 220-056N, propylene glycol with an average molecular weight of 2,000Da and a hydroxyl number of 56mg KOH/g, available from the Dow chemical company.

¹¹ 220-110N, propylene glycol having an average molecular weight of 1,000Da and a hydroxyl number of 110mg KOH/g, available from the Dow chemical company.

¹² 750, methoxypolyethylene glycols having an average molecular weight of 715Da to 785Da and an average hydroxyl number (mg KOH/g) of 71 to 78, available from the Dow chemical company.

¹³15-crown-5, 1,4,7,10, 13-pentaoxacyclopentadecane, available from TCI USA (TCI America).

Example 2

Curing profile of sealants incorporating polyether 2 or polyether 3

The shore a hardness during cure of the sealant of example 1 containing polyether 2 or polyether 3, as determined using a type a durometer according to ASTM D2240, was compared to a control sealant without the polyether synergist. The results are presented in table 5 and fig. 1 (polyether, wt%). The amount of polyether used in the various sealant compositions is expressed as wt% of the total weight of the curable sealant composition.

TABLE 5 Shore A hardness during curing.

Example 3

Curing profile of sealants incorporating polyether 1 or polyether 2

The shore a hardness of the sealant of example 1 containing polyether 1 or polyether 2 during cure was compared to a control sealant without the polyether synergist. The results are presented in table 6 and fig. 2 (polyether, wt%). The amount of polyether in each sealant composition is expressed as wt% of the total weight of the curable sealant composition.

TABLE 6 Shore A hardness during curing.

Example 4

Curing profile of sealants incorporating polyether 1 or polyether 2

The shore a hardness of the sealants containing polyether 1 or polyether 2 during curing was compared to the control sealant. The results are presented in table 7 and fig. 3 (polyether, wt%). The amount of polyether used in the various sealant compositions is expressed as wt% of the total weight of the curable sealant composition.

TABLE 7 Shore A hardness during curing.

Example 5

Curing curves for sealants incorporating polyethers 4-6

The shore a hardness of the sealant of example 1 containing polyether 4, polyether 5 or polyether 6 during curing was compared to the control sealant. The results are presented in table 8 and fig. 4 (polyether, wt%). The amount of polyether in each sealant composition is expressed as wt% of the total weight of the curable sealant composition. In addition, to determine the effect of water on the cure rate of the sealant, 1.7 wt% or 7.8 wt% water was added to both control sealant compositions.

TABLE 7 Shore A hardness during curing.

Example 6

Solvent resistance of cured sealants

The% swelling of the cured sealant of example 1 with polyether 1 or polyether 4 and the sealant without polyether is shown in table 9 and fig. 5 (polyether, wt%). The sealant was cured at 25 ℃ for 2 days, and then at 60 ℃ for 1 day. The cured sealant was then immersed in 3% NaCl or JRF type 1 for 7 days at 60 ℃. The tests were performed in triplicate.

TABLE 9 percent swell after immersion in 3% NaCl or JRF form I.

Example 7

Curing profile of sealants incorporating polyether 8 or polyether 9

The shore a hardness of the sealant of example 1 containing polyether 8 or polyether 9 during curing is shown in table 10 and fig. 6 (polyether, wt%). The sealant contains 4.3 wt% and 0.9 wt% of the corresponding polyethers, with the wt% based on the total weight of the curable sealant composition.

TABLE 10 Shore A hardness during curing.

Example 8

Sealants incorporating polyethers 10-13Curing curve of

In table 11 and fig. 7 (polyether, wt%), the shore a hardness of the sealant of example 1 containing one of polyethers 10-13 during curing was compared to a sealant without the polyether. The sealant contains 4.3 wt% of the corresponding polyether, where the wt% is based on the total weight of the curable sealant composition.

TABLE 11 Shore A hardness during curing.

Example 9

Effect of silica content on curing Curve

The effect of silica content on the efficacy of the polyether synergist was evaluated for different silica contents.

The composition of the base component is provided in table 1. To prepare the base component, the polysulfide resin and adhesion promoter are combined and mixed, and then the filler and remaining additives are combined and mixed. The materials were mixed intermittently using a Flaktek mixer (plug-in). Additional combined amounts of the remaining components were then added and mixed thoroughly using a Flaktek mixer.

Additional filler components are added to the encapsulant. The additional filler content contains varying amounts of porous hydrophobic silica ((R))D13) And an additional amount of calcium carbonate (C: (A)2G 13UF) to bring the amount of additional filler content to 1.2 wt% of the total weight of the curable sealant. The amount of porous hydrophobic silica in the additional filler component varies between 0 wt%, 50 wt%, 100 wt% and 125 wt%, based on the total weight of the additional filler component. Thus, the amount of porous hydrophobic silica is 0 wt%, 0.6 wt% based on the total weight of the sealant1.2 wt% and 1.5 wt%. The nominal amounts of calcium carbonate and porous hydrophobic silica are typically about 33 wt% and 1.2 wt%, respectively, based on the total weight of the sealant.

The base component is then combined with MnO using Flaktek₂The accelerator component (see example 1, table 2) was mixed in a ratio of 10:1 wt% to provide a curable sealant composition.

The sealant composition does not contain a polyether synergist.

The sealant composition was molded into a disc (2 inches (50.8mm) in diameter and 0.5 inches (12.7mm) deep) and cured in a controlled humidity chamber at 50% RH, 25 ℃ until a constant final hardness was achieved. Shore a hardness was measured at intervals during curing. The results are shown in Table 12 and FIG. 8 (polyether, wt%).

TABLE 12 Shore A hardness during curing.

Example 10

Effect of non-porous fillers on the curing Curve

Formulation of the base component was similar to example 9, except that the base component did not contain silica and did not have TiO₂(Rutile R900 grade), a blend of TiO₂Replacing by an equal weight% of calcium carbonate2G 13UF)。

The composition of the accelerator component is the same as in table 2.

Polysulfide cure accelerator DPTT (dipentamethylenethiuram tetrasulfide) was added to the final wt% of 1.4 wt% (50%) or 2.7 wt% (100%), based on the total weight of the accelerator component.

The binder and accelerator components were then mixed in a ratio of 10:1 wt% using a Flaktek mixer to provide a curable sealant composition.

The sealant composition was molded into a disc (2 inches (50.8mm) in diameter and 0.5 inches (12.7mm) deep) and cured in a controlled humidity chamber at 50% RH, 25 ℃ until a constant final hardness was achieved. Shore a hardness was measured at intervals during curing. The results are shown in table 13 and fig. 9.

TABLE 13 Shore A hardness during curing.

Example 11

Effect of hydrophilic silica on the curing Curve

Formulation of the base component was similar to example 4, except that hydrophilic silica (B)200 of a carrier; hydrophilic fumed silica, BET 175-²/g, 0.2 to 0.3. mu. m d50) instead of hydrophobic silica.

The binder and accelerator components were then mixed using Flaktek in a ratio of 10:1 wt% to provide a curable sealant composition.

The sealant composition was molded into a disc (2 inches (50.8mm) in diameter and 0.5 inches (12.7mm) deep) and cured in a controlled humidity chamber at 50% RH, 25 ℃ until a constant final hardness was achieved. Shore a hardness was measured at intervals during curing. The results are shown in table 14 and fig. 10.

TABLE 14 Shore A hardness during curing.

The results show that the sealant cure profiles are similar whether hydrophobic or hydrophilic silica is used.

Example 12

Effect of silica type on curing Curve

The formulation of the base component was similar to example 9, except that the silica was replaced by one of the following silicas: (1) inhibisil^TM73(I-73), a calcium-modified silica; (2) Lo-Vel^TM2018(LV 2018), a wax-treated silica; (3) Lo-Vel^TM6000(LV 6000), an untreated silica; and (4) Hi-Sil^TMT7000, a hydrophilic precipitated silica. Silica is available from PPG industries. With and without polyether 1: (350) Sealant formulations with various silicas were tested. Control sealants contain hydrophobic silica: (D13)。

The sealant composition was molded into a disc (2 inches (50.8mm) in diameter and 0.5 inches (12.7mm) deep) and cured in a controlled humidity chamber at 50% RH, 25 ℃ until a constant final hardness was achieved. Shore a hardness was measured at intervals during curing. The results are shown in Table 15 and FIG. 11 (polyether, wt%).

TABLE 15 Shore A hardness during curing.

As shown in table 15 and fig. 11, accelerated cure of the sealant containing the polyether synergist was observed regardless of the silica type.

Example 13

Filler properties

Table 16 shows some of the silicas and TiO used in the examples₂The nature of (c).

TABLE 16 Filler Properties.

Finally, it should be noted that there are alternative ways of implementing the embodiments disclosed herein. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, the claims should not be limited to the details given herein, and are entitled to their full scope and equivalents.