Multilayer systems and methods of making multilayer systems

Abstract

To provide multilayer systems and methods of making the multilayer systems.SOLUTION: Methods of making multilayer systems comprising a sealant layer by extruding a co-reactive sealant composition are disclosed. The methods can be used to fabricate multilayer systems in which individual layers have different cured properties. The individual layers can also have an inhomogeneous concentration of one or more constituents within a layer. The multilayer systems can be made using three-dimensional printing that facilitates the use of a wide range of co-reactive compositions.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 62 / 803,727, filed February 11, 2019, which is incorporated by reference in its entirety.

[0002] The present disclosure relates to a method for producing a multi-layer system comprising at least one sealant layer, a multi-layer system produced using this method, and the use of the multi-layer system. Each individual layer of the multi-layer system can be designed to have desired properties. The individual layers of the multi-layer system can also have a non-uniform concentration of one or more components in the individual layers. The multi-layer system can be produced using an extrusion method such as 3D printing. The multi-layer system can be used as a sealant. [Background technology]

[0003] Sealants are typically provided as homogeneous compositions that are applied to a substrate. In one-component systems, the sealant is applied to a substrate and curing is initiated by the application of energy, such as exposure to ultraviolet light. In two-component systems, the individual components are combined and mixed prior to use, and the curing reaction proceeds when the reactive components are combined. Performance attributes of the cured sealant may include, for example, one or more of chemical resistance, low temperature flexibility, hydrolytic stability, high temperature resistance, tensile strength, elongation, substrate adhesion, adhesion to adjacent layers, tack-free time, time to Shore 10A hardness, electrical conductivity, EMI / RFI shielding, static dissipation, thermal conductivity, low density, corrosion resistance, surface hardness, fire resistance, UV resistance, and rain erosion resistance. Multilayer systems with at least one sealant and methods for producing sealant systems with one or more of these attributes are desirable. Summary of the Invention [Means for solving the problem]

[0004] According to the present invention, a method of making a multi-layer system comprising two or more layers, one or more of the layers comprising a sealant layer, comprises the steps of: (a) mixing a first component and a second component to form a co-reactive sealant composition, the co-reactive sealant composition comprising a first reactive compound and a second reactive compound, the first reactive compound being reactive to the second reactive compound; (b) extruding the co-reactive sealant composition to form an extrudate; and (c) depositing the extrudate to form a sealant layer. The present invention provides, for example, the following items: (Item 1) 1. A method for producing a multi-layer system comprising two or more layers, one or more of said layers comprising a sealant layer, comprising: (a) mixing a first component and a second component to form a co-reactive sealant composition, the co-reactive sealant composition comprises a first reactive compound and a second reactive compound; the first reactive compound is reactive to the second reactive compound; (b) extruding the co-reactive sealant composition to form an extrudate; (c) depositing the extrudate to form the sealant layer. (Item 2) 2. The method of claim 1, wherein the depositing comprises three-dimensional printing. (Item 3) 3. The method of claim 1 or 2, wherein depositing comprises depositing the extrudate onto a bottom layer of the multi-layer system. (Item 4) depositing a first co-reactive composition underlying the deposited sealant layer to form an underlayer; and / or depositing a second co-reactive composition over the sealant layer to form an upper layer. wherein the first co-reactive composition and the second co-reactive composition comprise a different composition than the sealant layer. (Item 5) 5. The method of claim 4, wherein the first co-reactive composition is different from the second co-reactive composition. (Item 6) 6. The method of any one of items 1 to 5, wherein any of the co-reactive sealant compositions comprises a thermosetting composition. (Item 7) 7. The method according to any one of items 1 to 6, wherein the layers of the multi-layer system each comprise a thermosetting material. (Item 8) 8. The method of any one of items 1 to 7, wherein the cross-sectional profile of the extrudate has a uniform composition across the cross-sectional profile. (Item 9) 8. The method of any one of items 1 to 7, wherein the cross-sectional profile of the extrudate has a non-uniform composition across the cross-sectional profile. (Item 10) 10. The method according to any one of items 1 to 9, wherein an outermost layer of the two or more layers of the multi-layer system comprises a sealant layer. (Item 11) 11. The method of any one of items 1 to 10, wherein each of the layers of the multi-layer system independently comprises a sealant layer or a non-sealant layer. (Item 12) 12. The method of any one of the preceding claims, wherein the co-reactive sealant composition comprises a prepolymer comprising a chemically resistant backbone. (Item 13) 13. The method according to any one of the preceding claims, wherein the co-reactive sealant composition comprises a sulfur content of greater than 10 wt.%, the wt.% being based on the total weight of the organic components of the co-reactive sealant composition. (Item 14) 14. The method according to any one of the preceding claims, wherein the co-reactive sealant composition comprises a sulfur-containing prepolymer. (Item 15) Item 15. The method of item 14, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing. (Item 16) 16. The method of claim 14 or 15, wherein the sulfur-containing prepolymer comprises a sulfur content of more than 10 wt%, the weight percent being based on the total weight of the sulfur-containing prepolymer. (Item 17) 17. The method according to any one of items 1 to 16, wherein the first reactive compound is reactive to the second reactive compound at a temperature below 50° C. (Item 18) the first reactive compound is reactive to the second reactive compound in the presence of a catalyst and / or a polymerization initiator; 18. The method according to any one of items 1 to 17, wherein the catalyst and / or polymerization initiator is capable of catalyzing and / or initiating a reaction between the first reactive compound and the second reactive compound. (Item 19) 20. The method of claim 18, further comprising activating the polymerization initiator before, during, and / or after depositing the extrudate. (Item 20) the first component comprises the first reactive compound and the second reactive compound; 20. The method according to any one of items 1 to 19, wherein the second component comprises a catalyst, a cure activator, and / or a polymerization initiator for the reaction between the first reactive compound and the second reactive compound. (Item 21) 20. The method according to any one of items 1 to 19, wherein the first component comprises the first reactive compound and the second component comprises the second reactive compound. (Item 22) the first reactive compound comprises a polyamine and / or a polyol and the second reactive compound comprises a polyisocyanate; the first reactive compound comprises a polyamine and the second reactive compound comprises a polyepoxide; or the first reactive compound comprises a Michael acceptor and the second reactive compound comprises a Michael donor; or 22. The method of any one of items 1 to 21, wherein the first reactive compound comprises a polythiol and the second reactive compound comprises a polythiol, a polyisocyanate, a polyalkenyl, a polyalkynyl, a polyepoxide, a Michael acceptor, or any combination of the foregoing. (Item 23) pumping the first component into a mixer using a first pump; 23. The method of any one of items 1 to 22, further comprising pumping the second component into the mixer using a second pump. (Item 24) 24. The method according to any one of items 1 to 23, further comprising the step of curing the deposited extrudate after depositing the extrudate. (Item 25) 25. The method of claim 24, wherein curing comprises curing the deposited extrudate at a temperature of less than 30°C. (Item 26) further comprising the step of combining one or more additional co-reactive compositions with said co-reactive sealant composition; extruding comprises coextruding the co-reactive sealant composition and the one or more additional co-reactive compositions to form a coextrudate; 26. The method according to any one of the preceding claims, wherein depositing comprises depositing the coextrudate to form a multi-layer system comprising one or more sealant layers. (Item 27) 27. The method of claim 26, wherein the one or more additional co-reactive compositions each independently comprise an additional co-reactive sealant composition or a co-reactive non-sealant composition. (Item 28) 28. The method of claim 26 or 27, wherein the co-reactive sealant composition and the adjacent additional co-reactive composition comprise the same cure chemistry. (Item 29) 29. The method of any one of items 26 to 28, wherein the co-reactive sealant composition and the adjacent additional co-reactive composition comprise different cure chemistries. (Item 30) 30. The method of any one of items 26 to 29, wherein the co-reactive sealant composition is reactive to adjacent additional co-reactive compositions. (Item 31) further comprising the step of combining the additive-containing composition with a portion of the additional co-reactive composition to form an additive-modified additional co-reactive composition, the additive-containing composition comprising an additive; 31. The method of any one of items 26 to 30, wherein extruding comprises coextruding the co-reactive sealant composition and the additive-modified additional co-reactive composition to form a coextrudate. (Item 32) 32. The method of claim 31, wherein the cross-sectional profile of the coextrudate has a non-uniform additive concentration. (Item 33) 33. The method of claim 31 or 32, wherein the extrudate is characterized in that the concentration of the additive is non-uniform in the longitudinal dimension of the coextrudate. (Item 34) 34. The method of any one of items 26 to 33, further comprising mixing a third component with a fourth component to form the one or more additional coreactive compositions. (Item 35) combining an additive-containing composition with a portion of the co-reactive sealant composition to form an additive-modified co-reactive sealant composition, the additive-containing composition comprising an additive; 35. The method according to any one of the preceding claims, further comprising extruding the additive-modified co-reactive sealant composition to form an extrudate. (Item 36) 36. The method of claim 35, wherein the cross-sectional profile of the extrudate has a non-uniform additive concentration. (Item 37) 37. The method of claim 35 or 36, wherein the extrudate is characterized in that the concentration of the additive is non-uniform in the longitudinal dimension of the extrudate. (Item 38) further comprising the step of combining an adhesion promoting composition with said co-reactive sealant composition; 38. The method of any one of the preceding claims, wherein extruding comprises coextruding the first co-reactive composition and the adhesion promoting composition. (Item 39) 39. The method according to any one of the preceding claims, further comprising the step of applying an adhesion promoting layer to the extrudate prior to depositing the extrudate. (Item 40) 40. A multi-layer system comprising a sealant layer produced by the method according to any one of items 1 to 39. (Item 41) 41. The multilayer system according to item 40, wherein adjacent layers are chemically and / or physically bonded. (Item 42) 42. The multi-layer system according to item 40 or 41, wherein the fracture energy of the fully cured multi-layer sealant is substantially the same as the fracture energies of the individual layers, said fracture energies being determined according to ASTM D7313. (Item 43) 43. The multilayer system according to any one of items 40 to 42, wherein each of the layers comprises a thermosetting material. (Item 44) 44. The multilayer system according to any one of items 40 to 43, wherein the layers each comprise a different thermosetting material. (Item 45) 45. The multilayer system according to any one of items 40 to 44, wherein the multilayer system meets or exceeds the requirements for aerospace sealants as set forth in AMS 3277. (Item 46) 46. ​​The multi-layer system according to any one of items 40 to 45, wherein one or more of the layers of the multi-layer sealant have a non-uniform composition cross-sectional profile. (Item 47) 47. The multi-layer system according to any one of items 40 to 46, wherein one or more of the layers of the multi-layer sealant have a non-uniform composition in the longitudinal dimension. (Item 48) 48. A part comprising a multilayer system according to any one of items 40 to 47. (Item 49) 49. The part of claim 48, wherein the part comprises an automotive vehicle part or an aerospace vehicle part. (Item 50) 48. A vehicle comprising a multilayer system according to any one of items 40 to 47. (Item 51) 51. The vehicle of claim 50, wherein the vehicle comprises an aerospace vehicle or an automotive vehicle. [Brief description of the drawings]

[0005] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure.

[0006] [Figure 1A] 1 shows a cross-sectional view of a multi-layer system including at least one sealant layer provided by the present disclosure. [Figure 1B] 1 shows a cross-sectional view of a multi-layer system including at least one sealant layer provided by the present disclosure. [Figure 1C] 1 shows a cross-sectional view of a multi-layer system including at least one sealant layer provided by the present disclosure. [Figure 1D] 1 shows a cross-sectional view of a multi-layer system including at least one sealant layer provided by the present disclosure. [Figure 2A] 1 shows a cross-sectional view of a layer of a multi-layer system provided by the present disclosure in which the concentration of a component varies through the thickness of the layer. [Figure 2B] 1 shows a cross-sectional view of a layer of a multi-layer system provided by the present disclosure in which the concentration of a component varies in the lateral dimension of the layer. [Diagram 3] 1 shows a cross-sectional view of a multi-layer system provided by the present disclosure, including a coating. [Figure 4]1 shows a cross-sectional view of an example co-extruder. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] For purposes of the following detailed description, the embodiments provided by this disclosure are It should be understood that various alternative variations and step sequences can be envisioned unless expressly indicated otherwise. Moreover, other than in any operating example, or where otherwise indicated, for example, all numbers expressing quantities of ingredients used in the specification and claims should be understood in all instances as being modified by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties obtained by the present invention. At the very least, and without any 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.

[0008] 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, however, any numerical values ​​inherently contain certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0009] It is also to be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges having a minimum recited value of 1 to a maximum recited value of 10 (inclusive), i.e., a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0010] "Alkanearene" refers to a hydrocarbon group having one or more aryl and / or arenediyl groups and one or more alkyl and / or alkanediyl groups, where aryl, arenediyl, alkyl, and alkanediyl are defined herein. Each aryl and / or arenediyl group may be any of the following: 6~12 , C 6~10 Each alkyl and / or alkanediyl group may be C 1~6 , C 1~4 , C 1~3 , methyl, methanediyl, ethyl, or ethane-1,2-diyl. The alkanearene group can be C 4~18 Alkanarenes, C 4~16 Alkanarenes, C 4~12 Alkanarenes, C 4~8 Alkanarenes, C 6~12 Alkanarenes, C 6~10 Alkanarenes, or C 6~9 It may be an alkane arene. Examples of alkane arene groups include diphenylmethane.

[0011] "Alkanarenediyl" refers to a diradical of an alkanarene group. The alkanarenediyl group is C 6~18 Alkane Arendiyl, C 6~16 Alkane Arendiyl, C 6~12 Alkane Arendiyl, C 6~8 Alkane Arendiyl, C 6~12 Alkane Arendiyl, C 6~10 Alkanearyl, or C 6~9 It can be an alkanarenediyl. An example of an alkanarenediyl group is diphenylmethane-4,4'-diyl.

[0012] "Alkanecycloalkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanediyl groups and one or more alkyl and / or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl, and alkanediyl are defined herein. Each cycloalkyl and / or cycloalkanediyl group is selected from the group consisting of C 3~6 , C 5~6 Each alkyl and / or alkanediyl group can be C 1~6 , C 1~4 , C 1~3 , methyl, methanediyl, ethyl, or ethane-1,2-diyl. 6~18 Alkanecycloalkane, C 6~16 Alkanecycloalkane, C 6~12 Alkanecycloalkane, C 6~8 Alkanecycloalkane, C 6~12 Alkanecycloalkane, C 6~10 Arcanci Chloroalkane, or C 6~9 It can be an alkanecycloalkane. Examples of alkanecycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

[0013] "Alkanecycloalkanediyl" refers to a diradical of an alkanecycloalkane group. The alkanecycloalkanediyl group is C 4~18 Alkanecycloalkanediyl, C 4~16 Alkanecycloalkanediyl, C 4~12 Alkanecycloalkanediyl, C 4~8 Alkanecycloalkanediyl, C 6~12 Alkanecycloalkanediyl, C 6~10 Alkanecycloalkanediyl, or C 6~9It can be an alkanecycloalkanediyl. Examples of alkanecycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.

[0014] "Alkanediyl" refers to, for example, an alkanediyl having 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 carbon atoms (C 1~3 ) refers to a diradical of a saturated, branched, or straight chain acyclic hydrocarbon group. A branched alkanediyl will be recognized as having at least 3 carbon atoms. An alkanediyl is a C 2~14 Alkanediyl, C 2~10 Alkanediyl, C 2~8 Alkanediyl, C 2~6 Alkanediyl, C 2~4 Alkanediyl, or C 2~3 It may be alkanediyl. Examples of alkanediyl groups include methane-diyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl and isopropane-1,2-diyl (e.g., -CH2CH2CH2- and -CH(CH3)CH2-), butane-1,4-diyl (-CH2CH2CH2CH2-), pentane-1,5-diyl (-CH2CH2CH2CH2CH2-), hexane-1,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, and dodecane-1,12-diyl. The alkanediyl group may contain single, double, and / or triple bonds between carbon atoms.

[0015] An "alkenyl" group refers to the structure -CR=C(R), where the alkenyl group is a radical that is attached to a larger molecule. In such embodiments, each R can be independently selected from, for example, hydrogen and C 1~3Each R can be hydrogen and the alkenyl group can have the structure -CH=CH2.

[0016] "Alkoxy" refers to an -OR group, where R is alkyl, as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. An alkoxy group is a C 1~8 Alkoxy, C 1~6 Alkoxy, C 1~4 Alkoxy, or C 1~3 It may be alkoxy.

[0017] "Alkyl" refers to a monoradical of a saturated, 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. A branched alkyl will be recognized as having a minimum of 3 carbon atoms. An alkyl group is any of the groups listed below: 1~6 Alkyl, C 1~4 Alkyl, or C 1~3 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, and tetradecyl. 1~6 Alkyl, C 1~4 Alkyl, and C 1~3 It is an alkyl.

[0018] "Arenediyl" refers to a diradical monocyclic or polycyclic aromatic group. Examples of arenediyl groups include benzene-diyl and naphthalene-diyl. Arene The diyl group is C 6~12 Arendjiil, C 6~10 Arendjiil, C 6~9 It may be arene-diyl, or benzene-diyl.

[0019] "Catalyst" refers to a substance that increases the rate of a reaction without altering the overall standard Gibbs energy change in the reaction.

[0020] For example, when referring to a chemical group defined by a number of carbon atoms, the chemical group is intended to include all subranges of carbon atoms as well as the specific number of carbon atoms. 2~10 Alkanediyl is C 2~4 Alkanediyl, C 5~7 Includes alkanediyl, and other subranges, C2 alkanediyl, C6 alkanediyl, and other specified numbers of alkanediyls from 2 to 10 carbon atoms.

[0021] "Coating" refers to a thin film, such as a membrane, having a coating and dry thickness of less than 500 μm, less than 100 μm, or less than 50 μm. A coating may have a thickness less than the thickness of the layers that form the multilayer system.

[0022] "Component" refers to a composition that is not co-reactive until the components of the component are combined and mixed with another component to form a co-reactive composition.

[0023] A compound having a reactive functional group refers to a compound having a functional group that can react with a complementary reactive functional group of another compound. The reactive functional group can be attached to the terminus of the compound or can be attached to the backbone of the compound.

[0024] "Component" refers to an organic or inorganic compound. Compositions and components may include one or more components. Examples of components include prepolymers, monomers, polyfunctionalizing agents, and additives disclosed herein.

[0025] Multifunctionalizing Agent B(-V) z The "core" in refers to part B.

[0026] The "core" of a compound or polymer refers to the division between reactive groups. For example, the core of polythiol HS-R-SH is -R-. The core of a compound or prepolymer can also be called the backbone of a compound or the backbone of a prepolymer. The core of a polyfunctionalizing agent can be an atom or a structure such as a cycloalkane, substituted cycloalkane, heterocycloalkane, substituted heterocycloalkane, arene, substituted arene, heteroarene, or substituted heteroarene, to which a moiety having a reactive functional group is attached.

[0027] A "co-reactive composition" refers to a composition that includes at least two reactive compounds that can react with each other. A co-reactive composition refers to a composition that includes two or more co-reactive compounds that can react at temperatures, for example, below 50°C, below 40°C, below 30°C, or below 20°C. The reaction between the two or more reactive compounds can be initiated by combining and mixing the two or more co-reactive compounds, adding a catalyst to the co-reactive composition that includes the two or more co-reactive compounds, and / or activating a polymerization initiator in the co-reactive composition that includes the two or more co-reactive compounds. The co-reactive composition can be formed, for example, by combining and mixing a first reactive component that includes a first reactive compound and a second reactive component that includes a second reactive compound, where the first reactive compound can react with the second reactive compound. The co-reactive composition can be a thermosetting composition that forms a thermoset material upon curing.

[0028] "Co-reactive non-sealant composition" means a co-reactive composition that is not formulated as a sealant. Although the cured co-reactive non-sealant composition may exhibit some properties of a sealant, the primary function of the cured co-reactive non-sealant composition is not to act as a sealant.

[0029] "Co-reactive sealant composition" refers to a co-reactive composition that is formulated as a sealant.

[0030] "Co-reactive three-dimensional printing" refers to a method disclosed herein in which a co-reactive composition is extruded through a nozzle or by extrusion in successive layers to form a part.

[0031] "Cycloalkanediyl" refers to a diradical saturated monocyclic or polycyclic hydrocarbon group. A cycloalkanediyl group is a C 3~12 Cycloalkanediyl, C 3~8 Cycloalkanediyl, C 3~6 Cycloalkanediyl, or C 5~6 Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

[0032] "Cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon monoradical group. A cycloalkyl group is a C 3~12 Cycloalkyl, C 3~8 Cycloalkyl, C 3~6 Cycloalkyl, or C 5~6 It may be cycloalkyl.

[0033] "Heteroalkanediyl" refers to an alkanediyl group in which one or more of the carbon atoms have been replaced with a heteroatom such as N, O, S, or P. In a heteroalkanediyl, the one or more heteroatoms can include N or O.

[0034] "Cure time" refers to the period of time from when the curing reaction of the coreactive composition is first initiated, for example, by combining and mixing the coreactive components to form the coreactive composition and / or by exposing the coreactive composition to actinic radiation, until a layer prepared from the coreactive composition exhibits a hardness of Shore 30A at 25° C. and 50% relative humidity. For actinic radiation curable compositions, cure time refers to the period of time from when the coreactive composition is first exposed to actinic radiation to the point at which a layer prepared from the exposed coreactive composition exhibits a hardness of Shore 30A at 25° C. and 50% relative humidity.

[0035] A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent or between two atoms. For example, -CONH2 is bonded through a carbon atom.

[0036] "Derived from," as in "moiety derived from a compound," refers to a moiety formed upon reaction of a parent compound with a reactant. For example, a bis(alkenyl) compound, CH2=CH-R-CH=CH2, can react with another compound, such as a compound having a thiol group, to form a moiety, -(CH2)2-R-(CH2)2-, derived from the reaction of the alkenyl group with the thiol group. As another example, for a parent diisocyanate having the structure O=C=NRN=C=O, a moiety derived from the diisocyanate has the structure -C(O)-NH-R-NH-C(O)-.

[0037] "Derived from the reaction of -R with a thiol" refers to the moiety -R'- resulting from the reaction of a thiol group with a moiety that contains a group reactive to a thiol group. For example, the group R- can contain CH2=CH2-O-, where the alkenyl group CH2=CH- is reactive to a thiol group -SH. Upon reaction with a thiol group, the moiety -R'- is -CH2-CH2-CH2-O-.

[0038] "Extrudate" refers to a coreactive composition extruded through a nozzle or die. Coextrudate refers to two or more coreactive compositions extruded simultaneously through a nozzle or die.

[0039] "Formed from" or "prepared from" refers to open, e.g., inclusive, claim language. Thus, a composition "formed from" or "prepared from" a list of recited components is intended to be a composition that includes at least the recited components or reaction products of at least the recited components, and may further include other unrecited components used to form or prepare the composition.

[0040] "Energy to Break" is determined in accordance with ASTM D7313.

[0041] Glass transition temperature T g was determined by dynamic mechanical analysis (DMA) using a TA Instruments Q800 instrument with a frequency of 1 Hz, an amplitude of 20 microns, and a temperature ramp from -80°C to 25°C. g is identified as a peak in the tan δ curve.

[0042] "Heterocycloalkanediyl" refers to a cycloalkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom such as N, O, S, or P. In a heterocycloalkanediyl, the one or more heteroatoms can include N or O.

[0043] Monomer refers to a low molecular weight compound, and may have, for example, a molecular weight of less than 1,000 Da, less than 800 Da, less than 600 Da, less than 500 Da, less than 400 Da, or less than 300 Da. Monomers may have, for example, a molecular weight of 100 Da to 1,000 Da, 100 Da to 800 Da, 100 Da to 600 Da, 150 Da to 550 Da, or 200 Da to 500 Da. Monomers may have a molecular weight of more than 100 Da, more than 200 Da, more than 300 Da, more than 400 Da, more than 500 Da, more than 600 Da, or more than 800 Da. Monomers may have a reactive functionality of 2 or more than 2, for example, 2 to 6, 2 to 5, or 2 to 4. Monomers may have a functionality of 2, 3, 4, 5, 6, or any combination of the foregoing. The monomers can have an average reactive functionality of, for example, 2-6, 2-5, 2-4, 2-3, 2.1-2.8, or 2.2-2.6. Reactive functionality refers to the number of reactive functional groups per molecule. A combination of molecules with different numbers of reactive functional groups can have a non-integer average number of reactive functional groups.

[0044] "Polyalkenyl" refers to a compound having at least two alkenyl groups. At least two of the alkenyl groups may be alkenyl groups, and such polyalkenyl groups may be referred to as alkenyl-terminated compounds. The alkenyl groups may also be pendant alkenyl groups. The polyalkenyl may be a dialkenyl having two alkenyl groups. The polyalkenyl may have three or more than three alkenyl groups, for example, 3 to 6 alkenyl groups. The polyalkenyl may include a single type of polyalkenyl, may be a combination of polyalkenyls having the same alkenyl functional group, or may be a combination of polyalkenyls having different alkenyl functional groups.

[0045] The polyfunctionalizing agent may have the structure: B(-V) z In the formula, B is the core of the polyfunctionalizing agent, each V is a moiety terminated with a reactive functional group such as a thiol group, an alkenyl group, an epoxy group, an isocyanate group, or a Michael acceptor group, and z is an integer from 3 to 6, e.g., 3, 4, 5, or 6. Each -V may have the structure -R-SH or -R-CH=CH2, for example, where R is, for example, C 2~10 Alkanediyl, C 2~10 Heteroalkanediyl, substituted C 2~10 Alkanediyl or substituted C 2~10 The moiety V can be a heteroalkanediyl. Reacting the moiety V with another compound gives the moiety -V 1 - is obtained, which is said to result from reaction with another compound. For example, if V is -R-CH=CH2 and this is reacted with, for example, a thiol group, the moiety V 1 is -R-CH2-CH2- and is derived from this reaction.

[0046] "Polymerization initiator" refers to a compound capable of initiating a polymerization reaction after activation of the polymerization initiator. The polymerization initiator can be activated, for example, upon exposure to actinic radiation, heat, and / or shear forces.

[0047] "Prepolymer" refers to homopolymers and copolymers. For thiol-terminated prepolymers, the molecular weight is the number average molecular weight "Mn" determined by end group analysis using iodometric titration. For prepolymers that are not thiol-terminated, the number average molecular weight is determined by gel permeation chromatography using polystyrene standards. A prepolymer contains a backbone and reactive groups that can react with another compound, such as a curing agent or crosslinker, to form a cured polymer. A prepolymer contains multiple repeating moieties linked together, which may be the same or different. The multiple repeating moieties make up the backbone of the prepolymer.

[0048] "Prepolymer backbone" refers to the division between reactive functional groups of a prepolymer. The prepolymer backbone typically includes repeating moieties. For example, HS-(R)n The skeleton of polythiol having the -SH structure is -(R) n -It is.

[0049] "Reaction product of" means the chemical reaction product of at least the listed reactants, and may include partially reacted products, as well as fully reacted products, and other reaction products present in lesser amounts. For example, "a prepolymer comprising the reaction product of the reactants" refers to a prepolymer or combination of prepolymers that is the reaction product of at least the listed reactants. The reactants may further include additional reactants.

[0050] "Reactive compound" refers to a compound that is reactive to another compound. A reactive compound may contain one or more than one functional group that is reactive to a functional group of another compound.

[0051] "Sealant layer" refers to a layer that functions as a sealant upon curing. The sealant layer may be prepared from a co-reactive sealant composition.

[0052] Shore A hardness is measured using a Type A durometer according to ASTM D2240.

[0053] The specific gravity and density of the particles are determined according to ISO 787-11.

[0054] A "sulfur-containing prepolymer" is a polymer having a backbone that contains one or more thioether-S in the backbone of the prepolymer. n -group, where n can be, for example, 1 to 6. Prepolymers containing only thiols or other sulfur-containing groups as either the group or pendant groups of the prepolymer are not included in sulfur-containing prepolymers. A prepolymer backbone refers to the portion of the prepolymer that has repeating segments. Thus, HS-RR(-CH2-SH)-[-R-(CH2)2-S(O)2-(CH2)-S(O)2] nA prepolymer having the structure -CH=CH2, where each R is a moiety that does not contain a sulfur atom in the prepolymer backbone, is not included in the sulfur-containing prepolymer. Sulfur-containing prepolymers include those having the structure [(CH2)-S(O)2]-CH=CH2, where at least one R is a moiety containing a sulfur atom, such as a thioether group. Examples of sulfur-containing prepolymers include polythioether prepolymers, polysulfide prepolymers, sulfur-containing polyformal prepolymers, and monosulfide prepolymers.

[0055] "Substituted" refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituents. Substituents include, for example, halogen, -S(O)2OH, -S(O)2, -SH, -SR (where R is C 1~10 alkyl), -COOH, -NO2, -NR2 (wherein each R is independently hydrogen and C 1~10 (including alkyl), -CN, =O, C 1~10 Alkyl, -CF3, -OH, Phenyl, C 2~10 Heteroalkyl, C 5~6 Heteroaryl, C 1~10 Alkoxy, or -COR (wherein R is C 1~10 The substituents may include, for example, -OH, -NH2, or C 1~3 It may be alkyl.

[0056] "Tack-free time" refers to the time period from when the curing reaction of the coreactive composition is initiated, for example, by mixing two coreactive components or by exposing the coreactive composition to energy such as UV radiation, to the time when the coreactive composition is no longer tack-free. The tack-free property is determined by applying a polyethylene sheet to the surface of the layer with hand pressure and observing whether the sealant adheres to the surface of the polyethylene sheet, where the layer is considered tack-free if the polyethylene sheet easily separates from the layer. For actinic radiation curable coreactive compositions, the tack-free time refers to the time from when the coreactive composition is exposed to actinic radiation to the time when the layer prepared from the coreactive composition is no longer tack-free.

[0057] Tensile strength and elongation are measured in accordance with AMS3279.

[0058] "Thermoset" refers to a cured thermosetting polymer composition.

[0059] "Thermosetting composition" refers to a composition that contains a coreactive compound that is irreversibly transformed by curing into a pourable, insoluble polymer network. Curing is a chemical process that converts a prepolymer and a curing agent into a higher molecular weight polymer and then into a polymer network. The result of curing in a chemical reaction that produces extensive crosslinking between the polymer network is a highly branched structure in which virtually each building block is connected to each other and to macroscopic phase boundaries by many paths through the structure, the number of such paths increasing with the average number of intervening building blocks, and these paths must, on average, extend with the structure.

[0060] Reference will now be made to certain compounds, compositions, and methods of the invention. The disclosed compounds, compositions, and methods are not intended to limit the scope of the claims. On the contrary, the claims are intended to cover all alternatives, modifications, and equivalents.

[0061] A method of making a multi-layer system comprising two or more layers, one or more of the layers comprising a sealant layer, comprises: (a) mixing a first component and a second component to form a co-reactive sealant composition, the co-reactive sealant composition comprising a first reactive compound and a second reactive compound, the first reactive compound being reactive to the second reactive compound; (b) extruding the co-reactive sealant composition to form an extrudate; and (c) depositing the extrudate to form a sealant layer.

[0062] A sealant composition refers to a material that, when cured, forms a sealant that can withstand at least one of atmospheric conditions, such as moisture and / or temperature, and has the ability to at least partially block the permeation of substances such as water, solvents, fuels, hydraulic fluids, and other liquids and gases. The sealant may exhibit chemical resistance, such as resistance to fuels, hydraulic fluids, solvents, greases, lubricants, salt spray, gases, oils, and / or cleaning fluids. A chemically resistant material may exhibit a swelling rate of less than 25%, less than 20%, less than 15%, or less than 10% after immersion in a chemical at 70° C. for 7 days, as determined according to EN ISO 10563. The multilayer system prepared using the method provided by the present disclosure may meet or exceed the requirements for aerospace sealants as set forth in AMS 3277. The sealant is designed to minimize the penetration of gases and liquids into the surface in the service environment of the sealed component.

[0063] A multi-layer system may include two or more layers, each of which may be designed to optimize one or more properties of the multi-layer system. At least one of these layers may include a sealant layer. In a multi-layer system, the outer or outermost layer may include a sealant and may be designed, for example, to exhibit chemical resistance, and the inner layer may be designed, for example, to exhibit low density, substrate adhesion, and / or high tensile strength and elongation. As another example, the outer layer of a multi-layer system may exhibit a fast cure speed to facilitate handling and manufacturability, and the lower layer may have a slower cure speed that may facilitate, for example, enhanced adhesion and / or enhanced mechanical properties. A multi-layer system may also have the potential to reduce costs. Expensive materials may be used only for layers where these materials are desired for their properties, and other layers may use alternative materials.

[0064] A multi-layer sealant system may include any suitable number of layers, such as 2, 3, 4, 5, or 6 layers, and each layer may be formed from a different material and exhibit different properties. A multi-layer sealant system may include one sealant layer, two or more sealant layers, or each layer may include a sealant layer. A multi-layer system may include at least one sealant layer, and each of the other layers may independently include a sealant layer or a non-sealant layer. A non-sealant layer is a layer that is not intended to function primarily as a sealant in a multi-layer sealant system, but the non-sealant layer may have some ability to limit gas and liquid penetration.

[0065] Examples of multi-layer systems are shown in Figures 1A and 1B. The multi-layer system shown in Figure 1A includes an inner first layer 101 underneath an intermediate second layer 102 underneath an outer third layer 103. Figure 1B shows a multi-layer system covering a fastener 105 attached to a substrate 104, including an inner first layer 101, an intermediate second layer 102 thereon, and an outer third layer 103 thereon. Only the outer third layer 103 may include a sealant, or all layers 101 / 102 / 103 may include a sealant. For example, the inner layer 101 may include a composition configured to promote adhesion to a surface, and the intermediate layer 102 may include a composition having high tensile strength and / or elongation.

[0066] Another example of a multi-layer system is shown in FIG. 1C, where a first layer 106 is adjacent to a second layer 107. FIG. 1D shows a multi-layer system where a first layer 106 is adjacent to a second layer 107, and a third layer 108 is on both the first and second layers 106 / 107. In FIG. 1C, the first layer 106 and / or the second layer 107 can be a sealant. In FIG. 1D, the outer layer 108 can be a sealant layer, and layers 106 and 107 can be non-sealant layers. In FIG. 1D, layers 106 / 107 / 108 can each be independently selected from a sealant layer and a non-sealant layer, with at least one of layers 106 / 107 / 108 being a sealant layer. Other configurations of the various layers of the multi-layer system are possible.

[0067] At least one of the layers of the multi-layer system may be different from another layer of the multi-layer system. For example, the layers may differ in the type and / or amount of components such as prepolymers, monomers, and / or additives in the layer. The different types and / or amounts of components may cause the various layers of the multi-layer system to have different properties. Each of these layers may independently contain, for example, reactive compounds, catalysts, polymerization initiators, adhesion promoters, fillers, reactive diluents, colorants, rheology control agents, and / or photochromic agents, which may be the same or different from another layer of the multi-layer system, or may be present in different weight or volume percentages.

[0068] The components of one layer can differ from the components of another layer in, for example, composition, cure chemistry, molecular weight of the components, size of the components, weight % of the components, and / or volume % of the components.

[0069] For example, each layer can be independently configured to provide a cured layer that exhibits one or more of, for example, chemical resistance, low temperature flexibility, hydrolytic stability, high temperature resistance, high tensile strength / elongation, bonding to substrates, bonding to primer coatings, adhesion to adjacent layers, fast tack-free time, cure time to Shore 10A hardness, time to full cure, electrical conductivity, EMI / RFI shielding, static dissipation, corrosion resistance, cured hardness, low density, and / or sound attenuation.

[0070] Each layer of the multi-layer system may have the same or different cure chemistry as another layer of the multi-layer system and / or an adjacent layer of the multi-layer system. It may be desirable for adjacent layers to be chemically or physically bonded to provide a robust interface between the adjacent layers. The formation of a chemical or physical bond between layers may be facilitated by using a co-reactive composition for the adjacent layer that has the same cure chemistry and / or contains a compound that can co-react with a compound in the adjacent layer.

[0071] Adjacent layers of the coreactive composition can be chemically bonded and / or physically bonded to create a mechanically strong interlayer interface. The strength of the interlayer interface can be determined by measuring the fracture energy according to ASTM D7313. The chemically resistant multi-layer sealant produced using the method provided by the present disclosure can have a fracture energy that is substantially the same as that of the individual layers. For example, the fracture energy of the multi-layer sealant and the fracture energy of the individual cured layers of the coreactive composition can be within, for example, less than 10%, less than 5%, less than 2%, or less than 1%.

[0072] Each layer of the multi-layer system may be selected to enhance the desired properties of the individual cured layers. For example, the innermost layer may provide enhanced surface adhesion to the substrate, but not necessarily have a low density. For example, the outermost layer may be formulated to provide enhanced chemical resistance and / or to be able to dissipate electrostatic charges. An intermediate layer between the inner and outer layers may be of low density and formulated to exhibit enhanced mechanical properties. In this manner, each layer of the multi-layer system may be configured to optimize a different property or combination of properties without compromising the other properties of the layer, and other overall properties of the multi-layer system may be imparted by the other layers.

[0073] A layer of a multi-layer system may be non-uniform in the horizontal plane of the layer and / or perpendicular to the horizontal plane of the layer. The non-uniformity may be discrete or continuous. Figure 2A shows a cross-section of a layer containing an additive, e.g., a filler, in which the concentration of the filler, identified by strips, varies in the dimension perpendicular to the horizontal plane of the layer. Figure 2B shows a cross-section of a layer in which the concentration of the filler varies both in the horizontal plane of the layer and in certain regions, and in the dimension perpendicular to the horizontal plane of the layer.

[0074] The composition in a layer of a multi-layer system may also vary within the layer. The composition may vary across the thickness, i.e., the cross-sectional dimension, of the layer, and / or in the lateral dimension, i.e., the longitudinal dimension, of the layer. For example, the concentration of a component, such as a co-reactive compound and / or additive, may vary across the thickness of the layer, such that the concentration is higher toward one side of the layer than the other side of the layer, or the concentration may be higher in the center of the layer than either of the two sides. The concentration of one or more components may vary linearly, non-linearly, continuously, discontinuously, and / or discretely across the thickness of the layer. Similarly, the concentration of one or more components, such as a co-reactive compound and / or additive, may vary in the lateral dimension of the layer, such as the dimension perpendicular to the thickness of the layer. For example, the concentration of a component, such as a compound and / or additive, may be higher on one side of the layer than on another side of the layer. The concentration or component may vary within a particular region of the layer. The concentrations of the components may vary linearly, non-linearly, continuously, discontinuously, and / or discretely across the lateral dimension of the layer.

[0075] Each layer forming the multilayer system provided by the present disclosure can independently include an internal composition structure. For example, the composition can be substantially uniform throughout the thickness of the layer, or can vary throughout the thickness of the layer. By uniform, it is meant that the concentration of each component forming the layer is within 10%, within 5%, or within 1%, or within 0.1% of the nominal concentration throughout the layer, where nominal concentration refers to the average concentration of the component in the layer. For example, the composition can be uniform in the thickness dimension of the layer, or can vary in the lateral dimension of the layer, i.e., the dimension perpendicular to the thickness dimension.

[0076] The coreactive composition used to form the layers of the multi-layer system may include at least two coreactive compounds and one or more additives. In a layer, the concentration of the coreactive compounds and / or one or more additives may be substantially the same, for example, within + / -5%, within + / -1%, or within + / -0.5%. Alternatively, in a layer, the concentration of the coreactive compounds and / or one or more additives may vary. The concentration may vary across the thickness of the layer and / or in the longitudinal dimension of the layer. Also, the concentration of the coreactive compounds and / or one or more additives may vary in a portion of the thickness and / or in a portion of the longitudinal dimension of the layer.

[0077] These layers may be referred to as structured layers to indicate that the layers are characterized by an internal compositional structure and that the composition is not uniform throughout the layer.

[0078] The composition in the structured layer can vary discretely, continuously, discontinuously, linearly, non-linearly, or variably.

[0079] The concentration of a component in a layer may vary discretely across the thickness of the layer, for example, an electrically conductive filler may be present to a certain depth in the outer portion of the layer and absent in the inner portion of the layer.

[0080] The concentrations of the components of a layer composition can vary, for example, linearly or non-linearly across the thickness or portion of the thickness of the layer.

[0081] The concentration of one or more components of a layer can be, for example, greater toward one surface, greater toward both surfaces, or greater toward the center of the layer.

[0082] The multi-layer system may be formed of any suitable physical material suitable for sealing the parts that are intended to be sealed. For example, to seal a two-dimensional continuous surface, the multi-layer system can be in the form of a multi-layer sheet. To seal a small part, the multi-layer system can be in the form of a cap, a shell, or any other suitable shape.

[0083] Each layer of the multilayer system may independently have a substantially uniform thickness or a variable thickness. The thickness of each layer may be substantially the same as or different from another layer forming the multilayer system. For example, the thickness of a layer may be substantially the same as another layer, within 10%, within 5%, or within 1% of it. For example, the thickness of a layer may be different from the thickness of another layer, and may differ by more than 10%, more than 20%, more than 50%, or more than 100% of the thickness of another layer.

[0084] For example, a multi-layer system used to seal a two-dimensional continuous surface may include multiple layers, each layer having a substantially uniform thickness, and the thickness of each layer may be the same as or different from the thickness of another layer. For example, a layer having a substantially uniform thickness may have a thickness that does not vary by more than 10%, more than 5%, or more than 1% across the surface.

[0085] The multilayer system may have, for example, a total thickness of more than 2 mm, more than 4 mm, more than 6 mm, more than 8 mm, more than 10 mm, more than 12 mm, or more than 14 mm. The multilayer system may have, for example, a total thickness of 2 mm to 15 mm, 3 mm to 14 mm, 3 mm to 12 mm, 4 mm to 10 mm, or 6 mm to 8 mm.

[0086] Each layer of the multi-layer system can independently have a thickness of, for example, 0.1 mm to 25 mm, 0.5 mm to 25 mm, 1 mm to 20 mm, 2 mm to 15 mm, or 3 mm to 10 mm. Each layer of the multi-layer system can independently have a thickness of, for example, greater than 0.1 mm, greater than 0.5 mm, greater than 1 mm, greater than 5 mm, greater than 10 mm, greater than 15 mm, or greater than 20 mm. Each layer of the multi-layer system can independently have a thickness of, for example, less than 25 mm, less than 20 mm, less than 15 mm, less than 10 mm, less than 5 mm, or less than 1 mm.

[0087] The outermost layer of a multi-layer system may have a thickness greater than the thickness of each of the underlying layers, either individually or in combination. The outermost layer may have a thickness less than the thickness of each of the underlying layers, either individually or in combination.

[0088] The inner layer may have a thickness greater than the thickness of each of the overlying layers, either individually or in combination. The inner layer may have a thickness less than the thickness of each of the overlying layers, either individually or in combination.

[0089] To seal a three-dimensional part, the inner layer may have a variable cross-sectional thickness to cover and conform to the complex shape of the part and provide a smooth, continuous outer surface, and the top layer may have a substantially uniform thickness.

[0090] A multi-layer system can be formed by extruding the co-reactive sealant composition to form an extrudate and depositing the extrudate onto a substrate or onto a previously deposited layer to form a sealant layer. The previously deposited layer can be a sealant layer or a non-sealant layer. The previously deposited layer can be the outermost layer of a multi-layer system. One or more layers can be deposited onto the deposited sealant layer to form a multi-layer system.

[0091] Additive manufacturing techniques, such as 3D printing, can be used to apply multi-layer systems to substrates. Additive manufacturing facilitates the ability to apply multi-layer systems in a consistent and reproducible manner. Additionally, in part because it avoids the time constraints associated with manual sealant application methods, additive manufacturing allows for the use of alternative curing chemistries, such as fast-cure chemistries.

[0092] The co-reactive sealant composition may include a first reactive compound and a second reactive compound, where the first reactive compound is reactive to the second reactive compound. The first and second reactive compounds may react at a temperature of less than 50°C, for example, less than 40°C, less than 30°C, less than 25°C, less than 20°C, or less than 15°C. The first and second reactive compounds may react without a catalyst and / or an activated polymerization initiator. The first and second reactive compounds may react in the presence of a catalyst or a combination of catalysts. The first and second reactive compounds may react in the presence of an activated polymerization initiator, such as an activated photoinitiator. The catalyst and polymerization initiator may be suitable for catalyzing or initiating a chemical reaction between the first reactive compound and the second reactive compound.

[0093] The coreactive sealant composition may be a thermosetting composition, and thus the cured coreactive sealant composition may be a thermosetting material. Each of the layers of the multi-layer sealant system may comprise a thermosetting material.

[0094] The co-reactive sealant composition may be formed by combining and mixing a first component and a second component. The first component may include a first reactive compound and a second reactive compound, and the second component may include a catalyst and / or a polymerization initiator. The first component may include a first reactive compound, the second component may include a second reactive compound, and the first and / or second components may include a catalyst and / or a polymerization initiator. In addition to the first and second components, the co-reactive sealant composition may be formed by combining and mixing one or more additional components.

[0095] The co-reactive sealant composition can be formed, for example, by pumping the first and second components into a mixer and mixing the first and second components to form the co-reactive sealant composition.

[0096] The deposition system may include an in-line static and / or dynamic mixer, as well as a separate pressurized pumping section, to hold at least two components and feed the co-reactive component to the static and / or dynamic mixer. A mixer such as an active mixer may include a variable speed central impeller with a high shear blade in a conical nozzle. For example, a series of conical nozzles with exit orifice dimensions of 0.2 mm to 50 mm, 0.5 mm to 40 mm, 1 mm to 30 mm, or 5 mm to 20 mm may be used.

[0097] For example, a series of static and / or dynamic mixing nozzles having exit orifice dimensions of 0.6 mm to 2.5 mm and lengths of 30 mm to 150 mm may be used. For example, the exit orifice diameter may be 0.2 mm to 4.0 mm, 0.4 mm to 3.0 mm, 0.6 mm to 2.5 mm, 0.8 mm to 2 mm, or 1.0 mm to 1.6 mm. The static and / or dynamic mixers may have lengths of, for example, 10 mm to 200 mm, 20 mm to 175 mm, 30 mm to 150 mm, or 50 mm to 100 mm. The mixing nozzle may include a static and / or dynamic mixing section and a distribution section coupled to the static and / or dynamic mixing section. The static and / or dynamic mixing section may be configured to combine and mix the components. The distribution section may be, for example, a straight tube having any of the orifice diameters listed above. The length of the distribution section may be configured to provide an area in which the components may begin to react and increase in viscosity prior to deposition. The length of the dispensing section may be selected based on, for example, the deposition rate, the reaction rate of the co-reactant, and the desired viscosity. The co-reactive composition may have a residence time in the static and / or dynamic mixing nozzle of, for example, 0.25 seconds to 5 seconds, 0.3 seconds to 4 seconds, 0.5 seconds to 3 seconds, or 1 second to 3 seconds. Other residence times may be used, as needed, depending on the cure chemistry and cure rate. The flow rate may be, for example, 1 mL / min to 20 mL / min, 2 mL / min to 15 mL / min, 3 mL / min to 10 mL / min, or 4 mL / min to 8 mL / min through a nozzle having a diameter of, for example, 0.8 mm to 1 mm. In general, the preferred residence time is less than the gelation time of the coreactive composition. The preferred gelation time may be less than 10 minutes, less than 8 minutes, less than 6 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, or less than 1 minute. The gelation time of the coreactive composition may be, for example, 0.5 minutes to 10 minutes, 1 minute to 7 minutes, 2 minutes to 6 minutes, or 3 minutes to 5 minutes.

[0098] The coreactive composition for making the multi-layer sealant may have a gel time at 23C / 50% relative humidity of, for example, less than 12 hours, less than 8 hours, less than 4 hours, less than 1 hour, less than 30 minutes, less than 10 minutes, or less than 1 minute. The coreactive composition for making the multi-layer sealant may have a gel time at 23C / 50% relative humidity of, for example, 10 seconds to 12 hours, 1 minute to 8 hours, 30 minutes to 4 hours, or 1 hour to 3 hours. The coreactive composition for making the multi-layer sealant may have a gel time of, for example, more than 10 seconds, more than 1 minute, more than 30 minutes, more than 1 hour, more than 4 hours, or more than 8 hours. Gel time refers to the period from when the curing of the coreactive composition is initiated, for example, by either mixing the coreactive components or by exposure to energy such as UV radiation, until the coreactive composition can no longer be stirred by hand.

[0099] The static and / or dynamic mixing nozzles can be heated or cooled to control, for example, the rate of reaction between the coreactive compounds and / or the viscosity of the coreactive composition. The orifices of the deposition nozzles can have any suitable shape and size. The system can include multiple deposition nozzles. The nozzles can have fixed orifice sizes and shapes, or the nozzle orifices can be controllably adjusted. The mixers and / or nozzles can be cooled to control the heat generated by the reaction of the coreactive compounds.

[0100] One or more additional layers of the multi-layer system may be deposited by methods other than extrusion. For example, each layer below and / or above the sealant layer may be deposited using any suitable method, such as spraying, brushing, roller coating, and / or spreading. Each of the one or more below and / or above layers may independently comprise a sealant layer or a non-sealant layer.

[0101] In addition to the sealant layer of the multi-layer system, other layers of the multi-layer system can be formed by extruding a suitable co-reactive composition. One or more additional layers can be formed by combining and mixing the first and second components to form a co-reactive composition that includes a first reactive compound and a second reactive compound. One or more additional co-reactive compositions can be fused with the co-reactive sealant composition to form a co-extrudate, which can be deposited with other layers of the multi-layer system. Each additional co-reactive composition can be independently selected from additional co-reactive sealant compositions or co-reactive non-sealant compositions.

[0102] One or more additional layers may be formed by sequentially depositing the respective extrudates, where sequentially depositing means depositing an extrudate containing a first co-reactive composition, followed by a second extrudate containing a second co-reactive composition, in this manner building up a multi-layer system layer by layer.

[0103] Alternatively, one or more additional co-reactive compositions can be co-extruded with the co-reactive sealant composition to form a co-extrudate, which can then be deposited to form all or part of a multi-layer system simultaneously. Each additional coextruded coreactive composition can be formed by combining and mixing the first and second components to form each additional coreactive composition. Each additional coreactive composition can be merged with the coreactive sealant composition stream and coextruded through a coextrusion die to form a coextrudate. The coextrudate can be deposited to form a multi-layer system, at least one of the layers being a sealant.

[0104] Each additional coextruded coreactive composition can independently comprise a coreactive sealant composition or a coreactive non-sealant composition, with each layer comprising a sealant or a non-sealant. Each additional coextruded reactive composition comprises a thermosetting material that forms a thermoset material upon curing.

[0105] Adjacent co-reactive compositions forming the extrudate may contain the same or different cure chemistries and / or may contain reactive compounds that can react with reactive compounds in adjacent co-reactive compositions, allowing for bonding between adjacent co-reactive compositions such that adjacent layers are bonded together to provide a cured multi-layer system with high cohesive strength.

[0106] Each co-reactive composition of a multi-layer system, such as a co-reactive sealant composition or a co-reactive non-sealant composition, can independently comprise a first compound having a first functional group and a second compound including a second functional group, where the first functional group is capable of reacting with the second functional group.

[0107] The first and second functional groups can react at temperatures, for example, below 50° C., below 40° C., below 30° C., below 20° C., or below 15° C. The first and second functional groups can react at temperatures, for example, between 10° C. and 50° C., between 15° C. and 40° C., or between 20° C. and 30° C. The first and second functional groups can react at temperatures, for example, above 10° C., above 20° C., above 30° C., or above 40° C.

[0108] The co-reactive composition may be a one-component composition in which the curing reaction is initiated upon application of energy, such as by exposing the one-component co-reactive composition to actinic radiation, such as UV radiation. The co-reactive composition may be a two-component composition in which two co-reactive components are combined and mixed to initiate the curing reaction. For example, a first co-reactive component comprising a first compound comprising a first functional group may be combined and mixed with a second co-reactive component comprising a second compound comprising a second functional group to form a co-reactive composition, the first and second functional groups being co-reactive. The first and second co-reactive components may be combined and mixed prior to being introduced into the co-extruder, or may be combined and mixed within the co-extruder to form a co-reactive composition that is blended with another co-reactive composition stream.

[0109] The properties of the multilayer system and the layers forming the multilayer system, such as the viscosity and cure rate of the co-reactive composition, can be selected to promote the ability of the extrudate or co-extrudate to retain an intended shape after deposition on a surface.

[0110] The coreactive composition, upon deposition, can have an initial viscosity, such as, for example, 1E2 poise to 1E7 poise, 5E2 poise to 5E6 poise, 1E3 poise to 1E5 poise, or 5E3 poise to 5E4 poise, where the viscosity is determined using a Brookfield rheometer equipped with a #7 paddle at 2 rpm and 25° C. The coreactive composition can have an initial viscosity, for example, greater than 1E2 poise, greater than 5E2 poise, greater than 1E3 poise, greater than 5E3 poise, greater than 1E4 poise, greater than 1E5 poise, or greater than 1E6 poise. The coreactive composition can have an initial viscosity, for example, less than 1E7 poise, less than 1E6 poise, less than 1E5 poise, less than 1E4 poise, or less than 1E3 poise.

[0111] The coreactive composition may have a tack-free time of, for example, less than 24 hours, less than 10 hours, less than 1 hour, less than 30 minutes, less than 10 minutes, or less than 5 minutes at 23° C. / 50% relative humidity. The coreactive composition for making the layer sealant may have a tack-free time at 23° C. / 50% RH of, for example, more than 10 seconds, more than 1 minute, more than 1 hour, more than 6 hours, or more than 12 hours. The coreactive composition may have a tack-free time at 23° C. / 50% RH of, for example, 30 seconds to 24 hours, 1 minute to 12 hours, 1 hour to 10 hours, or 2 hours to 8 hours. "Tack-free time" refers to the period from when curing of the coreactive composition is initiated, for example, by either mixing the coreactive components or by exposure to energy such as UV radiation, to when the layer prepared from the coreactive composition is no longer tack-free, which is determined by applying a polyethylene sheet to the surface of the layer with hand pressure and observing whether the sealant adheres to the surface of the polyethylene sheet.

[0112] The coreactive composition may have a time to Shore 10A hardness at 23°C / 50% relative humidity of, for example, less than 2 minutes, less than 5 minutes, less than 30 minutes, less than 1 hour, less than 5 hours, less than 10 hours, or less than 20 hours. The coreactive composition may have a time to Shore 10A hardness at 23°C / 50% relative humidity of, for example, more than 30 seconds, more than 1 minute, more than 1 hour, more than 5 hours, or more than 10 hours. The coreactive composition may have a time to Shore 10A hardness at 23°C / 50% relative humidity of, for example, 30 seconds to 20 hours, 1 minute to 12 hours, or 1 hour to 10 hours.

[0113] The coreactive composition may have a cure time such as time to Shore 30A hardness of 1 to 7 days at 23° C. / 50% relative humidity.

[0114] The coreactive composition may have a long pot life and, following the end of the pot life, a rapid cure time. Pot life refers to the time from when the coreactive compounds are first combined and mixed to form the coreactive composition until the coreactive composition can no longer be stirred by hand, or the time from when the catalyst is added and / or the polymerization initiator is activated to react the coreactive compounds until the coreactive composition can no longer be stirred by hand.

[0115] Each coreactive composition used to form the multi-layer system may independently include one or more prepolymers, one or more monomers, and one or more additives.

[0116] The coreactive composition can be a thermosetting composition and can form a thermoset material upon curing.

[0117] The coreactive composition may be substantially free of solvent, for example, the coreactive composition may include less than 5 wt%, less than 2 wt%, less than 1 wt%, or less than 0.1 wt%, of solvent, where the wt% is based on the total weight of the coreactive composition.

[0118] The coreactive composition may include coreactive compounds that coreact and cure at room temperature, where room temperature refers to a temperature of 20°C to 25°C, 20°C to 22°C, or about 20°C.

[0119] The prepolymer can include any suitable backbone. The prepolymer backbone can be selected based, for example, on the end-use requirements of the multi-layer system and the desired attributes of the particular layer.

[0120] The coreactive composition may include a prepolymer or combination of prepolymers that may affect, for example, the tensile strength, elongation, hydrolytic stability, and / or chemical resistance, as well as other properties of the cured sealant.

[0121] The prepolymer may, for example, be less than 20,000 Da, less than 15,000 Da, less than 10,000 Da, less than 8,000 Da, less than 6,000 Da, less than 4,000 Da, or less than 2 The prepolymer may have a number average molecular weight of less than 2,000 Da. The prepolymer may have a number average molecular weight of, for example, more than 2,000 Da, more than 4,000 Da, more than 6,000 Da, more than 8,000 Da, more than 10,000 Da, or more than 15,000 Da. The prepolymer may have a number average molecular weight of, for example, 1,000 Da to 20,000 Da, 2,000 Da to 10,000 Da, 3,000 Da to 9,000 Da, 4,000 Da to 8,000 Da, or 5,000 Da to 7,000 Da.

[0122] The prepolymer may be a liquid at 25°C and may have a glass transition temperature, Tg, for example, less than -20°C, less than -30°C, or less than -40°C.

[0123] The prepolymer may exhibit a viscosity in the range of, for example, 20 poise to 500 poise (2 Pa·s to 50 Pa·s), 20 poise to 200 poise (2 Pa·s to 20 Pa·s), or 40 poise to 120 poise (4 Pa·s to 12 Pa·s), measured using, for example, a Brookfield CAP2000 viscometer with a No. 6 spindle at a speed of 300 rpm and a temperature of 25° C.

[0124] The prepolymer can have, for example, less than 12, less than 10, less than 8, less than 6, or less than 4 reactive functional groups. The first reactive compound and the second reactive compound can each include a prepolymer having, for example, 2 to 12, 2 to 8, 2 to 6, 2 to 4, or 2 to 3 respective reactive functional groups. The first reactive compound and the second reactive compound can each independently have, for example, 2, 3, 4, 5, or 6 functional groups.

[0125] The coreactive composition may include a prepolymer or combination of prepolymers having any suitable polymer backbone. The polymer backbone may be selected, for example, to impart solvent resistance to the cured coreactive composition, to impart desired physical properties such as tensile strength, elongation, Young's modulus, impact resistance, or other application-relevant properties. The prepolymer backbone may be terminated with one or more suitable functional groups, depending on the particular cure chemistry.

[0126] The prepolymer may contain segments with different chemical structures and properties within the prepolymer backbone. The segments may be random, ordered, or distributed in blocks. These segments may be used to impart specific properties to the prepolymer backbone. For example, these segments may contain flexible bonds, such as thioether bonds, to the polymer backbone. Segments with pendant groups may be incorporated into the prepolymer backbone.

[0127] For example, the prepolymer backbone may be a polythioether, polysulfide, polyformal, polyisocyanate, polyurea, polycarbonate, polyphenylene sulfide, polyethylene oxide, polystyrene, acrylonitrile-butadiene-styrene, polycarbonate, styrene acrylonitrile, poly(methyl methacrylate), polyvinyl chloride, polybutadiene, polybutylene terephthalate, poly(p-phenylene oxide), polysulfone, polyethersulfone, polyethyleneimine, polyphenylsulfone, acrylonitrile styrene acrylate, poly These may include ethylene, syndiotactic or isotactic polypropylene, polylactic acid, polyamides, ethyl-vinyl acetate homopolymers or copolymers, polyurethanes, copolymers of ethylene, copolymers of propylene, impact copolymers of propylene, polyetheretherketone, polyoxymethylene, syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), liquid crystal polymers (LCP), homopolymers and copolymers of butene, homopolymers and copolymers of hexene, and combinations of any of the foregoing.

[0128] Other suitable prepolymer backbones include polyolefins (e.g., polyethylene, Linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene, polypropylene, and olefin copolymers), styrene / butadiene rubber (SBR), styrene / ethylene / butadiene / styrene copolymer (SEBS), butyl rubber, ethylene / propylene copolymer (EPR), ethylene / propylene / diene monomer copolymer (EPDM), polystyrene (including high impact polystyrene), poly(vinyl acetate), ethylene / vinyl acetate copolymer (EVA), poly(vinyl alcohol), ethylene / vinyl alcohol copolymer (EVOH), poly(vinyl butyral), poly(methyl methacrylate), and other acrylate polymers and copolymers (including methyl methacrylate polymers, methacrylate copolymers, methyl polymers derived from one or more acrylates, methacrylates, methyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate, etc.), olefin and styrene copolymers, acrylonitrile / butadiene / styrene (ABS), styrene / acrylonitrile polymers (SAN), styrene / maleic anhydride copolymer, isobutylene / maleic anhydride copolymer, ethylene / acrylic acid copolymer, poly(acrylonitrile), polycarbonate (PC), polyamide, polyester, liquid crystal polymer (LCP), poly(lactic acid), poly(phenylene oxide) (PPO), PPO-polyamide alloy, polysulfone (PSU), polyetherketone (PEK), polyetheretherketone (PEEK), polyimide, polyoxymethylene (POM) homopolymer and copolymer, polyetherimide, fluorinated ethylene Polyethylene propylene polymers (FEP), poly(vinyl fluoride), poly(vinylidene fluoride), poly(vinylidene chloride) and poly(vinyl chloride), polyurethanes (thermoplastic and thermoset), aramids (such as Kevlar® and Nomex®), polytetrafluoroethylene (PTFE), polysiloxanes (including polydimethylene siloxane, dimethylsiloxane / vinylmethylsiloxane copolymers, vinyldimethylsiloxane terminated poly(dimethylsiloxane)), elastomers, epoxy polymers, polyureas, alkyds,These include cellulose polymers (such as ethyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate), polyethers, and glycols such as poly(ethylene oxide) (also known as poly(ethylene glycol)), poly(propylene oxide) (also known as poly(propylene glycol)), and ethylene oxide / propylene oxide copolymers, acrylic latex polymers, polyester acrylate oligomers and polymers, polyester diol diacrylate polymers, and UV curable resins.

[0129] The coreactive composition may include a prepolymer that includes an elastomeric backbone. "Elastomer," "elastomeric," and similar terms refer to a material that has "rubber-like" properties and generally has a low Young's modulus and high tensile strain. For example, an elastomer may have a Young's modulus / tensile strength of about 4 MPa to about 30 MPa. An elastomer may have a tensile strain (elongation at break) of about 100% to about 2,000%. Young's modulus / tensile strength and tensile strain may be determined according to ASTM D412.4893. An elastomer may exhibit a tear strength of, for example, 50 kN / m to 200 kN / m. The tear strength of the elastomer may be determined according to ASTM D624. The Young's modulus of the elastomer may range from 0.5 MPa to 6 MPa, as determined according to ASTM D412.4893.

[0130] Examples of suitable prepolymers having an elastomeric backbone include polyethers, polybutadienes, fluoroelastomers, perfluoroelastomers, ethylene / acrylic copolymers, ethylene propylene diene terpolymers, nitriles, polythiolamine, polysiloxanes, chlorosulfonated polyethylene rubber, isoprene, neoprene, polysulfides, polythioethers, silicones, styrene butadienes, and combinations of any of the foregoing. Elastomeric prepolymers include, for example, polymethylhydrosiloxanes, polydimethylsiloxanes, polyhydrodiethylsiloxanes, polydiethylene The elastomeric prepolymer may include a polysiloxane, such as a silanol group, a methyl siloxane, or a combination of any of the foregoing. The elastomeric prepolymer may include terminal functional groups, such as silanol groups, that are less reactive with amine and isocyanate groups.

[0131] Examples of prepolymers that exhibit high solvent resistance include fluoropolymers, ethylene propylene diene terpolymers (EPDM), and other chemically resistant prepolymers disclosed herein, cured polymer matrices having high crosslink density, chemically resistant organic fillers such as polyamides, polyphenylene sulfide, and polyethylene, or combinations of any of the foregoing.

[0132] Examples of prepolymers having a chemically resistant backbone include polytetrafluoroethylene, polyvinylidene difluoride, polyethylene tetrafluoroethylene, fluorinated ethylene propylene, perfluoroalkoxy, ethylene chlorotrifluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene propylene polymer polyamide, polyethylene, polypropylene, ethylene-propylene, fluorinated ethylene-propylene, polysulfone, polyarylethersulfone, polyethersulfone, polyimide, polyethylene terephthalate, polyetherketone, polyetheretherketone, polyetherimide, polyphenylene sulfide, polyarylsulfone, polybenzimidazole, polyamideimide, liquid crystal polymer, and combinations of any of the foregoing.

[0133] Examples of prepolymers that exhibit low temperature flexibility include silicones, polytetrafluoroethylene, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing.

[0134] Examples of prepolymers that exhibit hydrolytic stability include silicones, polytetrafluoroethylenes, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing, as well as compositions having high crosslink density.

[0135] Examples of prepolymers that exhibit high temperature resistance may include, for example, prepolymers such as silicones, polytetrafluoroethylene, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing, as well as compositions having high crosslink density.

[0136] Examples of prepolymers that exhibit high tensile properties include silicones and polybutadienes, compositions with high crosslink density, inorganic fillers, and combinations of any of the foregoing.

[0137] The coreactive sealant composition may include a sulfur-containing prepolymer or a combination of sulfur-containing prepolymers. The sulfur-containing monomers and prepolymers may impart solvent resistance to the cured sealant.

[0138] In applications where chemical resistance is required, prepolymers with sulfur-containing backbones may be used. Chemical resistance may be with respect to cleaning solvents, fuels, hydraulic fluids, lubricants, oils, and / or salt sprays. Chemical resistance refers to the ability of a part to maintain acceptable physical and mechanical properties after exposure to atmospheric conditions such as moisture and temperature, and after exposure to chemicals such as cleaning solvents, fuels, hydraulic fluids, lubricants, and / or oils. In general, chemically resistant parts exhibit a swelling ratio of less than 25%, less than 20%, less than 15%, or less than 10% after immersion in chemicals at 70° C. for 7 days, the swelling ratio being within the range of EN ISO 10563. is determined in accordance with

[0139] Sulfur-containing prepolymers are those that contain one or more thioether-S groups in the backbone of the prepolymer. n -group, where n can be, for example, 1 to 6. Prepolymers that contain only thiols or other sulfur-containing groups as either the terminal or pendant groups of the prepolymer are not included in sulfur-containing prepolymers. A prepolymer backbone refers to the portion of the prepolymer that has repeating segments. Thus, HS-RR(-CH2-SH)-[-R-(CH2)2-S(O)2-(CH2)-S(O)2] n Sulfur-containing prepolymers do not include prepolymers having the structure -CH=CH2 where each R is a moiety that does not contain a sulfur atom in the prepolymer backbone. Sulfur-containing prepolymers include prepolymers having the structure HS-RR(-CH2-SH)-[-R-(CH2)2-S(O)2-(CH2)-S(O)2]-CH=CH2 where at least one R is a moiety that contains a sulfur atom, such as a thioether group.

[0140] Sulfur-containing prepolymers with high sulfur content can impart chemical resistance to the cured coreactive composition. For example, the sulfur-containing prepolymer backbone can have a sulfur content of more than 10 wt%, more than 12 wt%, more than 15 wt%, more than 18 wt%, more than 20 wt%, or more than 25 wt%, where the weight percent is based on the total weight of the prepolymer backbone. The chemically resistant prepolymer backbone can have a sulfur content of, for example, 10 wt% to 25 wt%, 12 wt% to 23 wt%, 13 wt% to 20 wt%, or 14 wt% to 18 wt%, where the weight percent is based on the total weight of the prepolymer backbone. The sulfur content can be determined according to ASTM D297.

[0141] Examples of prepolymers having a sulfur-containing backbone include polythioether prepolymers, polysulfide prepolymers, sulfur-containing polyformal prepolymers, monosulfide prepolymers, and combinations of any of the foregoing.

[0142] The coreactive sealant composition may, for example, comprise 40% to 80%, 40% to 75%, 45% to 70%, or 50% to 70% by weight of the sulfur-containing prepolymer or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the coreactive composition. The coreactive sealant composition may, for example, comprise more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, or more than 90% by weight of the sulfur-containing prepolymer or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the coreactive sealant composition. The coreactive sealant composition may, for example, comprise less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, or less than 40% by weight of the sulfur-containing prepolymer or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the coreactive sealant composition.

[0143] A coreactive sealant composition for forming a cured sealant layer exhibiting fuel resistance may, for example, include a prepolymer having a sulfur content greater than 10 wt.%, where the wt.% is based on the total weight of the prepolymer, rubbers such as polybutadiene and ethylene propylene diene terpolymer (EPDM), highly crosslinked, chemically resistant organic fillers such as polyamides, polyphenylene sulfide and polyethylene, or any combination of the foregoing.

[0144] The sulfur-containing prepolymer can include a polythioether prepolymer or a combination of polythioether prepolymers.

[0145] The polythioether prepolymer comprises at least one moiety having a structure of formula (1), a thiol-terminated polythioether prepolymer of formula (1a), a terminal-modified polythioether prepolymer of formula (1b), ethers, or polythioether prepolymers comprising any combination of the foregoing: -SR 1 -[SASR 1 -] n -S- (1) HS-R 1 -[SASR 1 -] n -SH (1a) R 3 -SR 1 -[SASR 1 -] n -SR 3 (1b) During the ceremony, n may be an integer from 1 to 60; Each R 1 is independently 2~10 Alkanediyl, C 6~8 Cycloalkanediyl, C 6~14 Alkanecycloalkanediyl, C 5~8 Heterocycloalkanediyl, and -[(CHR) p -X-] q (CHR) r -, wherein p may be an integer from 2 to 6; q can be an integer from 1 to 5; r can be an integer from 2 to 10; Each R may be independently selected from hydrogen and methyl; Each X may be independently selected from O, S, and SS; Each A can independently be a moiety derived from a polyvinyl ether of formula (2) or a polyalkenyl polyfunctionalizing agent of formula (3): CH2=CH-O-(R 2 -O) m -CH=CH2(2) B(-R 4 -CH=CH2) z (3) During the ceremony, m may be an integer from 0 to 50; Each R 2 is independently 1~10 Alkanediyl, C 6~8 Cycloalkanediyl, C 6~14 Alkanecycloalkanediyl, and -[(CHR) p -X-] q (CHR) r -, wherein p, q, r, R, and X are selected from R 1 As defined in terms of B is a z-valent polyalkenyl polyfunctionalizing agent B(-R 4 -CH=CH2) z represents the core of z can be an integer from 3 to 6; Each R 4 is independently 1~10 Alkanediyl, C 1~10 Heteroalkanediyl, substituted C 1~10 Alkanediyl and substituted C 1~10 heteroalkanediyl, Each R 3 can independently be a moiety that includes a terminal reactive group.

[0146] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 is C2~10 It may be an alkanediyl.

[0147] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 -[(CHR) p -X-] q (CHR) r --It could be.

[0148] In the moieties of formula (1) and the prepolymers of formulas (1a) and (1b), X may be selected from O and S, and thus may be -[(CHR) p -X-] q (CHR) r -Ha-[(CHR) p -O-] q (CHR) r -or-[(CHR) p -S-] q (CHR) r P and r may be equally likely, such as when p and r are both likely to be 2.

[0149] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 is C 2~6 Alkanediyl and -[(CHR) p -X-] q (CHR) r - may be selected from.

[0150] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 teeth- [(CHR) p -X-] q (CHR) r -, X can be O, or X can be S.

[0151] The moiety of formula (1) and the prepolymer of formula (1a) and (1b) 1 -[(CHR) p -X-] q (CHR) r- may be, p may be 2, r may be 2, q may be 1, and X may be S, or p may be 2, q may be 2, r may be 2, and X may be O, or p may be 2, r may be 2, q may be 1, and X may be O.

[0152] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 -[(CHR) p -X-] q (CHR) r -, and each R can be hydrogen, or at least one R can be methyl.

[0153] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 -[(CH2) p -X-] q (CH2) r -, where each X may be independently selected from O and S.

[0154] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 -[(CH2) p -X-] q (CH2) r -, where each X can be O or each X can be S.

[0155] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), R 1 -[(CH2) p -X-] q (CH2) r -, where p can be 2, X can be O, q can be 2, r can be 2, and R 2 can be ethanediyl, m can be 2, and n can be 9.

[0156] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), each R 1can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2-(ethane-1,2-diylbis(sulfanyl))bis(ethane-1-thiol)), or each R 1 can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis(ethane-1-thiol)) and combinations thereof.

[0157] In the moiety of formula (1) and the prepolymers of formula (1a) and (1b), each p can be independently selected from 2, 3, 4, 5, and 6. Each p can be the same and can be 2, 3, 4, 5, or 6.

[0158] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), each q can independently be 1, 2, 3, 4, or 5. Each q can be the same and can be 1, 2, 3, 4, or 5.

[0159] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), each r can independently be 2, 3, 4, 5, 6, 7, 8, 9, or 10. Each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0160] In the moiety of formula (1) and the prepolymers of formulas (1a) and (1b), each r can independently be an integer from 2 to 4, from 2 to 6, or from 2 to 8.

[0161] In the divinyl ether of formula (2), m can be an integer from 0 to 50, for example, from 0 to 40, 0 to 20, 0 to 10, 1 to 50, 1 to 40, 1 to 20, 1 to 10, 2 to 50, 2 to 40, 2 to 20, or 2 to 10.

[0162] In the divinyl ether of formula (2), each R 2 is independently 2~10 n-Alkanediyl group, C 3~6 Branched alkanediyl groups, and -[(CH2) p -X-] q (CH2)r - groups.

[0163] In the divinyl ether of formula (2), each R 2 are independently C such as methanediyl, ethanediyl, n-propanediyl, or n-butanediyl. 2~10 It may be an n-alkanediyl group.

[0164] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q (CH2) r - group, where each X can be O or S.

[0165] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q (CH2) r - group.

[0166] In the divinyl ether of formula (2), each m can independently be an integer from 1 to 3. Each m can be the same and can be 1, 2, or 3.

[0167] In the divinyl ether of formula (2), each R 2 is independently 2~10 n-Alkanediyl group, C 3~6 Branched alkanediyl groups, and -[(CH2) p -X-] q (CH2) r - groups.

[0168] In the divinyl ether of formula (2), each R 2 is independently 2~10 It may be an n-alkanediyl group.

[0169] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q(CH2) r -group, and each X can be O or S.

[0170] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q (CH2) r - group, each X can be O or S, and each p can be independently 2, 3, 4, 5, and 6.

[0171] In the divinyl ether of formula (2), each p can be the same and can be 2, 3, 4, 5, or 6.

[0172] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q (CH2) r -group, each X can be O or S, and each q can independently be 1, 2, 3, 4, or 5.

[0173] In the divinyl ether of formula (2), each q can be the same and can be 1, 2, 3, 4, or 5.

[0174] In the divinyl ether of formula (2), each R 2 are independently -[(CH2) p -X-] q (CH2) r - group, each X can be O or S, and each r can independently be 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0175] In the divinyl ethers of formula (2), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9, or 10. In the divinyl ethers of formula (2), each r can independently be an integer from 2 to 4, from 2 to 6, or from 2 to 8.

[0176] Examples of suitable divinyl ethers include ethylene glycol divinyl ether (EG-DVE), butanediol divinyl ether (BD-DVE), hexanediol divinyl ether (HD-DVE), diethylene glycol divinyl ether (DEG-DVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polytetrahydrofuryl divinyl ether, cyclohexanedimethanol divinyl ether, and combinations of any of the foregoing.

[0177] The divinyl ether may include a sulfur-containing divinyl ether. Examples of suitable sulfur-containing divinyl ethers are disclosed, for example, in PCT Publication No. WO2018 / 085650.

[0178] In the moiety of formula (1), each A can be independently derived from a polyalkenyl polyfunctionalizing agent. The polyalkenyl polyfunctionalizing agent can have the structure of formula (3), where z can be 3, 4, 5, or 6.

[0179] In the polyalkenyl polyfunctionalizing agent of formula (3), each R 4 is independently 1~10 Alkanediyl, C 1~10 Heteroalkanediyl, substituted C 1~10 Alkanediyl or substituted C 1~10 The one or more substituents may be selected from, for example, -OH, =O, C 1~4 Alkyl, and C 1~4 The one or more heteroatoms may be selected from, for example, O, S, and combinations thereof.

[0180] Examples of suitable polyalkenyl polyfunctionalizing agents include triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione, 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione, 1,3-bis(2-methylallyl)-6-methylene-5-(2-oxopropyl)-1,3,5-triazinone-2,4-dione, tris(allyloxy)methane, pentaerythritol triallyl ether, 1- (allyloxy)-2,2-bis((allyloxy)methyl)butane, 2-prop-2-ethoxy-1,3,5-tris(prop-2-enyl)benzene, 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4-dione, and 1,3,5-tris(2-methylallyl)-1,3,5-triazinane-2,4,6-trione, 1,2,4-trivinylcyclohexane, trimethylolpropane trivinyl ether, and combinations of any of the foregoing.

[0181] In the moiety of formula (1) and the prepolymer of formula (1a)-(1b), the molar ratio of the moiety derived from the divinyl ether to the moiety derived from the polyalkenyl polyfunctionalizing agent can be, for example, 0.9 mol % to 0.999 mol %, 0.95 mol % to 0.99 mol %, or 0.96 mol % to 0.99 mol %.

[0182] In the moiety of formula (1) and the prepolymer of formulas (1a)-(1b), each R 1 Ha-(CH 2)2 -O-(CH2)2-O-(CH2)2-, where each R 2 can be -(CH2)2-, and m can be an integer from 1 to 4.

[0183] In the moiety of formula (1) and the prepolymer of formulas (1a)-(1b), each R 2 can be derived from a divinyl ether, such as diethylene glycol divinyl ether, a polyalkenyl polyfunctionalizing agent, such as triallyl cyanurate, or a combination thereof.

[0184] In the moiety of formula (1) and the prepolymer of formula (1a)-(1b), each A may be independently selected from the moiety of formula (2a) and the moiety of formula (3a): -(CH2)2-O-(R 2 -O) m -(CH2)2- (2a) B{-R 4 -(CH2)2-}2{-R 4 -(CH2)2-S-[-R 1 -SASR 1 -] n -SH} z-2 (3a) In the formula, m, R 1 , R 2 , R 4 , A, B, m, n, and z are as defined in Equation (1), Equation (2), and Equation (3).

[0185] In the moiety of formula (1) and the prepolymer of formulas (1a)-(1b), each R 1 can be -(CH2)2-O-(CH2)2-O-(CH2)2-, and each R 2 can be -(CH2)2-, m can be an integer from 1 to 4, and the polyfunctionalizing agent B(-R 4 -CH=CH2) z comprises triallyl cyanurate, where z is 3 and each R 4 can be -O-CH2-CH=CH2.

[0186] Methods for synthesizing sulfur-containing polythioethers are disclosed, for example, in US Pat. No. 6,172,179.

[0187] The backbone of the thiol-terminated polythioether prepolymer can be modified to enhance one or more properties, such as adhesion, tensile strength, elongation, UV resistance, hardness, and / or flexibility of sealants prepared using the polythioether prepolymer. For example, adhesion-promoting groups, antioxidants, metal ligands, and / or urethane linkages can be incorporated into the backbone of the polythioether prepolymer to improve one or more performance attributes. Examples of backbone-modified polythioether prepolymers are disclosed, for example, in U.S. Patent No. 8,138,273 (urethane-containing), U.S. Patent No. 9,540,540 (sulfone-containing), U.S. Patent No. 8,952,124 (bis(sulfonyl)alkanol-containing), U.S. Patent No. 9,382,642 (metal ligand-containing), U.S. Patent Application Publication No. 2017 / 0114208 (antioxidant-containing), PCT International Publication No. WO2018 / 085650 (sulfur-containing divinyl ether), and PCT International Publication No. WO2018 / 031532 (urethane-containing), each of which is incorporated by reference in its entirety.Polythioether prepolymers include those described in U.S. Patent Application Publication Nos. 2017 / 0369737 and 2016 / 0090507.

[0188] Examples of suitable thiol-terminated polythioether prepolymers are disclosed, for example, in U.S. Patent No. 6,172,179. The thiol-terminated polythioether prepolymers may include Permapol® P3.1E, Permapol® P3.1E-2.8, Permapol® L56086, or any combination of the foregoing, each of which is available from PPG Aerospace. These Permapol® products are encompassed by the thiol-terminated polythioether prepolymers of formulas (1), (1a), and (1b). Thiol-terminated polythioethers include the prepolymers described in U.S. Patent No. 7,390,859, and the urethane-containing polythiols described in U.S. Patent Application Publication Nos. 2017 / 0369757 and 2016 / 0090507.

[0189] The sulfur-containing prepolymer may include a polysulfide prepolymer or a combination of polysulfide prepolymers.

[0190] A polysulfide prepolymer is a polymer that contains one or more polysulfide bonds, i.e., -S, in the prepolymer backbone. x -linkages, where x is 2 to 4. The polysulfide prepolymers may have two or more than two sulfur-sulfur bonds. Suitable thiol-terminated polysulfide prepolymers are commercially available, for example, from AkzoNobel and Toray Industries, Inc. under the trade names Thioplast® and Thiokol-LP®, respectively. is.

[0191] Examples of suitable polysulfide prepolymers are disclosed, for example, in U.S. Pat. Nos. 4,623,711, 6,172,179, 6,509,418, 7,009,032, and 7,879,955.

[0192] Examples of suitable thiol-terminated polysulfide prepolymers include Thioplast® G polysulfides, such as Thioplast® G1, Thioplast® G4, Thioplast® G10, Thioplast® G12, Thioplast® G21, Thioplast® G22, Thioplast® G44, Thioplast® G122, and Thioplast® G131, available commercially from AkzoNobel. Suitable thiol-terminated polysulfide prepolymers, such as Thioplast® G resins, are liquid thiol-terminated polysulfide prepolymers that are blends of difunctional and trifunctional molecules, where the difunctional thiol-terminated polysulfide prepolymer has the structure of formula (4) and the trifunctional thiol-terminated polysulfide polymer can have the structure of formula (5): HS-(-R 5 -SS-) n -R 5 -SH (4) HS-(-R 5 -SS-) a -CH2-CH{-CH2-(-SSR 5 -) b -SH}{-(-SSR 5 -) c -SH} (5) In the formula, each R 5 is -(CH2)2-O-CH2-O-(CH2)2-, n=a+b+c, and the value of n can be from 7 to 38 depending on the amount of trifunctional crosslinker (1,2,3-trichloropropane; TCP) used during the synthesis of the polysulfide prepolymer. Thioplast® G polysulfides can have a number average molecular weight of less than 1,000 Da to 6,500 Da, an -SH content of 1% to more than 5.5% by weight, and a crosslink density of 0% to 2.0% by weight.

[0193] The polysulfide prepolymer may further comprise an end-modified polysulfide prepolymer having a structure of formula (4a), an end-modified polysulfide prepolymer having a structure of formula (5a), or a combination thereof: R 3 -S-(-R 5 -SS-) n -R 5 -SR 3 (4a) R 3 -S-(-R 5 -SS-) a -CH2-CH{-CH2-(-SSR 5 -) b -S-}{-(-SSR 5 -) c -SR 3} (5a) In the formula, n, a, b, c, and R 5 is as defined for equations (4) and (5), and R 3 is the moiety that contains the terminal reactive group.

[0194] Examples of suitable thiol-terminated polysulfide prepolymers include Thiokol® LP polysulfide, Thiokol® LP2, Thiokol® LP3, Thiokol® LP12, Thiokol® LP23, Thiokol® LP33, and Thiokol® LP55, available from Toray Industries, Inc. Thiokol® LP polysulfide has a number average molecular weight of 1,000 Da to 7,500 Da, an -SH content of 0.8% to 7.7%, and a crosslink density of 0% to 2%. The Thiokol® LP polysulfide prepolymer can have the structure of formula (6), and the end-modified polysulfide prepolymer can have the structure of formula (6a): HS-[(CH2)2-O-CH2-O-(CH2)2-SS-] n -(CH2)2-O-CH2-O-(CH2)2-SH (6) R 3 -S-[(CH2)2-O-CH2-O-(CH2)2-SS-] n -(CH2)2-O-CH2-O-(CH2)2-SR 3 (6a) In the formula, n is a number average molecular weight of 1,000 Da to 7,500 Da, for example For example, each R may be an integer from 8 to 80. 3 is a moiety that contains a terminal reactive functional group.

[0195] The thiol-terminated sulfur-containing prepolymer may include Thiokol-LP® polysulfide, Thioplast® G polysulfide, or a combination thereof.

[0196] The polysulfide prepolymer may comprise a polysulfide prepolymer comprising a moiety of formula (7), a thiol-terminated polysulfide prepolymer of formula (7a), an end-modified polysulfide prepolymer of formula (7b), or a combination of any of the foregoing: -R 6 -(S y -R 6) t - (7) HS-R 6 -(S y -R 6 ) t -SH (7a) R 3 -SR 6 -(S y -R 6 ) t -SR 3 (7b) During the ceremony, t may be an integer from 1 to 60; Each R 6 are independently branched alkanediyl, branched arenediyl, and -(CH2) p -O-(CH2) q -O-(CH2) r -, wherein q may be an integer from 1 to 8; p can be an integer from 1 to 10; r can be an integer from 1 to 10; y may have an average value in the range of 1.0 to 1.5; Each R 3 is a moiety that contains a terminal reactive functional group.

[0197] In the moiety of formula (7) and the prepolymer of formula (7a)-(7b), R 6 Between 0% and 20% of the groups may comprise branched alkanediyl or branched arenediyl, R 6 80% to 100% of the groups are -(CH2) p -O-(CH2) q -O-(CH2) r --It could be.

[0198] In the moiety of formula (7) and the prepolymer of formula (7a) to (7b), the branched alkanediyl or branched arenediyl is -R(-A) n -, where R is a hydrocarbon group, n is 1 or 2, and A is a branch point. The branched alkanediyl can have the structure -CH2(-CH(-CH2-)-)-.

[0199] Examples of thiol-terminated polysulfide prepolymers of formula (7a) and (7b) are disclosed, for example, in U.S. Application Publication No. 2016 / 0152775, U.S. Pat. No. 9,079,833, and U.S. Pat. No. 9,663,619.

[0200] The polysulfide prepolymer may comprise a polysulfide prepolymer comprising a moiety of formula (8), a thiol-terminated polysulfide prepolymer of formula (8a), an end-modified polysulfide prepolymer of formula (8b), or a combination of any of the foregoing: -(R 7 -O-CH2-OR 7 -S m -) n-1 -R 7 -O-CH2-OR 7 - (8) HS-(R 7 -O-CH2-OR 7 -S m -) n-1 -R 7 -O-CH2-OR 7 -SH (8a) R 3 -S-(R 7 -O-CH2-OR 7 -S m -) n-1 -R 7 -O-CH2-OR 7 -SR 3 (8b) In the formula, R 7 is C 2~4 alkanediyl, m is an integer of 2 to 8, n is an integer of 2 to 370, and each R 3 is independently a moiety that contains a terminal reactive functional group.

[0201] Moieties of formula (8) and prepolymers of formulae (8a)-(8b) are disclosed, for example, in JP62-53354.

[0202] The sulfur-containing prepolymer may include a sulfur-containing polyformal prepolymer or a combination of sulfur-containing polyformal prepolymers. Sulfur-containing polyformal prepolymers useful for sealant applications are disclosed, for example, in U.S. Patent No. 8,729,216 and U.S. Patent No. 8,541,513.

[0203] The sulfur-containing polyformal prepolymer may comprise a moiety of formula (9), a thiol-terminated sulfur-containing polyformal prepolymer of formula (9a), a terminal-modified sulfur-containing polyformal prepolymer of formula (9b), a thiol-terminated sulfur-containing polyformal prepolymer of formula (9c), a terminal-modified sulfur-containing polyformal prepolymer of formula (9d), or a combination of any of the foregoing: -R 8 -(S) p -R 8 -[OC(R 9 )2-OR 8 -(S) p -R 8 -] n - (9) R 10 -R 8 -(S) p -R 8 -[OC(R 9 )2-OR 8 -(S) p -R 8 -] n -R 10 (9a) R 3 -R 8 -(S) p -R 8 -[OC(R 9 )2-OR 8 -(S) p -R 8 -] n -R 3 (9b) {R 10 -R 8 -(S) p -R 8 -[OC(R 9 )2-OR 8 -(S) p -R8 -] n -OC(R 9 )2-O-} m Z (9c) {R 3 -R 8 -(S) p -R 8 -[OC(R 9 )2-OR 8 -(S) p -R 8 -] n -OC(R 9 )2-O-} m Z (9d) wherein n can be an integer from 1 to 50, each p can be independently selected from 1 and 2, and each R 8 is C 2~6 Each R may be an alkanediyl. 9 are independently hydrogen, C 1~6 Alkyl, C 7~12 Phenylalkyl, substituted C 7~12 Phenylalkyl, C 6~12 Cycloalkylalkyl, substituted C 6~12 Cycloalkylalkyl, C 3~12 Cycloalkyl, substituted C 3~12 Cycloalkyl, C 6~12 Aryl and substituted C 6~12 aryl, and each R 10 is a moiety containing a terminal thiol group, and each R 3 are independently moieties containing terminal reactive functional groups other than thiol groups, and Z is an m-valent parent polyol, Z(OH), m It may originate from the core of

[0204] The sulfur-containing prepolymer may include a monosulfide prepolymer or a combination of monosulfide prepolymers.

[0205] The monosulfide prepolymer can include a moiety of formula (10), a thiol-terminated monosulfide prepolymer of formula (10a), a thiol-terminated monosulfide prepolymer of formula (10b), a terminal-modified monosulfide prepolymer of formula (10c), a terminal-modified monosulfide prepolymer of formula (10d), or a combination of any of the foregoing: -SR 13 -[-S-(R 11 -X) p -(R 12 -X) q -R 13 -] n -S- (10) HS-R 13 -[-S-(R 11 -X) p -(R 12 -X) q -R 13 -] n -SH (10a) {HS-R 13 -[-S-(R 11 -X) p -(R 12 -X) q -R 13 -] n -S-V'-} z B (10b) R 3 -SR 13 -[-S-(R 11 -X) p -(R 12 -X) q -R 13 -] n -SR 3 (10c) {R 3 -SR 13 -[-S-(R 11 -X) p -(R 12 -X) q -R 13 -] n -S-V'-} z B (10d) During the ceremony, Each R 11 is independently2~10 Alkanediyl, e.g., C 2~6 Alkanediyl;C 2~10 Branched alkanediyl, for example, C 3~6 Branched alkanediyl, or e.g. C having one or more pendant groups which may be alkyl groups such as methyl or ethyl groups. 3~6 Branched alkanediyl; C 6~8 Cycloalkanediyl;C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 alkylarenediyl; Each R 12 is independently 1~10 n-Alkanediyl, e.g., C 1~6 n-Alkanediyl, C 2~10 Branched alkanediyl, e.g., C having one or more pendant groups which may be alkyl groups such as methyl or ethyl groups. 3~6 Branched alkanediyl; C 6~8 Cycloalkanediyl;C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 alkylarenediyl; Each R 13 is independently 1~10 n-Alkanediyl, e.g., C 1~6 n-Alkanediyl, C 2~10 Branched alkanediyl, e.g., C having one or more pendant groups which may be alkyl groups such as methyl or ethyl groups. 3~6 Branched alkanediyl; C 6~8 Cycloalkanediyl group; C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 alkylarenediyl; Each X may be independently selected from O and S; p can be an integer from 1 to 5; q may be an integer from 0 to 5; n may be an integer from 1 to 60, for example, from 2 to 60, from 3 to 60, or from 25 to 35; Each R 3 is independently selected from reactive functional groups; B is a z-valent polyfunctionalizing agent B(-V) z represents a core of the formula: z can be an integer from 3 to 6; Each V can be a moiety that includes a terminal group reactive to a thiol group, Each -V'- can result from the reaction of -V with a thiol.

[0206] Methods for synthesizing thiol-terminated monosulfide containing moieties of formula (10) or prepolymers of formulas (10b)-(10c) are disclosed, for example, in US Pat. No. 7,875,666.

[0207] The monosulfide prepolymer can comprise a moiety of formula (11), a thiol-terminated monosulfide prepolymer comprising a moiety of formula (11a), a thiol-terminated monosulfide prepolymer of formula (11b), a thiol-terminated monosulfide prepolymer of formula (11c), a thiol-terminated monosulfide prepolymer of formula (11d), or a combination of any of the foregoing: -[-S-(R 14 -X) p -C(R 15 )2-(XR 14 ) q -] n -S- (11) H-[-S-(R 14 -X) p -C(R 15 )2-(XR 14 ) q -] n -SH (11a) R 3 -[-S-(R 14 -X) p -C(R 15 )2-(XR 14 ) q -]n -SR 3 (11b) {H-[-S-(R 14 -X) p -C(R 15 )2-(XR 14 ) q -] n -S-V'-} z B (11c) {R 3 -[-S-(R 14 -X) p -C(R 15 )2-(XR 14 ) q -] n -S-V'-} z B (11d) During the ceremony, Each R 14 is independently 2~10 Alkanediyl, e.g., C 2~6 Alkanediyl;C 3~10 Branched alkanediyl, for example, C 3~6 C having one or more pendant groups which may be branched alkanediyl or alkyl groups such as methyl or ethyl groups. 3~6 Branched alkanediyl; C 6~8 Cycloalkanediyl;C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 alkylarenediyl; Each R 15 are independently hydrogen, C 1~10 n-Alkanediyl, e.g., C 1~6 n-Alkanediyl, C 3~10 Branched alkanediyl, e.g., C having one or more pendant groups which may be alkyl groups such as, for example, methyl or ethyl groups. 3~6 Branched alkanediyl; C 6~8 Cycloalkanediyl group; C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C8~10 alkylarenediyl; Each X may be independently selected from O and S; p can be an integer from 1 to 5; q can be an integer from 1 to 5; n may be an integer from 1 to 60, for example, from 2 to 60, from 3 to 60, or from 25 to 35; Each R 3 is a moiety containing a terminal functional group, B is a z-valent polyfunctionalizing agent B(-V) z represents a core of the formula: z can be an integer from 3 to 6; Each V can be a moiety that includes a terminal group reactive to a thiol group, Each -V'- can result from the reaction of -V with a thiol.

[0208] Methods for synthesizing the monosulfides of formulae (11) to (11d) are disclosed, for example, in US Pat. No. 8,466,220.

[0209] The prepolymer may include a terminally modified prepolymer, such as a terminally modified sulfur-containing prepolymer, which refers to a sulfur-containing prepolymer that includes a terminal reactive functional group other than a thiol group.

[0210] R 3 The terminal reactive functional group such as may be selected from, for example, alkenyl, alkynyl, epoxy, isocyanate, hydroxyl, amine, Michael acceptor, Michael donor, or another reactive functional group. A terminal-modified sulfur-containing prepolymer may be prepared, for example, by reacting a thiol-terminated sulfur-containing prepolymer with a compound that includes a terminal functional group and a group reactive to a thiol group.

[0211] Examples of suitable groups that react with thiol groups include alkenyl groups, alkynyl groups, epoxy groups, Michael acceptor groups, and isocyanate groups.

[0212] For example, alkenyl-terminated sulfur-containing prepolymers can be prepared by reacting a polyalkenyl compound with a thiol-terminated sulfur-containing prepolymer, epoxy-terminated sulfur-containing prepolymers can be prepared by reacting a polyepoxide with a thiol-terminated sulfur-containing prepolymer, isocyanate-terminated sulfur-containing prepolymers can be prepared by reacting a polyisocyanate with a thiol-terminated sulfur-containing prepolymer, and Michael acceptor-terminated sulfur-containing prepolymers can be prepared by reacting a multifunctional Michael acceptor with a thiol-terminated sulfur-containing prepolymer.

[0213] The coreactive composition may include a reactive monomer or a combination of reactive monomers. The coreactive monomer may include a functional group that is reactive to a prepolymer and / or another monomer.

[0214] The reactive monomer may have, for example, a molecular weight of less than 1,000 Da, less than 800 Da, less than 600 Da, less than 500 Da, less than 400 Da, or less than 300 Da. The monomer may have, for example, a molecular weight of 100 Da to 1,000 Da, 100 Da to 800 Da, 100 Da to 600 Da, 150 Da to 550 Da, or 200 Da to 500 Da. The monomers may have a molecular weight of greater than 100 Da, greater than 200 Da, greater than 300 Da, greater than 400 Da, greater than 500 Da, greater than 600 Da, or greater than 800 Da.

[0215] The reactive monomers may have reactive functionalities of 2 or more than 2, such as 2 to 6, 2 to 5, or 2 to 4. The reactive monomers may have a functionality of 2, 3, 4, 5, or 6. The reactive monomers may have an average reactive functionality of, for example, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 2.1 to 2.8, or 2.2 to 2.6.

[0216] The reactive monomer can include any suitable functional group, such as, for example, a thiol, alkenyl, alkynyl, epoxy, isocyanate, Michael acceptor, Michael donor, hydroxyl, amine, silanol, polyalkoxysilyl, or other suitable reactive functional group.

[0217] The reactive monomers may include, for example, polythiols, polyalkenyls, polyalkynyls, polyepoxides, multi-functional Michael acceptors, multi-functional Michael donors, polyisocyanates, polyols, polyamines, multi-functional silanols, multi-functional polyalkoxysilyls, or combinations of any of the foregoing.

[0218] The monomers may include sulfur-containing monomers.

[0219] The sulfur-containing monomer may have, for example, a sulfur content of 0% to 80%, 2% to 75%, 5% to 70%, 10% to 65%, 15% to 60%, or 20% to 50% by weight, where the weight percentage is based on the total molecular weight of the monomer. The monomer may have, for example, a sulfur content of more than 0%, more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, or more than 80% by weight, where the weight percentage is based on the total molecular weight of the monomer. The monomer may have, for example, a sulfur content of less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, or less than 5% by weight, where the weight percentage is based on the total molecular weight of the monomer.

[0220] The reactive monomer may include a multifunctionalizing agent or a combination of multifunctionalizing agents.

[0221] The multifunctionalizing agent may have a functionality of three or more than three functional groups that may be included in the composition to increase the crosslink density of the cured polymer matrix. The multifunctionalizing agent may contain functional groups that are reactive to reactive prepolymers and / or reactive monomers.

[0222] The polyfunctionalizing agent may, for example, comprise an average functionality of 3 to 6, such as 3 to 5 or 3 to 4. The polyfunctionalizing agent may have a functionality of 3, 4, 5, or 6.

[0223] The polyfunctionalizing agent may include, for example, a polythiol, a polyalkenyl, a polyalkynyl, a polyepoxide, a multifunctional Michael acceptor, a multifunctional Michael donor, a polyisocyanate, a polyol, a polyamine, a multifunctional silanol, a multifunctional polyalkoxysilyl, or a combination of any of the foregoing.

[0224] The first reactive compound and the second reactive compound can each independently include at least two first functional groups, and the second compound can include at least two second functional groups, where the second functional groups are reactive to the first functional groups.

[0225] For example, the first functional group can be a thiol group and the second functional group can be an alkenyl group, an alkynyl group, an epoxy group, a Michael acceptor group, an isocyanate group, or any of the foregoing. It can be any combination of.

[0226] The particular functional groups and cure chemistries may be selected to provide a desired cure rate and / or impart desired properties to the cured layer of the multi-layer system.

[0227] Examples of useful curing chemistries include hydroxyl / isocyanate, amine / isocyanate, epoxy / epoxy, and Michael acceptor / Michael donor reactions.

[0228] Thus, the first functional group can include an isocyanate and the second functional group can include a hydroxyl group, an amine group, or a combination thereof.

[0229] The first functional group can include an amine group and the second functional group can include an epoxy group.

[0230] The first functional group can include an epoxy group and the second functional group can include an epoxy group.

[0231] The first functional group can include a Michael acceptor group and the second functional group can include a Michael donor group.

[0232] The first functional group can be a saturated functional group, and the second functional group can be an unsaturated group. The first functional group and the second functional group can each include a saturated functional group. The first functional group and the second functional group can each include an unsaturated functional group. Saturated functional group refers to a functional group that does not have a double bond. Examples of saturated functional groups include thiol, hydroxyl, primary amine, secondary amine, and epoxy groups. Unsaturated functional group refers to a group that has a reactive double bond. Examples of unsaturated functional groups include alkenyl groups, Michael acceptor groups, isocyanate groups, acyclic carbonates, acetoacetate groups, carboxylic acid groups, vinyl ether groups, (meth)acrylate groups, and malonate groups.

[0233] The first functional group can be a carboxylic acid group and the second functional group can be an epoxy group.

[0234] The first functional group can be a Michael acceptor group, such as a (meth)acrylate, maleic acid, or fumaric acid group, and the second functional group can be a primary amine or secondary amine group.

[0235] The first functional group can be an isocyanate group and the second functional group can be a primary amine group, a secondary amine group, a hydroxyl group, or a thiol group.

[0236] The first functional group can be a cyclic carbonate group, an acetoacetate group, or an epoxy group, and the second functional group can be a primary amine group or a secondary amine group.

[0237] The first functional group can be a thiol group, and the second functional group can be an alkenyl group, a vinyl ether group, or a (meth)acrylate group.

[0238] The first functional group can be a Michael acceptor group such as a (meth)acrylate group, cyanoacrylate, vinyl ether, vinylpyridine, or an α,β-unsaturated carbonyl group, and the second functional group can be a malonate group, acetylacetonate, nitroalkane, or other activated alkenyl group.

[0239] The first functional group can be a thiol group and the second functional group can be an alkenyl group, an epoxy group, an isocyanate group, an alkynyl group, or a Michael acceptor group.

[0240] The first functional group can be a Michael donor group and the second functional group can be a Michael acceptor group.

[0241] Both the first functional group and the second functional group can be a thiol group.

[0242] Both the first functional group and the second functional group can be an alkenyl group.

[0243] Both the first and second functional groups can be Michael acceptor groups, such as (meth)acrylate groups.

[0244] For example, the first reactive compound may include a polyamine and / or a polyol, the second reactive compound may include a polyisocyanate, the first reactive compound may include a Michael acceptor and the second reactive compound may include a Michael donor, or the first reactive compound may include a polythiol and the second reactive compound may include a polythiol, polyisocyanate, polyalkenyl, polyalkynyl, polyepoxide, Michael acceptor, or a combination of any of the foregoing.

[0245] The functional groups may be selected to co-react at temperatures, for example, below 50° C., below 40° C., below 30° C., below 20° C., or below 10° C. The functional groups may be selected to co-react at temperatures, for example, above 5° C., above 10° C., above 20° C., above 30° C., or above 40° C. The functional groups may be selected to co-react at temperatures, for example, between 5° C. and 50° C., between 10° C. and 40° C., between 15° C. and 35° C., or between 20° C. and 30° C.

[0246] The cure rate of any of these co-reactive chemical reactions can be modified by including an appropriate catalyst or combination of catalysts in the co-reactive composition. The cure rate of any of these co-reactive chemical reactions can be modified by increasing or decreasing the temperature of the co-reactive composition. For example, the co-reactive composition can be cured at temperatures below 30° C., e.g., below 25° C. or below 20° C., but the reaction rate can be accelerated by heating the co-reactive composition, which may be desirable under certain circumstances, such as to accommodate increased printing speeds. Increasing the temperature of the co-reactive components and / or the co-reactive composition can also serve to adjust the viscosity to facilitate mixing of the co-reactive components and / or deposition of the co-reactive composition.

[0247] To form a multi-layer system, it may be desirable for certain layers to cure faster than others, for example, outer layers to cure quickly to promote the ability of the applied multi-layer system to hold its intended shape, and inner layers to cure slowly to develop adhesion and / or desired physical properties over time.

[0248] Each coreactive composition used to prepare a layer of a multilayer system may, for example, independently include one or more additives such as, for example, catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, fillers, colorants, photochromic agents, rheology modifiers, cure activators and accelerators, corrosion inhibitors, flame retardants, UV stabilizers, rain erosion inhibitors, or combinations of any of the foregoing.

[0249] The coreactive composition may include one or more additives selected to impart one or more desired properties to the cured layer of the multi-layer system. Examples of properties of the cured layer and additives for providing properties to the layer are described in the following paragraphs.

[0250] The coreactive composition may include a catalyst or a combination of catalysts.

[0251] A catalyst or combination of catalysts can be selected to catalyze the reaction of a co-reactant in the co-reactive composition, such as the reaction of a first reactive compound and a second reactive compound. The appropriate catalyst will depend on the curing chemistry. For example, a thiol-ene or thiol epoxy can include an amine catalyst.

[0252] The coreactive composition can include, for example, 0.1 wt % to 1 wt %, 0.2 wt % to 0.9 wt %, 0.3 wt % to 0.7 wt %, or 0.4 wt % to 0.6 wt % of a catalyst or combination of catalysts, where the wt % is based on the total weight of the coreactive composition.

[0253] The catalyst may include a latent catalyst or a combination of latent catalysts. Latent catalysts include catalysts that have little or no activity until released or activated, for example, by physical and / or chemical mechanisms. Latent catalysts may be contained within the structure or may be chemically blocked. Controlled release catalysts may release the catalyst upon exposure to ultraviolet light, heat, ultrasound, or moisture. Latent catalysts may be sequestered within a core-shell structure or entrapped within a matrix of crystalline or semi-crystalline polymers, and the catalyst may diffuse out of the inclusion over time or upon activation, such as by application of thermal or mechanical energy.

[0254] The coreactive composition may include a dark cure catalyst or a combination of dark cure catalysts. A dark cure catalyst refers to a catalyst that can generate free radicals without exposure to electromagnetic energy.

[0255] Dark cure catalysts include, for example, combinations of metal complexes and organic peroxides, trialkylborane complexes and peroxide-amine redox initiators. Dark cure catalysts can be used in conjunction with photoinitiators or independently of photoinitiators.

[0256] Coreactive compositions based on thiol / thiol curing chemistry can include a curing activator or a combination of curing activators to initiate the thiol / thiol polymerization reaction. Curing activators can be used, for example, in coreactive compositions where the first reactive compound and the second reactive compound both include a thiol-terminated sulfur-containing prepolymer, such as a thiol-terminated polysulfide prepolymer.

[0257] The cure activator may include an oxidizing agent capable of oxidizing mercaptan 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 dichromates.

[0258] The cure activator may include an inorganic activator, an organic activator, or a combination thereof.

[0259] Examples of suitable inorganic activators include metal oxides. Examples of suitable metal oxide activators include zinc oxide (ZnO), lead oxide (PbO), lead peroxide (PbO3), manganese dioxide (MnO2), sodium perborate (NaBO3H2O), potassium permanganate (KMnO4), calcium peroxide (CaCO3), barium peroxide (BaO3), cumene hydroperoxide, and any combination of the above. The cure activator can be MnO2.

[0260] Coreactive compositions based on thiol / thiol curing chemistry can include, for example, 1 wt. % to 10 wt. % of a curing activator or combination of curing activators, where the wt. % is based on the total weight of the coreactive composition. For example, the coreactive composition can include 1 wt. % to 9 wt. %, 2 wt. % to 8 wt. % of a curing activator or combination of curing activators, where the wt. % is based on the total weight of the coreactive composition. The coreactive composition may comprise between 1 wt%, 3 wt%, 7 wt%, or 4 wt% to 6 wt% of an activator or combination of curing activators, where the weight percent is based on the total weight of the coreactive composition. For example, the coreactive composition may comprise more than 1 wt%, more than 2 wt%, more than 3 wt%, more than 4 wt%, more than 5 wt%, or more than 6 wt% of a curing activator or combination of curing activators, where the weight percent is based on the total weight of the coreactive composition.

[0261] Co-reactive compositions based on thiol / thiol curing chemistry can include a cure accelerator or a combination of cure accelerators.

[0262] The cure accelerator can act as a sulfur donor to generate active sulfur fragments that can react with the thiol groups of the thiol-terminated polysulfide prepolymer.

[0263] Examples of suitable cure accelerators include thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldehyde amines, and combinations of any of the foregoing.

[0264] The cure accelerator may include a thiuram polysulfide, a thiuram disulfide, or a combination thereof.

[0265] Other suitable examples of cure accelerators include triazines and sulfides or metal and amine salts of dialkyl dithiophosphoric acids and dithiophosphates, such as triazines and sulfides or metal and amine salts of dialkyl dithiophosphoric acids, and also combinations of any of the foregoing. Examples of non-sulfur-containing cure accelerators include tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water, and base.

[0266] The coreactive composition may, for example, comprise from 0.01% to 2% by weight of the cure accelerator or combination of cure accelerators, from 0.05% to 1.8% by weight, from 0.1% to 1.6% by weight, or from 0.5% to 1.5% by weight of the cure accelerator or combination of cure accelerators, where the weight percentages are based on the total weight of the coreactive composition. The coreactive composition may, for example, comprise less than 2% by weight, less than 1.8% by weight, less than 1.6% by weight, less than 1.4% by weight, less than 1.2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or less than 0.05% by weight of the cure accelerator or combination of cure accelerators, where the weight percentages are based on the total weight of the coreactive composition.

[0267] The coreactive composition can include one or more free radical initiators, such as a thermally activated free radical initiator or a free radical initiator activated by actinic radiation.

[0268] Co-reactive compositions, such as sealant compositions based on thiol / alkenyl, thiol / alkynyl, and alkenyl / alkenyl curing chemistries, may be curable by actinic radiation. Co-reactive compositions that are curable by visible or ultraviolet light may include a photoinitiator or a combination of photoinitiators.

[0269] The coreactive composition may include a photoinitiator or a combination of photoinitiators. The radiation may be actinic radiation capable of applying energy effective to generate a species from the photoinitiator upon irradiation by the photoinitiator, broadly including alpha radiation, gamma radiation, X-rays, ultraviolet (UV) radiation (including UVA, UVA, and UVC spectrum), visible light, blue light, infrared, near infrared, or electron beam. For example, the photoinitiator may be a UV photoinitiator.

[0270] Examples of suitable UV photoinitiators include α-hydroxyketones, benzophenones, α,α- diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2-hydroxy-2-propyl ketone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, O-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosuberone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyclophosphine oxide, benzophenone photoinitiators, oxime photoinitiators, phosphine oxide photoinitiators, and combinations of any of the foregoing.

[0271] The coreactive composition may comprise 0.05 wt% to 5 wt%, 0.1 wt% to 4.0 wt%, 0.25 wt% to 3.0 wt%, 0.5 wt% to 1.5 wt% of a photoinitiator or combination of photoinitiators, where the wt% is based on the total weight of the coreactive composition.

[0272] The coreactive composition may include a thermally activated free radical initiator. The thermally activated free radical initiator may be activated at elevated temperatures, such as temperatures above 25°C.

[0273] Examples of suitable thermally activated free radical initiators include organic peroxy compounds, azobis(organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations of any of the foregoing. Examples of suitable organic peroxy compounds that can be used as thermal polymerization initiators include peroxymonocarbonate esters, such as tertiary butylperoxy 2-ethylhexyl carbonate and tertiary butylperoxy isopropyl carbonate; peroxyketals, such as 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane; peroxydicarbonate esters, such as di(2-ethylhexyl)peroxydicarbonate, di(sec-butyl)peroxydicarbonate and diisopropylperoxydicarbonate; diacyperoxy. Peroxy compounds include peroxy esters such as tert-butyl peroxypivalate, tert-butyl peroxyoctylate, and tert-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, acetylcyclohexanesulfonyl peroxide, and combinations of any of the foregoing. Other examples of suitable peroxy compounds include 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and / or 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane. Examples of suitable azobis(organonitrile) compounds that can be used as thermal polymerization initiators include azobis(isobutyronitrile), 2,2'-azobis(2-methyl-butanenitrile), and / or azobis(2,4-dimethylvaleronitrile). Thermally activated free radical initiators can include 1-acetoxy-2,2,6,6-tetramethylpiperidine and / or 1,3-dicyclohexyl-O-(N-cyclohexylideneamino)-isourea.

[0274] The coreactive composition may include an adhesion promoter or combination of adhesion promoters. The adhesion promoter may enhance adhesion of the sealant to an underlying substrate such as a metal, composite, polymer, or ceramic surface, or to a coating such as a primer coating or other coating layer. The adhesion promoter may enhance adhesion to fillers and to other layers of a multi-layer system.

[0275] Adhesion promoters include phenolic adhesion promoters and combinations of phenolic adhesion promoters. , an organofunctional silane, a combination of organofunctional silanes, or a combination of any of the foregoing. The organofunctional alkoxysilane can be an amine-functional alkoxysilane. The organo group can be selected from, for example, a thiol group, an amine group, an epoxy group, an alkenyl group, an isocyanate group, or a Michael acceptor group.

[0276] The phenolic adhesion promoter may include heat-treated phenolic resins, unheat-treated phenolic resins, or combinations thereof. Examples of suitable adhesion promoters include phenolic resins, such as Methylon® phenolic resins, and organosilanes, such as epoxy, mercapto, or amine functional silanes, e.g., Silquest® organosilanes. Heat-treated phenolic resins refer to phenolic resins that have been co-reacted with a monomer or prepolymer.

[0277] The phenolic adhesion promoter may comprise the reaction product of a condensation reaction between a phenolic resin and one or more thiol-terminated polysulfides. The phenolic adhesion promoter may be thiol-terminated.

[0278] Examples of suitable 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)cyclohexa-2,4-dien-1-yl)methyl)-1,3-phenylene)dimethanol, (4-hydroxy-5-((2-hydroxy-3,5-bis(hydroxymethyl)cyclohexa-2,4-dien-1-yl)methyl)-1,3-phenylene)dimethanol, and those synthesized from any combination of the foregoing.

[0279] Suitable phenolic resins may be synthesized by the base catalyzed reaction of phenol with formaldehyde.

[0280] Phenolic adhesion promoters may include reaction products of the condensation reaction of Methylon® resins, Varcum® resins, or Durez® resins available from Durez Corporation with thiol-terminated polysulfides, such as Thioplast® resins.

[0281] Examples of Methylon® resins include Methylon® 75108 (an allyl ether of methylol phenol, see U.S. Pat. No. 3,517,082) and Methylon® 75202.

[0282] Examples of Varcum® resins include Varcum® 29101, Varcum® 29108, Varcum® 29112, Varcum® 29116, Varcum® 29008, Varcum® 29202, Varcum® 29401, Varcum® 29159, Varcum® 29181, Varcum® 92600, Varcum® 94635, Varcum® 94879, and Varcum® 94917.

[0283] An example of a Durez® resin is Durez® 34071.

[0284] The coreactive composition may include an organofunctional alkoxysilane adhesion promoter, such as an organofunctional alkoxysilane. The organofunctional alkoxysilane may include a hydrolyzable group and at least one organofunctional group bonded to a silicon atom. The organofunctional alkoxysilane may include an R 2 0 -(CH2) n -Si(-OR) 3-n R n and R 20 is an organofunctional group, n is 0, 1, or 2, and R is an alkyl, such as methyl or ethyl. Examples of organofunctional groups include epoxy, amino, methacryloxy, or sulfide groups. The organofunctional alkoxysilane can 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 can be a combination of a monoalkoxysilane and a dipodal alkoxysilane. For amino-functional alkoxysilanes, R 20 can be -NH2.

[0285] Examples of suitable amino-functional alkoxysilanes under the Silquest® trade name include gamma-aminopropyltriethoxysilane (Silquest® A-1100), gamma-aminopropylsilsesquioxane (Silquest® A-1108), gamma-aminopropyltrimethoxysilane (Silquest® A-1110), N-β-(aminoethyl)-gamma-aminopropyltrimethoxysilane (Silquest® 1120), benzylaminosilane (Silquest® 1128), trimethoxysilane (Silquest® A-1130), trimethoxysilane (Silquest® A-1132), trimethoxysilane (Silquest® A-1134), trimethoxysilane (Silquest® A-1136), trimethoxysilane (Silquest® A-1138), trimethoxysilane (Silquest® A-1139), trimethoxysilane (Silquest® A-1140), trimethoxysilane (Silquest® A-1141), trimethoxysilane (Silquest® A-1142), trimethoxysilane (Silquest® A-1143), trimethoxysilane (Silquest® A-1144), trimethoxysilane (Silquest® A-1145), trimethoxysilane (Silquest® A-1146), trimethoxysilane (Silquest® A-1147), trimethoxysilane (Silquest® A-1148), trimethoxysilane (Silquest® A-1149), trimethoxysilane (Silquest® A-1150), trimethoxysilane (Silquest® A-1151), trimethoxysilane (Silquest® A-1152), trimethoxysilane (Silquest® A-1153), trimethoxysilane (Silquest® A-1154), trimethoxysilane (Silquest® A-1155), trimethoxysilane (Silquest® A-1156), trimethoxysilane (Silquest® A-1 Included are amino-functional silanes (Silquest® A-1130), bis-(γ-triethoxysilylpropyl)amine (Silquest® Y-11699), bis-(γ-trimethoxysilylpropyl)amine (Silquest® A-1170), polyazamides (Silquest® A-1387), ethoxy-based polyazamides (Silquest® Y-19139), and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (Silquest® A-2120).

[0286] Suitable amine-functional alkoxysilanes are commercially available from, for example, Gelest Inc., Dow Corning Corporation, and Momentive.

[0287] The co-reactive composition 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 % of an adhesion promoter or combination of adhesion promoters, where the wt % is based on the total weight of the co-reactive composition.

[0288] The co-reactive composition may comprise 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 combination of adhesion promoters, where the weight percentages are based on the total weight of the co-reactive composition.

[0289] The coreactive compositions for forming the layers of the multi-layer system can include a filler or a combination of fillers. The fillers can include, for example, inorganic fillers, organic fillers, low density fillers such as fillers having a specific gravity less than 1, conductive fillers, or a combination of any of the foregoing.

[0290] The coreactive compositions for forming the multi-layer systems may include an inorganic filler or a combination of inorganic fillers.

[0291] Inorganic fillers may be included, for example, to provide mechanical reinforcement and to control the rheological properties of the composition. Inorganic fillers may be added to the composition to impart desired physical properties, such as, for example, to increase impact strength, to control viscosity, or to modify the electrical properties of the cured coreactive composition.

[0292] Inorganic fillers useful in the sealant composition include carbon black, calcium carbonate, precipitated calcium carbonate, calcium hydroxide, hydrated alumina (aluminum hydroxide), talc, mica, titanium dioxide, alumina silicate, carbonates, chalk, silicates, glass, metal oxides, graphite, and combinations of any of the foregoing.

[0293] Suitable calcium carbonate fillers may include products such as Socal® 31, Socal® 312, Socal® U1S1, Socal® UaS2, Socal® N2R, Winnofil® SPM, and Winnofil® SPT available from Solvay Special Chemicals. The calcium carbonate filler may include a combination of precipitated calcium carbonates.

[0294] The inorganic filler can be surface treated to provide a hydrophobic or hydrophilic surface that can facilitate dispersion of the inorganic filler and compatibility of the inorganic filler with other components of the coreactive composition. The inorganic filler can include surface-modified particles, such as surface-modified silica. The surface of the silica particles can be modified, for example, to adjust the hydrophobicity or hydrophilicity of the surface of the silica particles. The surface modification can affect the dispersibility, viscosity, cure speed, and / or adhesion of the particles.

[0295] The coreactive composition may include an organic filler or a combination of organic fillers.

[0296] The organic filler may be selected to have a low specific gravity and to be resistant to solvents such as JRF Type I and / or to reduce the density of the layer. Suitable organic fillers may also have acceptable adhesion to the sulfur-containing polymer matrix. The organic filler may include solid powders or particles, hollow powders or particles, or a combination thereof.

[0297] The organic filler may have, for example, a specific gravity of 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 organic filler may have, for example, a specific gravity 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.

[0298] The organic filler may include a thermoplastic, a thermosetting material, or a combination thereof. Examples of suitable thermoplastic and thermosetting materials include epoxy, epoxyamide, ethylene tetrafluoroethylene copolymer, nylon, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylidene chloride, polyvinyl fluoride, tetrafluoroethylene, polyamide, polyimide, ethylene propylene, perfluorohydrocarbon, fluoroethylene, polycarbonate, polyetheretherketone, polyetherketone, polyphenylene oxide, polyphenylene sulfide, polystyrene, polyvinyl chloride, melamine, polyester, phenols, epichlorohydrin, fluorinated hydrocarbons, polycyclic materials, polybutadiene, polychloroprene, polyisoprene, polysulfide, polyurethane, isobutylene isoprene, silicone, styrene butadiene, liquid crystal polymer, and any combination of the above.

[0299] Examples of suitable polyamide 6 and polyamide 12 particles are available from Toray Plastics as grades SP-500, SP-10, TR-1, and TR-2. Suitable polyamide powders are also available from Arkema Group under the trade name Orgasol® and from Evonik Industries under the trade name Vestosin®.

[0300] The organic filler can have any suitable shape. For example, the organic filler can be in a desired size range. The organic filler may comprise a fraction of ground polymer that has been filtered to select a particle size distribution. The organic filler may comprise substantially spherical particles. The particles may be solid or porous.

[0301] The organic filler may have an average particle size in the range of, for example, 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 organic filler may have an average particle size of, 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 may be determined by using a Fisher subsieve sizer or by optical inspection.

[0302] The organic filler may include a low density filler such as a modified expanded thermoplastic microcapsule. Suitable modified expanded thermoplastic microcapsules may include an outer coating of melamine or urea / formaldehyde resin.

[0303] The coreactive composition may include low density microcapsules. The low density microcapsules may include thermally expandable microcapsules.

[0304] Thermally expandable microcapsules refer to hollow shells containing a volatile material that expands at a given temperature. Thermally expandable thermoplastic microcapsules may have an average initial particle size of 5 μm to 70 μm, sometimes 10 μm to 24 μm, or even 10 μm to 17 μm. The term "average initial particle size" refers to the average particle size (number weighted average of the particle size distribution) of the microcapsules before any expansion. The particle size distribution may be determined by using a Fisher subsieve sizer or by optical inspection.

[0305] 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 these polymers and copolymers. A crosslinking agent may be included with the material that forms the walls of the thermally expandable microcapsules.

[0306] Examples of suitable thermoplastic microcapsules include Expancel™ microcapsules, such as Expancel™ DE microspheres available from AkzoNobel. Examples of suitable Expancel™ DE microspheres include Expancel™ 920DE40 and Expancel™ 920DE80. Suitable low density microcapsules are also available from Kureha Corporation.

[0307] Low density fillers, such as low density microcapsules, may be characterized by a specific gravity in the range of 0.01-0.09, 0.04-0.09, 0.04-0.08, 0.01-0.07, 0.02-0.06, 0.03-0.05, 0.05-0.09, 0.06-0.09, or 0.07-0.09, where the specific gravity is determined in accordance with ISO 787-11. Low density fillers, such as low density microcapsules, may be characterized by a specific gravity 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, where the specific gravity is determined in accordance with ISO 787-11.

[0308] Low density fillers, such as low density microcapsules, may be characterized as having an average particle size of 1 μm to 100 μm and a substantially spherical shape. Substantially spherical particles may have a maximum cross-sectional dimension that is less than the minimum cross-sectional dimension of a low density filler particle, such as a low density microcapsule, and may have an average particle size of 10 μm to 100 μm, for example, as determined according to ASTM D6913. m, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm.

[0309] Low density fillers, such as low density microcapsules, may include expanded microcapsules or microballoons having a coating of an aminoplast resin, such as a melamine resin. Aminoplast resin-coated particles are described, for example, in U.S. Pat. No. 8,993,691. Such microcapsules may be formed by heating a microcapsule containing a blowing agent surrounded by a thermoplastic shell. Uncoated low density microcapsules may be reacted with an aminoplast resin, such as a urea / formaldehyde resin, to provide a coating of a thermosetting resin on the outer surface of the particle.

[0310] Depending on the coating of the aminoplast resin, the aminoplast coated microcapsules may be characterized by a specific gravity in the range of, for example, 0.02-0.08, 0.02-0.07, 0.02-0.06, 0.03-0.07, 0.03-0.065, 0.04-0.065, 0.045-0.06, or 0.05-0.06, the specific gravity being determined according to ISO 787-11.

[0311] The coreactive composition may include a microparticulated polyethylene oxide homopolymer. The organic filler may include a polyethylene, such as a polyethylene oxide powder. Suitable polyethylenes are available, for example, from Honeywell International, Inc. under the trade name ACumist®, from INEOS under the trade name Eltrex®, and from Mitsui Chemicals America, Inc. under the trade name Mipelon®.

[0312] The coreactive composition can include, for example, 1 wt. % to 90 wt. % low density filler, 1 wt. % to 60 wt. %, 1 wt. % to 40 wt. %, 1 wt. % to 20 wt. %, 1 wt. % to 10 wt. %, or 1 wt. % to 5 wt. % low density filler, where the wt. % is based on the total weight of the coreactive composition.

[0313] The coreactive composition may comprise greater than 1 wt.% low density filler, greater than 1 wt.%, greater than 2 wt.%, greater than 3 wt.%, greater than 4 wt.%, greater than 6 wt.%, or greater than 10 wt.% low density filler, where the wt.% is based on the total weight of the coreactive composition.

[0314] The coreactive composition can comprise 1% to 90% by volume of the low density filler, 5% to 70% by volume, 10% to 60% by volume, 20% to 50% by volume, or 30% to 40% by volume of the low density filler, where the volume percentages are based on the total volume of the coreactive composition.

[0315] The coreactive composition can comprise greater than 1 vol.% low density filler, greater than 5 vol.%, greater than 10 vol.%, greater than 20 vol.%, greater than 30 vol.%, greater than 40 vol.%, greater than 50 vol.%, greater than 60 vol.%, 70 vol.%, or greater than 80 vol.% low density filler, where the vol.% is based on the total volume of the coreactive composition.

[0316] The coreactive composition may include a conductive filler or a combination of conductive fillers. The conductive fillers may include electrically conductive fillers, semiconductive fillers, thermally conductive fillers, magnetic fillers, EMI / RFI shielding fillers, static dissipative fillers, electroactive fillers, or a combination of any of the foregoing. EMI / RFI shielding effectiveness may be determined according to ASTM D4935.

[0317] The coreactive composition may include an electrically conductive filler or a combination of electrically conductive fillers. .

[0318] To make the stiffened layer electrically conductive, the concentration of the electrically conductive filler may be above the electro-osmotic threshold, where a conductive network of electrically conductive particles is formed. Once the electro-osmotic threshold is reached, the increase in conductivity with filler loading can be modeled in a simple power form: σ c = σ f (φ-φ c ) t EQN.1 In the formula, φ is the volume fraction of the filler, and φ c is the percolation threshold, and σ fis the conductivity of the filler, φ is the composite conductivity, and t is a scaling component. The fillers do not need to be in direct contact for current to flow, and conduction can occur via tunneling between thin layers of binder surrounding the electrically conductive filler particles, and this tunneling resistance can be the limiting factor in the conductivity of the electrically conductive layer.

[0319] The conductive fillers can have any suitable shape and / or size. For example, the electrically conductive fillers can be in the form of particles, powders, flakes, platelets, filaments, fibers, crystals, or any combination of the foregoing.

[0320] The conductive fillers may include a combination of conductive fillers having different shapes, different dimensions, different properties (e.g., different thermal conductivities, electrical conductivities, magnetic permeabilities, electromagnetic properties, or any combination of the foregoing).

[0321] The conductive fillers can be solid or in the form of a matrix such as a particle having a coating of a conductive material. For example, the conductive fillers can be low density microcapsules having an outer conductive coating.

[0322] Examples of suitable electrically conductive, such as conductive fillers, include metals, metal alloys, conductive oxides, semiconductors, carbon, carbon fibers, and combinations of any of the foregoing.

[0323] Other examples of electrically conductive fillers include electrically conductive precious metal-based fillers such as pure silver; precious metal-plated precious metals such as silver-plated gold; precious metal-plated non-precious metals such as silver-plated copper, nickel, or aluminum, for example, silver-plated aluminum core particles or platinum-plated copper particles; precious metal-plated glass, plastic, or ceramic, such as silver-plated glass microparticles, precious metal-plated aluminum, or precious metal-plated plastic microparticles; precious metal-plated mica; and other such precious metal conductive fillers. Non-precious metal-based materials can also be used, including non-precious metal-plated non-precious metals such as copper-coated iron particles or nickel-plated copper; non-precious metals such as copper, aluminum, nickel, cobalt; non-precious metal-plated non-metals such as nickel-plated graphite, and non-metal materials such as carbon black and graphite. Combinations of electrically conductive fillers and shapes of electrically conductive fillers can be used to achieve the desired conductivity, EMI / RFI shielding effect, hardness, and other properties suitable for a particular application.

[0324] The amount and type of electrically conductive filler shall be such that when cured, it has a resistivity of 0.50 Ω / cm 2 Sheet resistance (four-point resistance) of less than 0.15 Ω / cm 2 The amount and type of filler may also be selected to provide effective EMI / RFI shielding over a frequency range of 1 MHz to 18 GHz for openings sealed using the multilayer compositions provided by the present disclosure.

[0325] Organic fillers, inorganic fillers, and low density fillers can be coated with metals to provide conductive fillers.

[0326] The electrically conductive filler may include graphene, which is a nanotube with a thickness equal to the atomic size of one carbon atom, i.e., sp 2It comprises a close-packed honeycomb crystal lattice made of carbon atoms with a single wall of hybridized carbon atoms.

[0327] Graphene may include graphene-based carbon particles, which are nanotubes densely packed in a honeycomb crystal lattice. 2 Refers to carbon particles having a structure that includes one or more layers of planar sheets of bonded carbon atoms, one atom thick. The average number of stacked layers can be less than 100, such as less than 50. The average number of stacked layers can be less than 30 or 30, such as less than 20 or 20, less than 10 or 10, or even less than 5 or 5. Graphene carbon particles can be substantially flat, but at least a portion of the planar sheets can be substantially curved, curled, folded, or distorted. Graphene carbon particles typically do not have an ellipsoidal or equiaxed morphology.

[0328] The grapheme carbon particles may have a thickness, measured in a direction perpendicular to the carbon atom layers, of, for example, 10 nm or less, 5 nm or less, or 4 nm or less, or 3 nm or less, or 2 nm or less, or 1 nm or less, for example, 3.6 nm or less. The grapheme carbon particles may have a thickness of 1 to 3, 6, 9, 12, 20, or 30 atomic layers or more. The grapheme carbon particles may have a width and length, measured in a direction parallel to the carbon atom layers, of at least 50 nm, for example, greater than 100 nm, greater than 100 nm to 500 nm, or greater than 100 nm to 200 nm. The graphene carbon particles can be provided in the form of ultra-thin flakes, platelets, or sheets having a relatively high aspect ratio, which is the ratio of the longest dimension of the particle to the shortest dimension of the particle, greater than 3:1, for example, greater than 10:1.

[0329] Graphene carbon particles can include exfoliated graphite and have different characteristics such as different size distribution, thickness, aspect ratio, structural morphology, oxygen content, and chemical functionality at the basal plane / edges compared to thermally produced graphene carbon particles.

[0330] Graphene carbon particles can be functionalized. Functionalized graphene carbon particles refer to graphene carbon particles in which organic groups are covalently bonded to the graphene carbon particles. Graphene carbon particles can be functionalized by forming 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 in the graphene carbon particles. Graphene carbon particles can also be functionalized by other reactions such as Diels-Alder addition reactions, 1,3-dipolar cycloaddition reactions, free radical addition reactions, and diazonium addition reactions. The hydrocarbon and phenyl groups can be further functionalized. In the case of graphene carbon particles with hydroxyl functional groups, the hydroxyl functional groups can be modified and extended by reacting these groups with, for example, organic isocyanates.

[0331] Different types of grapheme carbon particles can be used in the co-reactive composition.

[0332] The co-reactive 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 thermally produced grapheme carbon particles.

[0333] Fillers used to impart electrical conductivity and EMI / RFI shielding effects can be used in combination with graphene.

[0334] Electrically conductive non-metallic fillers such as carbon nanotubes, carbon fibers such as graphitized carbon fibers, and electrically conductive carbon black can also be used in combination with graphene in the co-reactive composition.

[0335] The conductive fillers may include magnetic fillers or a combination of magnetic fillers.

[0336] The magnetic filler may include a soft magnetic metal. This can improve the permeability of the magnetic molding resin. At least one magnetic material selected from Fe, Fe-Co, Fe-Ni, Fe-Al, and Fe-Si may be used as the main component of the soft magnetic metal. The magnetic filler may be a soft magnetic metal with high 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 (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 powder, Sm2Co 17 Powder, Nd-B-Fe powder, barium ferrite BaFe2O4, bismuth ferrite BiFeO3, chromium dioxide CrO2, SmFeN, NdFeB, and SmCo.

[0337] The surface of the magnetic filler may be insulatively coated or may have an insulative coating thickness of 10 nm or greater.

[0338] The surface of the magnetic filler can be insulating coated with metal oxides such as Si, Al, Ti, Mg or organic materials to improve the flowability, adhesion and insulating performance.

[0339] Examples of carbonaceous materials suitable for use as conductive fillers other than graphene and graphite include, for example, graphitized carbon black, 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.

[0340] The conductive filler may include a semiconductor or a combination of semiconductors.

[0341] Examples of suitable semiconductor materials include semiconductor nanomaterials such as nanoparticles, nanorods, nanowires, nanotubes, and nanosheets, semiconductor metal oxides such as tin oxide, antimony oxide, and indium oxide, semiconductor polymers such as PEDOT:PSS, polythiophenes, poly(p-phenylene sulfide), polyaniline, poly(pyrrole), poly(acetylene), poly(p-phenylene vinylene), polyparaphenylene, any other conjugated polymer, and semiconductor small molecules, e.g., semiconducting polymers having a molecular weight of less than 5,000 Da, such as rubrene, pentacene, anthracene, and aromatic hydrocarbons. Examples of semiconductor nanomaterials include quantum dots, III-V or II-VI semiconductors, Si, Ge, transition metal dichalcogenides (WS 2、 WSe2, and MoSe s etc.), graphene nanoribbons, semiconducting carbon nanotubes, and fullerenes and fullerene derivatives.

[0342] The filler material may include metal fibers such as steel, titanium, aluminum, gold, silver, and alloys of any of the foregoing.

[0343] Examples of suitable ceramic fibers include alumina fibers, alumina silicate fibers, and porosinitride fibers. Included are metal oxides such as uranium fibers, silicon carbide fibers, and combinations of any of the foregoing.

[0344] Examples of suitable inorganic fibers include carbon, alumina, basalt, calcium silicate, and rock wool.

[0345] 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 braided glass fibers or non-woven glass fibers.

[0346] The fibers may include carbon, for example, graphite fibers, glass fibers, ceramic fibers, silicon carbide fibers, polyimide fibers, polyamide fibers, or polyethylene fibers. The continuous fibers may include titanium, tungsten, boron, shape memory alloys, graphite, silicon carbide, boron, aramid, poly(p-phenylene-2,6-benzobisoxazole), and combinations of any of the foregoing.

[0347] Fibers capable of withstanding high temperatures include, for example, carbon fibers, high strength glass (SiO2) fibers, oxide fibers, alumina fibers, ceramic fibers, metal fibers, and fibers of high temperature thermoplastics or thermosets.

[0348] The filler may include carbon nanotubes. Suitable carbon nanotubes may be characterized by a thickness or length of, for example, 1 nm to 5,000 nm. Suitable carbon nanotubes may be cylindrical in shape and structurally related to fullerenes. Suitable carbon nanotubes may be open or capped at their ends. Suitable carbon nanotubes may include, for example, greater than 90% by weight, greater than 95% by weight, greater than 99% by weight, or greater than 99.9% by weight carbon, the weight percentage being based on the total weight of the carbon nanotubes.

[0349] Carbon nanotubes can be provided as single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs), e.g., nanotubes with one wall and nanotubes with more than one wall, respectively. In single-walled nanotubes, a one-atom-thick sheet of atoms, e.g., a one-atom-thick sheet of graphite, i.e., graphene, is seamlessly rolled to form a cylinder. A multi-walled nanotube consists of several such cylinders arranged concentrically.

[0350] Multi-walled carbon nanotubes can have, for example, an average of 5 to 15 walls.

[0351] Single-walled nanotubes may be characterized by a diameter of at least 0.5 nm, e.g., at least 1 nm or at least 2 nm. SWNTs may have a diameter of less than 50 nm, e.g., less than 30 nm or less than 10 nm. The length of a single-walled nanotube may be at least 0.05 μm, at least 0.1 μm, or at least 1 μm. The length may be less than 50 mm, e.g., less than 25 mm.

[0352] Multi-walled nanotubes may be characterized by an outer diameter of at least 1 nm, e.g., at least 2 nm, 4 nm, 6 nm, 8 nm, or at least 9 nm. The outer diameter may be less than 100 nm, less than 80 nm, less than 60 nm, less than 40 nm, or less than 20 nm. The outer diameter may be between 9 nm and 20 nm. The length of the multi-walled nanotube may be less than 50 nm, less than 75 nm, or less than 100 nm. The length may be less than 500 μm or less than 100 μm. The length may be between 100 nm and 10 μm. Multi-walled carbon nanotubes may have an average outer diameter between 9 nm and 20 nm and / or an average length between 100 nm and 10 μm.

[0353] Carbon nanotubes, for example, are 200 m 2 / g~400m 2 / g. The carbon nanotubes may have an average number of walls from 5 to 15. The BET surface area may be determined according to ASTM D6556.

[0354] The coreactive composition may include a thermally conductive filler or a combination of thermally conductive fillers.

[0355] Thermally conductive fillers may include, for example, metal nitrides such as boron nitride, silicon nitride, aluminum nitride, boron arsenide, carbon compounds such as diamond, graphite, carbon black, carbon fibers, graphene, and graphene-based carbon particles, metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, silicon dioxide, titanium oxide, nickel oxide, zinc oxide, copper oxide, tin oxide, metal hydroxides such as aluminum hydroxide or magnesium hydroxide, carbides such as silicon carbide, minerals such as agate and emery, ceramic microspheres, mullite, silica, silicon carbide, carbonyl iron, cerium (III) molybdate, copper, zinc, or combinations of any of the foregoing.

[0356] The coreactive composition may comprise greater than 5 wt%, greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, greater than 90 wt%, or greater than 95 wt% of the conductive filler, where the weight percentages are based on the total weight of the coreactive composition. The coreactive composition may comprise less than 5 wt%, less than 10 wt%, less than 20 wt%, less than 30 wt%, less than 40 wt%, less than 50 wt%, less than 60 wt%, less than 70 wt%, less than 80 wt%, less than 90 wt%, or less than 95 wt% of the conductive filler, where the weight percentages are based on the total weight of the coreactive composition. The coreactive compositions provided by the present disclosure may have 1 wt% to 95 wt% conductive filler, 5 wt% to 75 wt%, 10 wt% to 60 wt%, or 20 wt% to 50 wt% conductive filler, where the weight percentages are based on the total weight of the coreactive composition.

[0357] The coreactive composition may comprise more than 5 vol.%, more than 10 vol.%, more than 20 vol.%, more than 30 vol.%, more than 40 vol.%, more than 50 vol.%, more than 60 vol.%, more than 70 vol.%, more than 80 vol.%, more than 90 vol.%, or more than 95 vol.% of the conductive filler, where the volume percent is based on the total volume of the coreactive composition. The coreactive composition may comprise less than 5 vol.%, less than 10 vol.%, less than 20 vol.%, less than 30 vol.%, less than 40 vol.%, less than 50 vol.%, less than 60 vol.%, less than 70 vol.%, less than 80 vol.%, less than 90 vol.%, or less than 95 vol.% of the conductive filler, where the volume percent is based on the total volume of the coreactive composition. The coreactive compositions provided by the present disclosure may have 1 vol.% to 95 vol.% conductive filler, 5 vol.% to 75 vol.%, 10 vol.% to 60 vol.%, or 20 vol.% to 50 vol.% conductive filler, where the vol.% is based on the total volume of the coreactive composition.

[0358] The coreactive composition may include a reactive diluent or a combination of reactive diluents. The reactive diluent may be used to reduce the initial viscosity of the coreactive composition. The reactive diluent may be a compound having at least one functional group that can react with at least one of the main reactants of the composition and become part of a crosslinked network. The reactive diluent may have, for example, one functional group or two functional groups. The reactive diluent may be used to control the viscosity of the composition or to improve the wetting of the filler in the coreactive composition.

[0359] The co-reactive composition may include a hydroxyl-functional vinyl ether or a combination of hydroxyl-functional vinyl ethers as a reactive diluent.

[0360] The hydroxyl functional vinyl ether can have the structure of formula (12): CH2=CH-O-(CH2) w -OH (12) In the formula, w is an integer from 2 to 10. In the hydroxyl functional vinyl ether of formula (12), w can be 2, 3, 4, 5, or w can be 6. Examples of suitable hydroxyl functional vinyl ethers include 1-methyl-3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and combinations thereof. The hydroxyl functional vinyl ether can be 4-hydroxybutyl vinyl ether as a reactive diluent.

[0361] The coreactive composition can include, for example, 0.1 wt % to 10 wt %, 0.2 wt % to 9 wt %, 0.3 wt % to 0.7 wt %, and 0.4 wt % to 0.7 wt % of the hydroxyl-functional vinyl ether, where the wt % is based on the total weight of the coreactive composition.

[0362] The coreactive composition may include an amino-functional vinyl ether or a combination of amino-functional vinyl ethers.

[0363] The amino-functional vinyl ether can have the structure of formula (13): CH2=CH-O-(CH2) t -NH2(13) In the formula, t is an integer from 2 to 10. In the amino-functional vinyl ether of formula (13), t can be 2, 3, 4, 5, or t can be 6. Examples of suitable amino-functional vinyl ethers include 1-methyl-3-aminopropyl vinyl ether, 4-aminobutyl vinyl ether, and combinations of any of the foregoing. The amino-functional vinyl ether can be 4-aminobutyl vinyl ether.

[0364] The coreactive composition may include an epoxy-functional vinyl ether or a combination of epoxy-functional vinyl ethers.

[0365] The hydroxyl functional vinyl ether can have the structure of formula (14): CH2=CH-O-(CH2) w -R (14) where w is an integer from 2 to 10, and R is an epoxy group. In the epoxy-functional vinyl ether of formula (14), w can be 2, 3, 4, 5, or w can be 6. The epoxy-functional vinyl ether can be 2-(4(vinyloxy)butyl)oxirane.

[0366] The coreactive composition can include, for example, 0.1 wt % to 10 wt %, 0.2 wt % to 9 wt %, 0.3 wt % to 0.7 wt %, and 0.4 wt % to 0.7 wt % of the amino-functional vinyl ether, where the wt % is based on the total weight of the coreactive composition.

[0367] The coreactive composition may include as reactive diluents vinyl diluents such as styrene, alpha-methylstyrene, and para-vinyltoluene; vinyl acetate; and / or n-vinylpyrrolidone.

[0368] The coreactive composition may contain a plasticizer or combination of plasticizers. The plasticizers may be included to adjust the initial viscosity of the coreactive composition and facilitate application.

[0369] Examples of suitable plasticizers include phthalates, terephthalic acid, isophthalic acid, hydrogenated terphenyls, quaterphenyls and higher polyphenyls, phthalate esters, chlorinated paraffins, modified polyphenyls, tung oil, benzoates, dibenzoates, thermoplastic polyurethane plasticizers, phthalates, naphthalene sulfonates, trimellitates, adipates, sebacates, maleates, sulfonamides, organic phosphates, polybutenes, butyl acetate, butyl cellosolve, butyl carbitol acetate, dipentene, tributyl phosphate, hexadecanol, diallyl phthalate, sucrose acetate isobutyrate, butyl phosphate ... esters of isooctyl tallow, epoxy esters of isooctyl tallow, benzophenone, as well as combinations of any of the foregoing.

[0370] The co-reactive composition may comprise 0.5% to 7% by weight of a plasticizer or combination of plasticizers, 1% to 6%, 2% to 5%, or 2% to 4% by weight of a plasticizer or combination of plasticizers, where the weight percentages are based on the total weight of the co-reactive composition. The co-reactive composition may comprise less than 8% by weight of a plasticizer, less than 6%, less than 4%, or less than 2% by weight of a plasticizer or combination of plasticizers, where the weight percentages are based on the total weight of the co-reactive composition.

[0371] The co-reactive composition may include a corrosion inhibitor or a combination of corrosion inhibitors.

[0372] Examples of suitable corrosion inhibitors include zinc phosphate based corrosion inhibitors, lithium silicate corrosion inhibitors such as lithium orthosilicate (Li4SiO4) and lithium metasilicate (Li2SiO3), MgO, azoles, monomeric amino acids, dimeric amino acids, oligomeric amino acids, nitrogen-containing heterocyclic compounds (such as azoles, oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, indolizines and triazines, tetrazoles, and / or tolyltriazoles), corrosion resistant particles such as inorganic oxide particles (including, for example, zinc oxide (ZnO), magnesium oxide (MgO), cerium oxide (CeO2), molybdenum oxide (MoO3), and / or silicon dioxide (SiO2)), and combinations of any of the foregoing.

[0373] The co-reactive composition may 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 based on the total weight of the co-reactive composition. The co-reactive composition may include, for example, more than 0.1 wt.%, more than 0.5 wt.%, more than 1 wt.%, or more than 2 wt.% of a corrosion inhibitor, where the wt.% is based on the total weight of the co-reactive composition.

[0374] The co-reactive composition may include a flame retardant or a combination of flame retardants.

[0375] The flame retardant may include an inorganic flame retardant, an organic flame retardant, or a combination thereof.

[0376] 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.

[0377] Examples of suitable organic flame retardants include halocarbons, halogenated esters, halogenated ethers, chlorinated and / or brominated flame retardants, halogen-free compounds such as organophosphorus compounds, organonitrogen compounds, and combinations of any of the foregoing.

[0378] The coreactive composition may, for example, comprise from 1 wt% to 30 wt%, e.g., from 1 wt% to 20 wt% or from 1 wt% to 10 wt% of a flame retardant or combination of flame retardants, based on the total weight of the coreactive composition. For example, the coreactive composition may comprise 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 coreactive composition.

[0379] The co-reactive composition may include a moisture control additive or a combination of moisture control additives.

[0380] 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, alkoxysilanes, and combinations of any of the foregoing.

[0381] The co-reactive composition may comprise less than 5 wt.% of a moisture control additive or a combination of moisture control additives, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, or less than 0.5 wt.% of a moisture control additive or a combination of moisture control additives, where the wt.% is based on the total weight of the co-reactive composition.

[0382] The coreactive composition may include a UV stabilizer or a combination of UV stabilizers. The UV stabilizer may include a UV absorber and a hindered amine light stabilizer. Examples of suitable UV stabilizers include Cyasorb® (Solvay), Uvinul® (BASF), and Tinuvin® (BASF) brand name products.

[0383] The co-reactive composition may include a colorant, such as a pigment and / or a dye.

[0384] Examples of suitable inorganic pigments include metal-containing inorganic pigments such as those containing cadmium, carbon, chromium, cobalt, copper, iron oxide, lead, mercury, titanium, tungsten, and zinc. Examples further include ultramarine blue, ultramarine violet, reduced tungsten oxide, cobalt aluminate, cobalt phosphate, manganese ammonium pyrophosphate, and / or metal-free inorganic pigments. Inorganic pigment nanoparticles can include ultramarine blue, ultramarine violet, Prussian blue, cobalt blue, and / or reduced tungsten oxide. Examples of specific organic pigments include indanthrone, quinacridone, phthalocyanine blue, copper phthalocyanine blue, and perylene anthraquinone.

[0385] Further examples of suitable pigments include iron oxide pigments in all shades of yellow, brown, red, and black; in all their physical forms and particle categories; titanium oxide pigments in all different inorganic surface treatments; chromium oxide pigments, even co-precipitated with nickel and nickel titanate; black pigments from organic combustion (e.g. carbon black); blue and green pigments derived from copper phthalocyanines, also chlorinated and brominated, in various α, β, and ε crystal forms; yellow pigments derived from lead sulfochromate; yellow pigments derived from lead bismuth vanadate; orange pigments derived from lead sulfochromate molybdate; yellow pigments of organic nature based on arylamides; orange pigments of organic nature based on naphthol; orange pigments of organic nature based on diketo-pyrrolo-pyrroles; red pigments based on manganese salts of azo dyes; red pigments based on manganese salts of beta-oxynaphthoic acid; red organic quinacridone pigments; and red organic anthraquinone pigments.

[0386] Examples of suitable dyes include acridine, anthraquinone, arylmethane dyes, azo dyes, phthalocyanine dyes, quinone-imine dyes (including azine dyes), indamine, indophenyl, oxazine, oxazone, and thiazine, thiazole dyes, safranine dyes, xanthene dyes (including fluorene dyes). Examples of suitable dyes include alcian blue, alcian yellow, alizarin, alizarin red, alizarin yellow, azophloxine, Bismarck Brown R, Bismarck Brown Y, brilliant cresyl blue, chrysoidine R, chrysoidine Y, Congo red, crystal violet, ethyl green, fuchsinic acid, gentian violet, Janus green, lissamine fast yellow, malachite green, martilus yellow, meldola blue, metanil yellow, methyl orange, methyl red, naphthalene black, naphthol green, Examples of pigments that may be used include chloroquine, naphthol yellow, orange G, purpurin, rose bengal, sudan II, titan yellow, tropaeolin O, tropaeolin OO, tropaeolin OOO, victoria blue, and xylene cyanol.

[0387] The co-reactive composition can include a photochromic material or a combination of photochromic materials.

[0388] The photochromic material may be a reversible photochromic material or a non-reversible photochromic material. The photochromic material may be a thermally reversible photochromic material or a thermally irreversible photochromic material.

[0389] Photochromic materials can be compounds that are activated by absorbing actinic radiation having a particular wavelength, such as UV radiation, which causes a change in the characteristics of the photochromic material. The change in characteristic is an identifiable change in the characteristics of the photochromic material that can be detected using an instrument or visually. Examples of changes in characteristic include changes in color or color intensity, as well as changes in structure or other interactions with energy in the visible UV, infrared (IR), near IR or far IR portions of the electromagnetic spectrum, such as absorbance and / or reflectance. A color change at visible wavelengths refers to a color change at wavelengths ranging from 400 nm to 800 nm.

[0390] Photochromic materials can be activated by absorbing radiation energy (visible and non-visible) having a specific wavelength, such as UV light, to undergo a change in characteristic, such as a change in color. The change in characteristic can be only a change in the characteristic of the photochromic material, or a change in the characteristic of the co-reactive composition. Examples of suitable photochromic materials include spiropyrans, spiropyrimidines, spirooxazines, diarylethenes, photochromic quinones, azobenzenes, other photochromic dyes, and combinations thereof. These photochromic materials can undergo a reversible or irreversible change in characteristic when exposed to radiation, and the first and second states can be different colors or different intensities of the same color.

[0391] The coreactive composition may include a photochromic agent that is sensitive to the degree of cure or exposure to actinic radiation. The cure indicator may change color upon exposure to actinic radiation, which may be permanent or reversible. The cure indicator may be initially clear and become colored upon exposure to actinic radiation, or may be initially colored and become clear upon exposure to actinic radiation.

[0392] Layers of the multi-layer systems provided by the present disclosure that exhibit low temperature flexibility may include prepolymers such as, for example, silicones, polytetrafluoroethylene, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing.

[0393] Layers of the multi-layer systems provided by the present disclosure that exhibit hydrolytic stability may include prepolymers, or compositions with high crosslink density, such as, for example, silicones, polytetrafluoroethylenes, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing, and / or may include elastomers.

[0394] Layers of the multi-layer systems provided by the present disclosure that exhibit high temperature resistance may be made of, for example, silicones, polytetrafluoroethylene, polythioethers, polysulfides, polyformals, polybutadienes, certain elastomers, and combinations of any of the foregoing. The composition may include a prepolymer having a high crosslink density.

[0395] Layers of the multi-layer systems provided by the present disclosure that exhibit high tensile strength may include, for example, elastomeric prepolymers such as silicones and polybutadienes, compositions with high crosslink density, inorganic fillers, and combinations of any of the foregoing.

[0396] Layers of the multi-layer systems provided by the present disclosure that exhibit high elongation can include, for example, elastomeric prepolymers such as silicone and polybutadiene, compositions with high crosslink density, inorganic fillers, and combinations of any of the foregoing.

[0397] The layers of the multi-layer systems provided by the present disclosure that exhibit substrate bonding or bonding to a primer coating may include adhesion promoters such as, for example, organofunctional alkoxysilanes, phenolic resins, heat treated phenolic resins, and combinations of any of the foregoing, titanates, partially hydrolyzed alkoxysilanes, or combinations thereof.

[0398] Layers of the multi-layer systems provided by the present disclosure that exhibit interlayer adhesion can include, for example, adhesion promoters, unreacted functional groups that are reactive to compounds in adjacent layers, and combinations thereof.

[0399] Layers of the multi-layer systems provided by the present disclosure that exhibit fast tack-free times can include, for example, co-reactants having fast-cure chemistries, systems curable by actinic radiation, catalysts, and combinations of any of the foregoing.

[0400] A layer of a multi-layer system provided by the present disclosure may exhibit, for example, a tack-free time of less than 5 minutes from when the co-reactants are first mixed until a cotton ball no longer adheres to the surface of the cured sealant.

[0401] The layers of the multi-layer systems provided by the present disclosure having fast time to Shore 10A hardness can include, for example, co-reactants having fast-cure chemistries, systems curable by actinic radiation, catalysts, and combinations of any of the foregoing.

[0402] Layers of the multi-layer systems provided by the present disclosure that exhibit electrical conductivity, EMI / RFI shielding, and / or static dissipative properties can include, for example, an electrically conductive filler or a combination of electrically conductive fillers.

[0403] Layers of the multi-layer systems provided by the present disclosure that exhibit low density may include low density fillers such as, for example, low density organic fillers, hollow particulates, coated particulates, or combinations of any of the foregoing.

[0404] Layers of the multi-layer systems provided by the present disclosure that exhibit corrosion resistance can include, for example, one or more corrosion inhibitors.

[0405] Layers of the multi-layer systems provided by the present disclosure that exhibit corrosion resistance can include, for example, one or more inorganic fillers.

[0406] Upon curing, the multi-layer systems provided by the present disclosure may exhibit, for example, one or more of the desired solvent resistance, low temperature flexibility, hydrolytic stability, high temperature resistance, high tensile strength / elongation, bonding to substrates, bonding to primer coatings, adhesion to adjacent layers, fast tack-free time, fast time to Shore 10A hardness, electrical conductivity, EMI / RFI shielding, static dissipation, corrosion resistance, sound attenuation, or any combination of the foregoing.

[0407] For example, after exposure to a jet reference fluid (JRF Type 1) according to ISO 1817 for 168 hours at 60° C., the cured multilayers provided by the disclosed systems provided by the present disclosure can exhibit a tensile strength, determined according to ISO 37, of greater than 1.4 MPa, a tensile elongation, determined according to ISO 37, of greater than 150%, and a hardness, determined according to ISO 868, of greater than Shore 30A, with these tests being performed at a temperature of 23° C. and a relative humidity of 55%.

[0408] After exposure to an ice melting solution according to ISO 11075 Type 1 at 60° C. for 168 hours, the cured multi-layer systems provided by the present disclosure can exhibit a tensile strength, determined according to ISO 37, of greater than 1 MPa and a tensile elongation, determined according to ISO 37, of greater than 150%, with these tests being performed at a temperature of 23° C. and a humidity of 55% relative humidity.

[0409] The chemically resistant multi-layer systems provided by the present disclosure may exhibit a swelling ratio of less than 25%, less than 20%, less than 15%, or less than 10% after immersion in a chemical at 70° C. for 7 days, the swelling ratio being determined according to EN ISO 10563.

[0410] The multilayer systems provided by the present disclosure that exhibit low swelling ratios may, for example, include high crosslink density. The swelling ratio may be determined by immersing the cured composition in a particular solvent at 70° C. for 7 days according to EN ISO 10563.

[0411] Multi-layer systems provided by the present disclosure may, for example, exhibit a tensile strength when cured of at least 1 MPa, determined according to ISO 37 at 23° C. / 55% relative humidity.

[0412] Multi-layer systems provided by the present disclosure may, for example, exhibit an elongation upon cure of at least 150% as determined according to ISO 37 at 23° C. / 55% relative humidity.

[0413] The multi-layer systems provided by the present disclosure can exhibit a fast time to hardness of Shore 10A in less than 10 minutes, the hardness being determined according to ISO 868 at 23° C. / 55% relative humidity.

[0414] The electrically conductive multilayer system or layers of the multilayer system provided by the present disclosure may be, for example, 10 6 Less than 10 Ohms / sq 5 Less than 10 Ohms / sq 4 Less than 10 Ohms / sq 3 Less than 10 Ohms / sq 2 Less than 10Ω / sq. Less than 10Ω / sq. -1 Less than Ω / sq or 10 -2 The surface of the electrically conductive multilayer system or layer of the multilayer system provided by the present disclosure can exhibit a surface resistivity of, for example, 10 -2 ~10 2 , 10 2 Ω / sq~10 6 Ω / sq, or 10 3 Ω / sq~10 5It may have a surface resistivity of Ω / sq. Surface resistivity may be determined according to ASTM D257 at 23° C. / 55% relative humidity.

[0415] The multilayer system or layers of the multilayer system provided by the present disclosure may be, for example, 10 6 <10 Ohms / cm 5 <10 Ohms / cm 4 <10 Ohms / cm 3 <10 Ohms / cm 2 Less than Ω / cm, Less than 10Ω / cm, 10 -1 Less than Ω / cm or 10 -2 The electrically conductive multi-layer system or layers of the multi-layer system may have a volume resistivity of, for example, 10 -2 Ω / cm~10 1 Ω / cm, 10 2 Ω / cm~10 6 Ω / cm, or 10 3 Ω / cm~10 5 The volume resistivity may be determined according to ASTM D257 at 23° C. / 55% relative humidity.

[0416] The multilayer system or layers of the multilayer system provided by the present disclosure may, for example, be 1 Scm -1 Super, 10Scm -1 Over 100Scm -1 Super, 1,000Scm -1 or over 10,000Scm -1 The electrically conductive multilayer system can have an electrical conductivity of more than 1 Scm. -1 ~10,000Scm -1 , 10Scm -1 ~1,000cm -1 , or 10Scm -1 ~500Scm -1 The electrical conductivity is determined according to ASTM D257 at 23° C. / 55% relative humidity.

[0417] A multilayer system or layer of a multilayer system provided by the present disclosure may exhibit, for example, attenuation of more than 10 dB, more than 30 dB, more than 60 dB, more than 90 dB, or more than 120 dB at frequencies ranging from 10 KHz to 20 GHz. An electrically conductive multilayer system provided by the present disclosure may exhibit, for example, attenuation in the range of 10 dB to 120 dB, 20 dB to 100 dB, 30 dB to 90 dB, or 40 dB to 70 dB at frequencies ranging from 10 KHz to 20 GHz. Shielding effectiveness is determined at 23° C. / 55% relative humidity according to ASTM D4935.

[0418] The multilayer systems or layers of the multilayer systems provided by the present disclosure exhibit a thermal conductivity of 0.1-50 W / (mK), 0.5-30 W / (mK), 1-30 W / (mK), 1-20 W / (mK), 1-10 W / (mK), 1-5 W / (mK), 2-25 W / (mK), or 5-25 W / (mK), as measured at 23° C. / 55% relative humidity according to ASTM D1461.

[0419] Multilayer systems or layers of multilayer systems provided by the present disclosure may, for example, exhibit a specific gravity of less than 1.1, less than 1.0, less than 0.9, less than 0.8, or less than 0.7, where specific gravity is determined at 23° C. / 55% relative humidity according to ISO 2781.

[0420] The multi-layer systems or layers of the multi-layer systems provided by the present disclosure may exhibit, for example, a hardness of greater than Shore 20a, greater than Shore 30A, greater than Shore 40A, greater than Shore 50A, or greater than Shore 60a, where the hardness is determined according to ISO 868 at 23° C. / 55% relative humidity.

[0421] The cured multi-layer system may have acceptable properties for use in vehicle and aerospace sealant applications. In general, sealants used in aircraft and aerospace applications desirably exhibit the following properties: peel strength of greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS) 3265B substrates, determined under dry conditions after immersion in JRF Type I for 7 days and after immersion in 3% NaCl aqueous solution according to AMS 3265B test specifications; tensile strength of 300 pounds per square inch (psi) to 400 psi (2.75 MPa); tensile strength of greater than 50 pounds per linear inch (pli) (8.75 N / mm); elongation of 250% to 300%; and hardness of greater than 40 durometer A. These and other properties suitable for aircraft and aerospace applications are disclosed in AMS 3265B. Additionally, multi-layer systems of the present disclosure used in aircraft and aircraft applications, once cured, desirably exhibit a volume expansion of 25% or less after immersion for one week at 60° C. and ambient pressure in Jet Reference Fluid (JRF) Type I. Other properties, ranges, and / or thresholds may be appropriate for other sealant applications.

[0422] The multi-layer system provided by the present disclosure can be fuel resistant. The term "fuel resistant" can mean that the composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that exhibits a volume swelling of 40% or less than 40%, in some cases 25% or less than 25%, in some cases 20% or less than 20%, and in other cases 10% or less than 10% after immersion in JRF Type I at 60°C and ambient pressure for one week according to a method similar to that described in ASTM D792 (American Society for Testing and Materials) or AMS3269 (Aerospace Materials Specification). JRF Type I, used to determine fuel resistance, has the following composition: toluene: 28±1% by volume; cyclohexane (technical): 34±1% by volume; isooctane: 38±1% by volume; and tertiary dibutyl disulfide: 1±0.005% by volume (see e.g. AMS 2629, published July 1, 1989, §3.1.1, available from SAE (Society of Automotive Engineers)).

[0423] The chemically resistant multi-layer systems provided by the present disclosure may exhibit a tensile elongation of at least 200% and a tensile strength of at least 200 psi when measured according to the procedures set forth in AMS 3279 § 3.3.17.1, test procedure AS5127 / 1 § 7.7.

[0424] The multi-layer systems provided by the present disclosure may exhibit lap shear strengths of greater than 200 psi (1.38 MPa), e.g., at least 220 psi (1.52 MPa), at least 250 psi (1.72 MPa), and in some cases at least 400 psi (2.76 MPa), when measured according to the procedure set forth in paragraph 7.8 of SAE AS5127 / 1.

[0425] The multi-layer systems provided by the present disclosure may meet or exceed the requirements for aerospace sealants set forth in AMS3277.

[0426] A layer of the multi-layer system provided by the present disclosure that imparts sound attenuation properties can include an epoxy-containing compound, which includes an epoxy / polyol adduct, a polythiol, and a curing agent.

[0427] The multi-layer system provided by the present disclosure may impart sound attenuation properties to a structure. For example, when the multi-layer system having sound attenuation properties is applied to a substrate, the substrate may exhibit a sound attenuation loss factor of at least 0.06 at 800 Hz, at least 0.04 at 400 Hz, or at least 0.02 at 200 Hz, measured according to SAE test methods J1637 and ASTM E756 on a steel plate 240 mm long, 10 mm wide, and 1 mm thick coated along a length of 215 mm, at 10° C. and with a sealant thickness of 2.5 mm.

[0428] A multi-layer system may include one or more coatings. A coating may be provided on the outer surface of an inner layer of a multi-layer system, on the outer surface of an outer layer of a multi-layer system, and / or between one or more layers of a multi-layer system. A coating refers to a layer that is less thick than the layers of a multi-layer system.

[0429] The multi-layer system provided by the present disclosure may include intermediate coatings between layers, inner coatings, outer coatings, or any combination of the foregoing. An intermediate coating refers to a coating between adjacent layers, an inner coating refers to a coating adjacent to a surface, and an outer coating is on the outer surface of the multi-layer system. Examples of coatings are shown in FIG. 3. FIG. 3 shows a cross-sectional view of a multi-layer system having a first layer 302 on a substrate 305 and a second layer 301 on the first layer 302. The first coating 304 is disposed between the first layer 302 and the substrate 305, for example, to enhance adhesion and / or corrosion resistance. The second coating 303 is disposed between the first layer and the second layer 301 / 302, for example, to enhance interlayer adhesion. A third coating 306 may be on the outer surface of the multi-layer system and may be configured to enhance, for example, chemical resistance, abrasion resistance, or electrical conductivity of one or more layers of the multi-layer system.

[0430] The intermediate coating, inner coating, or outer coating may have a thickness of, for example, 0.001 to 2 mm, 0.01 mm to 1 mm, 0.05 mm to 0.5 mm, or 0.1 mm to 0.4 mm. The coating may have a thickness of, for example, less than 2 mm, less than 1 mm, less than 0.5 mm, less than 0.1 mm, or less than 0.05 mm. The thickness of the coating may be less than the thickness of the layers forming the multilayer system. The intermediate coating may be used to enhance or provide a desired property to the multilayer system, such as, for example, interlayer adhesion, electrical conductivity, EMI / RFI shielding, or any combination of the foregoing.

[0431] The intermediate coating may include a compound that includes a functional group reactive to the reactive compound of the underlayer and / or overlayer. For example, if the overlayer and / or underlayer includes a co-reactive compound having a thiol functional group, the intermediate coating layer may include a compound having a group reactive to the thiol group, such as an alkenyl group, an alkynyl group, an isocyanate group, a thiol group, or an epoxy group.

[0432] The inner coating may provide adhesion to the substrate, may provide corrosion resistance, or may provide a combination thereof. For example, the inner coating may include, for example, an adhesion promoter, a corrosion inhibitor, a partially hydrolyzed / condensed organofunctional alkoxysilane, and combinations of any of the foregoing.

[0433] The outer coating may be configured to provide aesthetics, static dissipation, electrical conductivity, EMI / RFI shielding, or a combination of any of the foregoing. For example, the outer coating may include, for example, a colorant, an electrically conductive filler, or a combination thereof.

[0434] The multi-layer system may include an outer coating, such as a clear coat, an abrasion-resistant coating, a color coating, a textured coating, a solvent-resistant coating, a UV protective coating, a tactile, or a combination of any of the foregoing, over the multi-layer system. Surface coatings may be used to impart desired surface properties, such as, for example, electrical conductivity, reflectivity, such as IR reflectivity, color, wavelength-dependent absorbency, wavelength-dependent reflectivity, scratch resistance, abrasion resistance, stain resistance, fingerprint resistance, cleaning fluid resistance, to impart aesthetic qualities, and / or to impart tactile properties. The coating may include a multi-layer coating. The coating may be a tactile coating, such as a soft-touch coating. The coating may be applied to the extrudate using an extrusion coating die.

[0435] The multi-layer systems provided by the present disclosure can be prepared by depositing an extrudate comprising the co-reactive sealant composition, or a co-extrudate comprising the co-reactive sealant composition and one or more additional co-reactive compositions, onto a substrate.

[0436] The multi-layer system can be applied using additive manufacturing, which is widely used to include robotic manufacturing, including, for example, 3D printing, extrusion, and co-extrusion.

[0437] Using additive manufacturing methods, multi-layer systems including individual layers of the coreactive composition can be applied directly to a substrate and subsequently cured and / or cured to provide a cured multi-layer system.

[0438] The multi-layer system may be applied by coextrusion. Coextrusion is used broadly to refer to the method in which the multi-layer system is applied to a substrate using pressure. Pressure may be applied manually or automatically. Coextrusion includes processes involving extrusion or merging of parallel streams of co-reactive compositions through a coextrusion die.

[0439] Coextrusion facilitates the ability to apply a multi-layer system to a substrate in a single process. By applying the layers of the multi-layer system simultaneously, it can facilitate the ability to maintain the consistency, reproducibility, and integrity of the multi-layer system.

[0440] The first and second coreactive compositions may be coextruded through a coextrusion die having a suitable shape to provide a coextrudate.

[0441] A schematic example of a co-extruder is shown in FIG. 4. The co-extruder comprises a barrel 401, a first inlet 402 for a first coreactive composition 403, a second inlet 404 for a second coreactive composition 405, and an exit nozzle 406. The inlets may be coupled to a pump that controls the flow of the coreactive compositions into the co-extruder. The barrel of the co-extruder may include a sensor coupled to the pump for controlling the flow of the coreactive compositions into the barrel of the extruder. The flow of the coreactive compositions may be controlled so that the flows merge but do not mix. At the exit nozzle 406, the fused coreactive composition 408 may be shaped to provide a co-extrudate 409. As shown in FIG. 4, the co-extruder is in the form of a sheet with the first coreactive composition 403 overlying the second coreactive composition 405. The co-extruder may be applied to a part or surface to be sealed.

[0442] The co-extruder can include pressure controls, extrusion dies, co-extrusion dies, coating applicators, temperature control elements, elements for irradiating the co-reactive sealant composition, or any combination of the foregoing.

[0443] For automated production, the co-extruder can be attached to an apparatus for moving the nozzle relative to the surface. The automated production apparatus, including the co-extruder, can be controlled by a processor.

[0444] The coextrusion process is versatile enough that a wide range of coextrusion structures can be fabricated.

[0445] For example, in the case of a three-dimensional multi-layer system, the coextrudate may have a core-shell configuration with an inner layer comprising a first composition and an outer layer comprising a second composition. The core-shell coextrudate may be applied directly to a three-dimensional surface as a single unit.

[0446] In the case of two-dimensional multilayer systems, the coextrusion may be in the form of a sheet with two or more upper layers. The surface may be sealed by applying a successive sheet of the multilayer system adjacent to a previously deposited sheet of the multilayer system.

[0447] The multi-layer system can be fabricated as separate components that can then be applied to the surface to be sealed. For example, the multi-layer system can be fabricated as a sheet or preform having the desired shape and partially or fully cured. The partially or fully cured multi-layer system components can then be applied to the surface.

[0448] The multi-layer system can be applied directly to the surface to be sealed. For example, the individual layers of the multi-layer system can be applied sequentially to the surface, where one or more of the layers are applied using the co-reactive three-dimensional printing method provided by the present disclosure. The multi-layer system provided by the present disclosure can be co-extruded directly onto the surface to be sealed.

[0449] As a result of having multiple layers, there may be interfaces between each of the layers of the multi-layer system, and the integrity of the layer interfaces may be maintained with respect to the overall performance requirements of the multi-layer system.

[0450] Interlayer adhesion between adjacent layers of a multi-layer system can be enhanced in several ways. For example, an adhesion-promoting coating can be applied between adjacent layers. The adhesion-promoting coating can include adhesion promoters and / or reactive groups that can non-covalently or covalently bond to one or more components of the adjacent layers.

[0451] Adhesion between adjacent strips of a multi-layer system can be enhanced by promoting the ability of adjacent layers to bond chemically and / or physically. This can be achieved, for example, by providing adjacent strips of a multi-layer system having reactive compounds that can chemically react with compounds in adjacent co-reactive compositions. This can be accomplished by including a co-reactive composition in the coating. For example, in the case of layers based on thiol-ene chemistry, the adhesion-promoting interlayer coating can include a compound having unreacted groups that can react with the thiol and / or alkenyl groups of the upper and lower layers.

[0452] The rate of interlayer crosslinking between adjacent layers of a multilayer system can be controlled to promote interlayer reaction and thereby improve interlayer strength. For example, it may be desirable for adjacent layers to be able to chemically bond to each other. To achieve this, a second layer can be deposited on a first layer before the first layer is fully cured, so that the first layer has unreacted functional groups that can react with the functional groups of the second layer. The rate of interlayer crosslinking can be controlled, for example, by adjusting the time between deposition of successive layers, adjusting the temperature, adjusting the concentration of the catalyst, and / or adjusting the components of the composition, such as the amount of monomer and prepolymer.

[0453] A layer may be uniform, or a layer may be non-uniform. In the case of a non-uniform layer, the cross-section of the layer may have different chemical compositions across the profile. For example, to improve interlayer adhesion, a portion of a layer may have an excess of a specific co-reactive functional group, which may then react with the excess co-reactive functional group of the upper layer. Similarly, to improve interlayer adhesion, a lower portion of a layer may have an excess of a specific co-reactive functional group, which may then react with the excess co-reactive functional group of the lower layer. To improve interlayer bonding and / or adhesion, a tie coating, film, or other treatment may be applied or deposited on the deposited layer before or during deposition of the upper layer. An interlayer tie layer may, for example, include a compound reactive to the adjacent layer, a catalyst, and / or an adhesion promoter. An interlayer tie coat may be applied to the surface of the extrudate by coextrusion.

[0454] The layer may be applied to at least a portion of the surface of the co-reactive composition and / or the co-extrudate. The layer may be applied, for example, by passing the co-extrudate through a liquid composition to provide a coating on the outer surface or a portion of the outer surface of the co-extrudate. The coating may include a material that enhances adhesion between adjacent strips of the multi-layer system. For example, the thin film coating may include a compound having groups reactive to the functional groups of the co-reactive composition that forms the multi-layer system.

[0455] Coextruded multi-layer systems can also be configured to promote adhesion to multiple substrates. For example, the adhesive package can be optimized to bond the inner layer of the multi-layer system to a particular substrate. However, the adhesive package may not be optimal to promote bonding to different substrates. For example, different adhesive packages can be optimized for bonding to different metals, such as aluminum and titanium, or to composites and metals. The innermost layer of the multi-layer system can include two or more parts with different adhesive packages, and the other components of the coreactive composition forming the inner layer can be substantially the same or different. In this way, the bonding of the multi-layer system to substrates containing different materials can be enhanced.

[0456] The extrudate or co-extrudate can be deposited in any orientation. For example, the nozzle can be oriented downward, upward, sideways, or at any angle in between. In this way, the multilayer system can be deposited as a vertical wall or as a protrusion. The extrudate or co-extrudate can be deposited on a vertical wall, on the underside of an inclined wall, or on the bottom of a horizontal surface. The use of an extrudate or co-extrudate with a fast-curing chemistry can facilitate the ability to deposit an upper layer adjacent to a lower layer so that an angled surface can be fabricated. The angled surface can be angled upward relative to the horizontal or angled downward relative to the horizontal.

[0457] The coreactive composition may have a volumetric flow rate of, for example, 0.1 mL / min to 20,000 mL / min, such as, for example, 1 mL / min to 12,000 mL / min, 5 mL / min to 8,000 mL / min, or 10 mL / min to 6,000 mL / min. The reaction rate may depend on the viscosity of the extrusion mixture, the extrusion pressure, the nozzle diameter, and the reaction rate of the coreactive compound.

[0458] The coreactive composition may be used at a printing speed of, for example, 1 mm / s to 400 mm / s, e.g., 5 mm / s to 300 mm / s, 10 mm / s to 200 mm / s, or 15 mm / s to 150 mm / s. The printing speed may depend, for example, on the viscosity of the coreactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the coreactive components. Printing speed refers to the speed at which the nozzle used to extrude the coreactive composition moves relative to the surface on which the coreactive composition is deposited.

[0459] The multi-layer systems including the sealant layers provided by the present disclosure can be used in any application where a sealant is used to protect a surface from the environment. For example, the multi-layers can be used to seal automotive and aerospace vehicle parts and surfaces.

[0460] The multi-layer system may be applied or deposited directly onto the surface of the substrate or over a coating such as a primer coating or an adhesion promoting coating.

[0461] The multi-layer systems provided by the present disclosure may be applied to or deposited on any of a variety of substrates. Examples of substrates to which the multi-layer systems may be applied may include metals such as titanium, stainless steel, steel alloys, aluminum, and aluminum alloys, any of which may be anodized, primed, organically coated, or chromate coated, or may include epoxies, urethanes, graphite, fiberglass composites, Kevlar®, acrylics, polycarbonates, and combinations of any of the foregoing.

[0462] The cured multi-layer systems provided by the present disclosure may exhibit acceptable properties for use in vehicle applications such as automotive and aerospace sealant applications. In general, sealants used in aircraft and aerospace applications desirably exhibit the following properties: peel strength of greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS) 3265B substrates, determined under dry conditions after immersion in JRF Type I for 7 days and after immersion in a 3% NaCl solution according to AMS 3265B test specifications; tensile strength of 300 pounds per square inch (psi) to 400 psi (2.75 MPa); tensile strength of greater than 50 pounds per linear inch (pli) (8.75 N / mm); elongation of 250% to 300%; and hardness of greater than 40 durometer A. These and other cured properties of multi-layer systems suitable for aircraft and aerospace applications are disclosed in AMS 3265B. Additionally, multi-layer systems used in aircraft and aircraft applications, once cured, desirably exhibit a volume swell of 25% or less after immersion for one week at 60° C. and ambient pressure in Jet Reference Fluid (JRF) Type 1. Other properties, ranges, and / or thresholds may be appropriate for other sealant applications, such as automotive applications.

[0463] The multi-layer systems provided by the present disclosure may exhibit a tensile elongation of at least 200% and a tensile strength of at least 200 psi, when measured according to the procedures set forth in AMS 3279 §3.3.17.1, test procedure AS5127 / 1 §7.7.

[0464] The multi-layer systems provided by the present disclosure may exhibit lap shear strengths of greater than 200 psi (1.38 MPa), e.g., at least 220 psi (1.52 MPa), at least 250 psi (1.72 MPa), and in some cases at least 400 psi (2.76 MPa), when measured according to the procedure set forth in paragraph 7.8 of SAE AS5127 / 1.

[0465] Multi-layer systems prepared using the methods provided by the present disclosure are described in AMS3277. The present invention can meet or exceed the requirements for aerospace sealants.

[0466] Prior to environmental exposure, the multi-layer systems provided by the present disclosure have a modulus of elasticity of 1.2 g / cm as determined according to ISO 2781. 3 The material exhibits a density of less than 200 nm (specific gravity less than 1.2), a tensile strength determined in accordance with ISO 37 of greater than 1 MPa, a tensile elongation determined in accordance with ISO 37 of greater than 150%, and a hardness determined in accordance with ISO 868 of greater than 40 Shore A, the tests being carried out at temperatures ranging from 21° C. to 25° C. and humidities ranging from 45% relative humidity to 55% relative humidity.

[0467] After exposure to aviation fuel (JRF type 1) at 60°C for 168 hours according to ISO 1817, the multi-layer system may exhibit a tensile strength, determined according to ISO 37, of greater than 1.4 MPa, a tensile elongation, determined according to ISO 37, of greater than 150%, and a hardness, determined according to ISO 868, of greater than 30 Shore A, with these tests being performed at temperatures ranging from 21°C to 25°C and humidities ranging from 45% relative humidity to 55% relative humidity.

[0468] After exposure to a 3% aqueous NaCl solution at 60° C. for 168 hours, the multilayer system can exhibit a tensile strength, determined according to ISO 37, of greater than 1.4 MPa, a tensile elongation, determined according to ISO 37, of greater than 150%, and a hardness, determined according to ISO 868, of greater than 30 Shore A, with these tests being performed at temperatures ranging from 21° C. to 25° C. and humidities ranging from 45% relative humidity to 55% relative humidity.

[0469] After exposure to de-icing fluid according to ISO 11075 Type 1 at 60° C. for 168 hours, the cured multi-layer systems provided by the present disclosure can exhibit a tensile strength, determined according to ISO 37, of greater than 1 MPa and a tensile elongation, determined according to ISO 37, of greater than 150%, with these tests being performed at temperatures ranging from 21° C. to 25° C. and humidities of 45% to 55% relative humidity.

[0470] After exposure to a phosphate ester hydraulic fluid (Skydrol® LD-4) for 1,000 hours at 70° C., the multi-layer systems provided by the present disclosure can exhibit a tensile strength, determined according to ISO 37, of greater than 1 MPa, a tensile elongation, determined according to ISO 37, of greater than 150%, and a hardness, determined according to ISO 868, of greater than Shore 30A, with these tests being performed at temperatures ranging from 21° C. to 25° C. and humidities of 45% to 55% relative humidity.

[0471] The multilayer systems provided by the present disclosure can have a glass transition temperature of, for example, less than -10°C, less than -20°C, less than -30°C, less than -40°C, less than -50°C, or less than -60°C.

[0472] The methods of making multi-layer systems and the multi-layer systems made using these methods can be used to seal any suitable part, such as, for example, a vehicle part or surface.

[0473] The term "vehicle" is used in a very broad sense and includes all kinds of aerospace vehicles, marine vehicles, and ground vehicles. For example, vehicles may include aerospace vehicles such as airplanes, including private aircraft, and small, medium, or large commercial passenger, cargo, and military aircraft; helicopters, including private, commercial, and military helicopters; rockets and spacecraft. Vehicles may include ground vehicles such as, for example, automobiles, trailers, trucks, buses, vans, construction vehicles, golf carts, motorcycles, bicycles, trains, and railroad cars. Vehicles may also include marine vehicles, such as, for example, ships, boats, and hovercraft.

[0474] The multi-layer system is used in F / A-18 jets or related aircraft, such as the F / A-18E Super Hornet and F / A-18F (Boeing Commercial The present invention may be used in the Boeing 787 Dreamliner, 737, 747, 717 jetliners, and related aircraft (manufactured by NAVAIR and Sikorsky), in the V-22 Osprey, VH-92, S-92, and related aircraft (manufactured by NAVAIR and Sikorsky), in the G650, G600, G550, G500, G450, and related aircraft (manufactured by Gulfstream), and in the A350, A320, A330, and related aircraft (manufactured by Airbus). The multi-layer system may be used in any suitable commercial, military, or general aviation aircraft, such as those produced by Bombardier Inc. and / or Bombardier Aerospace, such as the Canadair Regional Jet (CRJ) and related aircraft, those produced by Lockheed Martin, such as the F-22 Raptor, F-35 Lightning, and related aircraft, those produced by Northrop Grumman, such as the B-2 Spirit and related aircraft, those produced by Pilatus Aircraft Ltd., those produced by Eclipse Aviation Corporation, or those produced by Eclipse Aerospace (Kestrel Aircraft).

[0475] The multi-layer systems provided by the present disclosure can be used to seal vehicle parts and surfaces, such as fuel tank surfaces and other surfaces exposed or potentially exposed to solvents, hydraulic fluids, lubricants, oils, and fuels.

[0476] The present invention includes parts sealed with the multi-layer system provided by the present disclosure, as well as assemblies and devices that include parts sealed with the multi-layer system provided by the present disclosure. Vehicle openings, surfaces, fillets, joint surfaces (including openings, surfaces, fillets, joints, and face surfaces) sealed with the multi-layer system are included within the scope of the present invention. Parts such as vehicle parts, including automotive vehicle parts and aerospace vehicle parts, sealed using the method provided by the present disclosure are included within the scope of the present invention.

[0477] The present invention includes vehicles that include components such as surfaces sealed by the multi-layer system provided by the present disclosure. For example, aircraft that include a fuel tank or a portion of a fuel tank sealed by the multi-layer system are within the scope of the present invention. Vehicles such as automotive vehicles and aerospace vehicles that include components sealed using the method provided by the present disclosure are within the scope of the present invention.

[0478] The multi-layer system provided by the present disclosure can be used to seal fasteners.Fasteners can be, for example, fasteners on the surface of vehicles, including motor vehicles, automobiles, trucks, buses, vans, motorcycles, scooters, recreational motor vehicles, trains, trams, bicycles, aerospace vehicles, airplanes, rockets, spacecraft, jet planes, helicopters, military vehicles including jeeps, transport vehicles, combat support vehicles, personnel carriers, infantry fighting vehicles, mine-protected vehicles, light armored vehicles, light utility vehicles, military trucks, ships, boats and marine vessels including recreational vessels.The fasteners sealed using the multi-layer system provided by the present disclosure are included in the scope of the present invention.

[0479] Aspects of the invention The present invention may be further defined by one or more of the following aspects.

[0480] Aspect 1. A method of making a multi-layer system comprising two or more layers, one or more of the layers comprising a sealant layer, comprising the steps of: (a) mixing a first component and a second component to form a co-reactive sealant composition, the co-reactive sealant composition comprising a first reactive compound and a second reactive compound, the first reactive compound being reactive to the second reactive compound; and (b) extruding the co-reactive sealant composition. (c) depositing the extrudate to form a sealant layer.

[0481] Embodiment 2. The method of embodiment 1, wherein the depositing comprises three-dimensional printing.

[0482] Embodiment 3. The method of embodiment 1 or 2, wherein depositing comprises depositing an extrudate onto a bottom layer of a multi-layer system.

[0483] Embodiment 4. The method of any one of embodiments 1-3, further comprising depositing a first co-reactive composition beneath the deposited sealant layer to form an underlayer, and / or depositing a second co-reactive composition above the sealant layer to form an overlayer, wherein the first co-reactive composition and the second co-reactive composition comprise a different composition than the sealant layer.

[0484] Embodiment 5. The method of embodiment 4, wherein the first coreactive composition is different from the second coreactive composition.

[0485] Embodiment 6 The method of any one of embodiments 1-5, wherein any of the co-reactive sealant compositions comprises a thermosetting composition.

[0486] Embodiment 7. The method of any one of embodiments 1-6, wherein each layer of the multi-layer system comprises a thermoset material.

[0487] Example 8. The method of any one of Examples 1-7, wherein the cross-sectional profile of the extrudate has a uniform composition across the cross-sectional profile.

[0488] Example 9. The method of any one of examples 1-7, wherein the cross-sectional profile of the extrudate has a non-uniform composition across the cross-sectional profile.

[0489] Embodiment 10. The method of any one of embodiments 1-9, wherein an outermost layer of the two or more layers of the multi-layer system comprises a sealant layer.

[0490] Embodiment 11. The method of any one of embodiments 1-10, wherein each layer of the multi-layer system independently comprises a sealant layer or a non-sealant layer.

[0491] Embodiment 12. The method of any one of embodiments 1-11, wherein the co-reactive sealant composition comprises a prepolymer that includes a chemically resistant backbone.

[0492] Example 13. The method of any one of Examples 1-12, wherein the co-reactive sealant composition comprises a sulfur content of greater than 10 wt.%, the wt. % being based on the total weight of the organic components of the co-reactive sealant composition.

[0493] Embodiment 14 The method of any one of embodiments 1-13, wherein the co-reactive sealant composition comprises a sulfur-containing prepolymer.

[0494] Example 15. The method of example 14, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.

[0495] 16. The sulfur-containing prepolymer comprises a sulfur content of greater than 10% by weight, the weight percentage being sulfur. 16. The method of claim 14 or 15, based on the total weight of the yellow-containing prepolymer.

[0496] Embodiment 17 The method of any one of embodiments 1-16, wherein the first reactive compound is reactive to the second reactive compound at a temperature less than 50° C.

[0497] Embodiment 18. The method of any one of embodiments 1-17, wherein the first reactive compound is reactive to the second reactive compound in the presence of a catalyst and / or polymerization initiator, and the catalyst and / or polymerization initiator can catalyze and / or initiate a reaction between the first reactive compound and the second reactive compound.

[0498] Example 19. The method of any one of examples 18, further comprising activating a polymerization initiator before, during, and / or after depositing the extrudate.

[0499] Embodiment 20. The method of any one of embodiments 1-19, wherein the first component comprises a first reactive compound and a second reactive compound, and the second component comprises a catalyst, a cure activator, and / or a polymerization initiator for the reaction between the first reactive compound and the second reactive compound.

[0500] Embodiment 21 The method of any one of embodiments 1-19, wherein the first component comprises a first reactive compound and the second component comprises a second reactive compound.

[0501] Embodiment 22. The method of any one of embodiments 1-21, wherein the first reactive compound comprises a polyamine and / or polyol and the second reactive compound comprises a polyisocyanate, or the first reactive compound comprises a polyamine and the second reactive compound comprises a polyepoxide, or the first reactive compound comprises a Michael acceptor and the second reactive compound comprises a Michael donor, or the first reactive compound comprises a polythiol and the second reactive compound comprises a polythiol, polyisocyanate, polyalkenyl, polyalkynyl, polyepoxide, Michael acceptor, or any combination of the foregoing.

[0502] Aspect 23. The method of any one of aspects 1-22, further comprising the steps of pumping the first component to the mixer using a first pump, and pumping the second component to the mixer using a second pump.

[0503] Example 24. The method of any one of examples 1 to 23, further comprising, after depositing the extrudate, curing the deposited extrudate.

[0504] Embodiment 25. The method of embodiment 24, wherein curing comprises curing the deposited extrudate at a temperature less than 30° C.

[0505] Embodiment 26. The method of any one of embodiments 1-25, further comprising the step of fusing one or more additional co-reactive compositions with the co-reactive sealant composition, wherein extruding comprises co-extruding the co-reactive sealant composition and the one or more additional co-reactive compositions to form a co-extrudate, and depositing comprises depositing the co-extrudate to form a multi-layer system including one or more sealant layers.

[0506] Embodiment 27. The method of embodiment 26, wherein the one or more additional co-reactive compositions each independently comprise an additional co-reactive sealant composition or a co-reactive non-sealant composition.

[0507] Example 28 The method of example 26 or 27, wherein the co-reactive sealant composition and the adjacent additional co-reactive composition comprise the same cure chemistry.

[0508] Embodiment 29. The method of any one of embodiments 26-28, wherein the co-reactive sealant composition and the adjacent additional co-reactive composition comprise different cure chemistries.

[0509] Embodiment 30 The method of any one of embodiments 26-29, wherein the co-reactive sealant composition is reactive to an adjacent additional co-reactive composition.

[0510] Embodiment 31. The method of any one of embodiments 26-30, further comprising combining the additive-containing composition with a portion of the additional co-reactive composition to form an additive-modified additional co-reactive composition, the additive-containing composition comprising an additive, and wherein extruding comprises co-extruding the co-reactive sealant composition and the additive-modified additional co-reactive composition to form a coextrudate.

[0511] Example 32. The method of example 31, wherein the cross-sectional profile of the coextrudate has a non-uniform additive concentration.

[0512] Example 33. The method of example 31 or 32, wherein the extrudate is characterized by a non-uniform concentration of the additive in the longitudinal dimension of the coextrudate.

[0513] Embodiment 34 The method of any one of embodiments 26-33, further comprising mixing the third component with the fourth component to form one or more additional coreactive compositions.

[0514] Example 35. The method of any one of examples 1-34, further comprising combining the additive-containing composition with a portion of the co-reactive sealant composition to form an additive-modified co-reactive sealant composition, the additive-containing composition comprising an additive, and extruding the additive-modified co-reactive sealant composition to form an extrudate.

[0515] Example 36 The method of example 35, wherein the cross-sectional profile of the extrudate has a non-uniform additive concentration.

[0516] Aspect 37. The method of aspect 35 or 36, wherein the extrudate is characterized by a non-uniform concentration of the additive in the longitudinal dimension of the extrudate.

[0517] Embodiment 38. The method of any one of embodiments 1 to 37, further comprising a step of fusing the adhesion promoting composition with the co-reactive sealant composition, and wherein the extrusion comprises co-extruding the first co-reactive composition and the adhesion promoting composition.

[0518] Example 39. The method of any one of examples 1 to 38, further comprising applying an adhesion-promoting layer to the extrudate prior to depositing the extrudate.

[0519] Example 40. A multi-layer system comprising a sealant layer produced by the method of any one of Examples 1-39.

[0520] Embodiment 41. The multilayer system according to embodiment 40, wherein adjacent layers are chemically and / or physically bonded.

[0521] Example 42. The multi-layer system according to example 40 or 41, wherein the fracture energy of the fully cured multi-layer sealant is substantially the same as the fracture energy of the individual layers, the fracture energy being determined according to ASTM D7313.

[0522] Embodiment 43. The multilayer system of any one of embodiments 40 to 42, wherein each layer comprises a thermosetting material.

[0523] Embodiment 44. The multilayer system of any one of embodiments 40 to 43, wherein the layers each comprise a different thermosetting material.

[0524] Embodiment 45. The multi-layer system of any one of embodiments 40 to 44, wherein the multi-layer system meets or exceeds the requirements for aerospace sealants as set forth in AMS 3277.

[0525] Embodiment 46. The multi-layer system of any one of embodiments 40-45, wherein one or more of the layers of the multi-layer sealant have a non-uniform composition cross-sectional profile.

[0526] Embodiment 47. The multi-layer system of any one of embodiments 40-46, wherein one or more of the layers of the multi-layer sealant have a non-uniform composition in the longitudinal dimension.

[0527] Embodiment 48. A component comprising the multilayer system according to any one of embodiments 40 to 47.

[0528] Aspect 49. The part of aspect 48, wherein the part comprises an automotive vehicle part or an aerospace vehicle part.

[0529] Embodiment 50. A vehicle comprising the multilayer system according to any one of embodiments 40 to 47.

[0530] Aspect 51. A vehicle as described in aspect 50, wherein the vehicle comprises an aerospace vehicle or an automotive vehicle. EXAMPLES

[0531] The embodiments provided by the present disclosure are further illustrated by reference to the following examples which describe methods of making and properties of the multi-layer systems. It will be apparent to those skilled in the art that many modifications, both to materials and methods, can be practiced without departing from the scope of the present disclosure.

[0532] Example 1 Synthesis of thiol-terminated polyepoxy extended copolymers Thiol-terminated polythioether polymer Permapol® P3.1E (384.32 g, available from PPG Aerospace, mercaptan equivalent weight 1650) and polyepoxide DEN® 431 (8.45 g, available from Dow Chemical) were combined in a plastic cup. These components were combined using a mixer (Hauschild Speed ​​Mixer, 2,300 rpm, 45 seconds). Amine Dabco® 33-LV (5.38 g, available from Air Products & Chemicals) was added to the mixture and combined using a high-speed mixer (Hauschild SpeedMixer®, 30 seconds at 2,300 rpm and 5 minutes at 800 rpm). The resulting thiol-terminated polyepoxy extended polythioether prepolymer was then allowed to sit at 23° C. for 24 hours before being combined with other components to prepare the co-reactive sealant composition. The thiol-terminated polyepoxy-extended polythioether prepolymer had a number average molecular weight of 4,716 Da and a thiol equivalent weight of 2,069 Da.

[0533] Example 2 Preparation of Skydrol®-resistant polythioether sealant A base co-reactive component (Part B) was prepared comprising the thiol-terminated polyepoxy-extended polythioether prepolymer of Example 1. The ingredients shown in Table 1 were combined and mixed to form the base component (Part B). [Table 1] 1 Available from Honeywell, Morris Plains, NJ. 2 Available commercially from Sakai Trading, New York, NY. 3 Available from Solvay. 4 Available from Cabot Corp. 5 Available from PPG Aerospace, Sylmar, CA. 6 Available from Momentive. 7 Available from Durez Corp.

[0534] An accelerator component (Part A) was prepared containing a polyepoxide curing agent. The components of the accelerator component (Part A) are shown in Table 2. [Table 2] 1 Available from Dow Chemical. 2 Polyurethane polyepoxide, epoxy equivalent weight 245; commercially available from Adeka Corporation, Tokyo, Japan. 3 Difunctional epoxy-terminated polythioether; epoxy equivalent weight 584; commercially available from PPG Aerospace, Sylmar, CA. 4 Available from Dow Chemical. 5 Available from Solvay. 6 Available from Sun Chemical Corp.

[0535] A Skydrol® LD-4 Resistant Co-reactive sealant composition was prepared by mixing 100 parts of the base component (B part) with 15.3 parts of the accelerator component (A part).

[0536] Example 3 multilayer system The multi-layer system was produced by first preparing a first inner layer containing the sealant and then applying a second outer layer over the first inner layer. The material used to prepare the first inner layer was not Skydrol® LD-4 resistant.

[0537] The inner layer was prepared by cutting samples of cured PR-2001 or PR-1776M sealant into 2" x 2" x 0.25" blocks. Both PR-2001 and PR-1776M are commercially available from PPG Aerospace. PR-2001 is a Class B, two-component, epoxy-cured Permapol® 3.1 thiol-terminated polythioether prepolymer-based sealant. PR-1776M is a Class B, two-component, manganese dioxide-cured Permapol® P-5 modified polysulfide-based sealant.

[0538] The inner sealant block was then coated with a layer of the Skydrol®-resistant co-reactive sealant composition of Example 2 having a variable thickness of 1 mm to 4 mm to provide an outer layer that covered the top, bottom, and sides of the block and was then cured.

[0539] The multi-layer systems (Multi-layer Systems 1-4) were immersed in Skydrol® LD-4 at 70° C. for 1-5 days and the Shore A hardness of the blocks was measured periodically.

[0540] Skydrol® LD-4 is a fire resistant hydraulic fluid based on phosphate ester chemistry available from Eastman Chemical Company. Skydrol® LD-4 has concentrations of about 58.2% by weight tributyl phosphate, about 20% to 30% by weight dibutylphenyl phosphate, about 5% to 10% by weight butyl diphenyl phosphate, less than about 10% by weight 2-ethylhexyl-7-oxabicyclo[4.1.0]heptane-3-carboxylate, and about 1% to 5% by weight 2,6-di-tert-butyl-p-cresol.

[0541] Hardness was determined according to ASTM D2240. The hardness of control sealants consisting of PR-2001 (sealant C1) or PR-1776M (sealant C2) sealant blocks without the layer of Skydrol® resistant sealant of Example 2 was also measured at intervals during immersion in Skydrol® LD-4 at 70° C.

[0542] The results are shown in Table 3. The results show that the multi-layer system including the sealant layer is more stable than the single-layer system. The results demonstrate that the mice exhibited greater resistance to Skydrol® LD-4 than to the conventional strain. [Table 3]

[0543] Finally, it should be noted that there are alternative ways of implementing the embodiments disclosed herein. Thus, the present embodiments should be considered as illustrative and not restrictive. Moreover, the claims should not be limited to the details given herein, but are entitled to their full scope and equivalents.

Claims

[Claim 1] Chemical resistance.

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