Linear sealing components and methods and compositions for additive manufacturing thereof

Abstract

An embodiment of the present disclosure relates to a sealing component including a first recess and a second recess, the first recess and the second recess defining a centerline, a first volume on a first side of the centerline, a second volume on a second side of the centerline, and a third volume between the first recess and the second recess, the third volume being such that the centerline passes through the third volume. The first recess is bounded by a first recess opening, a first tip of the first volume, a second tip of the second volume, and a first wall of the third volume. The second recess is bounded by a second recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 63 / 277,646, filed November 10, 2021, which is incorporated by reference in its entirety.

[0002] The present disclosure relates to a linear sealing component, and methods and compositions for additive manufacturing thereof. The present disclosure further relates to a sealing component that may have flame retardant and / or acoustic attenuation properties, and methods and compositions for additive manufacturing thereof. The linear sealing component may be used in aerospace applications. [Background technology]

[0003] Aircraft require precise construction and fit of their structural components. Slight mismatches can result in physical gaps between components. Even slightly mismatched aircraft interior structural components can result in poor acoustic attenuation properties between the cabin and other areas such as the aircraft avionics bay, baggage compartment, and landing gear wheel wells. In particular, noise can migrate from noisy areas of the aircraft to the cabin area through physical gaps, thus causing noise pollution. Currently, insulating tapes and foams are typically manually inserted into the physical gaps to improve barrier properties, but these are only marginally effective and not satisfactory. The ineffectiveness can be attributed, at least in part, to poor sealer properties, poor sealer-component interfaces, and various gap sizes.

[0004] What is needed is an improvement over the foregoing. Summary of the Invention

[0005] The present disclosure relates to an additively manufactured sealing component. The additively manufactured sealing component may include a first recess and a second recess opposite the first recess, where the first recess and the second recess define a centerline, a first volume on a first side of the centerline, a second volume on a second side of the centerline, and a third volume between the first recess and the second recess, where the centerline passes through the third volume. The first recess may be defined by a first recess opening, a first tip of the first volume, a second tip of the second volume, and a first wall of the third volume. The second recess may be defined by a second recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume. The elongated body may comprise a thermoset polymer formed by mixing at least a first co-reactive component and a second co-reactive component to form a co-reactive mixture, depositing the reactive mixture layer-by-layer to form the elongated body, and curing the deposited reactive mixture via an actinic radiation source.

[0006] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 illustrates an apparatus for additively manufacturing a linear sealing component.

[0008] [Figure 2A] 1 is an image showing a linear sealing component according to a first embodiment.

[0009] [Figure 2B] 2B is an image showing that the linear sealing component of FIG. 2A fits into a 1 / 2 inch panel gap between 1 / 8 inch panels.

[0010] [Figure 3A]13 is an image showing the linear sealing component of the second embodiment fitting into a 1 / 8 inch panel gap between 1 / 8 inch panels.

[0011] [Figure 3B] 3B is an image showing that the linear sealing component of FIG. 3A fits into a 1 / 2 inch panel gap between 3 / 8 inch panels.

[0012] [Figure 4] FIG. 1 illustrates a method for additively manufacturing a linear sealing component.

[0013] [Diagram 5] FIG. 1 illustrates an acoustic test setup.

[0014] [Figure 6] 1 is a graph showing frequency spectrum data of sound pressure levels with and without a linear sealing component installed.

[0015] [Figure 7] 1 is a graph showing overall sound pressure levels with and without the linear sealing component installed.

[0016] [Figure 8A] 1 is a graph showing the viscosity of a coreactive mixture at a range of shear rates.

[0017] [Figure 8B] 1 is a graph showing the post-shear viscosity of a coreactive mixture over time.

[0018] [Figure 9] FIG. 1 illustrates dimensions of a linear sealing component. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] definition For the purposes of the following detailed description, it should be understood that the present invention can take various alternative variations and sequences of steps, unless expressly specified to the contrary. Moreover, other than any operational examples, or where otherwise indicated, all numbers expressing the amounts of ingredients used in the specification and claims, for example, should be understood as being modified in all instances by the term "about". Thus, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired properties obtained by the present disclosure. 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 be construed at least in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0020] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure 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.

[0021] It is also to be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range "1 to 10" is intended to have all subranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., minimum values ​​equal to or greater than 1 and maximum values ​​equal to or less than 10.

[0022] The use of the singular includes the plural and the plural encompasses the singular unless specifically stated otherwise. Additionally, although "and / or" may be expressly used in certain instances, the use of "or" means "and / or" unless specifically stated otherwise.

[0023] "Alkanediyl" means an alkyl group 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 linear acyclic hydrocarbon group. 2~14 Alkanediyl, C 2~10 Alkanediyl, C 2~8 Alkanediyl, C 2~6 Alkanediyl, C 2~4 Alkanediyl, or C 2~3 The alkanediyl group may be methanediyl (-CH 2 -), ethane-1,2-diyl (-CH 2 CH 2 -), propane-1,3-diyl and isopropane-1,2-diyl (e.g., -CH 2 CH 2 CH 2 - and -CH(CH 3 )CH 2 -), butane-1,4-diyl (-CH 2 CH 2 CH 2 CH 2 -), pentane-1,5-diyl (-CH 2 CH 2 CH 2 CH 2 CH 2 -), hexane-1,6-diyl (-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -), heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, and dodecane-1,12-diyl.

[0024] "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. 4~18 Alkane Cycloalkane, C 4~16 Alkane Cycloalkane, C 4~12 Alkane Cycloalkane, C 4~8 Alkane Cycloalkane, C 6~12 Alkane Cycloalkane, C 6~10 Alkane Cycloalkane, or C 6~9 It may be an alkanecycloalkane. The alkanecycloalkane group may include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

[0025] "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 6~9 It can be an alkanecycloalkanediyl. The alkanecycloalkanediyl group can include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.

[0026] An "alkenyl" group is a group having the structure -CR=C(R) 2 where the alkenyl group is the terminal group attached to a larger molecule. In such cases, each R can independently be selected from hydrogen and C. 1~3 Each R can be hydrogen and an alkenyl group has the structure -CH=CH 2 may have:

[0027] "Alkoxy" refers to an -OR group, where R is alkyl, as defined herein. Exemplary alkoxy groups can include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. An alkoxy group can be any of the C 1~8 Alkoxy, C 1~6 Alkoxy, C 1~4 Alkoxy, or C 1~3 It may be alkoxy.

[0028] "Alkyl" refers to a monoradical of a saturated, branched, or linear acyclic hydrocarbon group having 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. An alkyl group is any of the C 1~6 Alkyl, C 1~4 Alkyl, or C 1~3 Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, and tetradecyl. The alkyl group can be C 1~6 Alkyl, C 1~4 Alkyl, and C 1~3 It may be alkyl.

[0029] "Arenediyl" refers to a diradical monocyclic or polycyclic aromatic group. Exemplary arenediyl groups can include benzene-diyl and naphthalene-diyl. Arenediyl groups are C 6~12 Arendjiil, C 6~10 Arendjiil, C 6~9 It may be arene-diyl, or benzene-diyl.

[0030] "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 Exemplary cycloalkanediyl groups can include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

[0031] "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.

[0032] "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 be N or O.

[0033] "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 be N or O.

[0034] The "backbone" of a prepolymer refers to the segments between the reactive end groups. The prepolymer backbone is typically a polythiol HS-[R] n It contains repeating subunits such as the -SH backbone.

[0035] A "co-reactive composition" refers to a composition that includes two or more co-reactive compounds that can react at temperatures such as less than 50°C, less than 40°C, less than 30°C, or less than 20°C. The reaction between the two or more compounds can be initiated by combining and mixing the two or more co-reactive compounds and / or by exposing the co-reactive composition that includes the two or more co-reactive compounds to actinic radiation. The co-reactive composition can be formed 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.

[0036] Multifunctionalizing Agent B(-V) z The "core" of refers to moiety B. The "core" of a compound or polymer refers to the segment between the reactive end groups, such as the core of polythiol HS-R-SH. The core of a compound or prepolymer may also be referred to as the backbone of a compound or the backbone of a prepolymer. The core of a polyfunctionalizing agent may be an atom or a structure, such as a cycloalkane, substituted cycloalkane, heterocycloalkane, substituted heterocycloalkane, arene, substituted arene, heteroarene, or substituted heteroarene, to which moieties bearing reactive functional groups are attached.

[0037] "Cure rate" and / or "cure time" can refer to the period of time from when the curing reaction of the coreactive composition is first initiated 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 Shore 30A hardness 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 when a layer prepared from the exposed coreactive composition exhibits a Shore 30A hardness at 25° C. and 50% relative humidity.

[0038] A dash ("-") that is not between two letters or symbols indicates the point of attachment of a substituent or -CONH 2 is used to indicate that the point of attachment between two atoms, such as is, is through a carbon atom.

[0039] "Derived from," as in "moiety derived from a compound," means that a moiety is produced upon reaction of a parent compound with a reactant. For example, the bis(alkenyl) compound CH 2 =CH-R-CH=CH 2 reacts with another compound, such as a compound that has a thiol group, to produce the moiety -(CH 2 ) 2 -R-(CH 2 ) 2 As another example, for a parent diisocyanate having the structure O=C=NRN=C=O, the moiety derived from the diisocyanate has the structure -C(O)-NH-R-NH-C(O)-.

[0040] "Derived from the reaction of -V with a thiol" means that the moiety -V'- results from the reaction of a thiol group with a moiety that contains an end group reactive to a thiol group. For example, the group V- can be CH 2 =CH-CH 2 -O- and may contain a terminal alkenyl group CH 2 =CH- is reactive to thiol groups -SH. When reacted with a thiol group, the moiety -V'- becomes -CH 2 -CH 2 -CH 2- It is O-.

[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] Monomers may refer to low molecular weight compounds and may have 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 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, such as 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 2 to 6, 2 to 5, 2 to 4, 2 to 3, 2.1 to 2.8, or 2.2 to 2.6, etc.

[0043] "Polyalkenyl" refers to a compound having at least two alkenyl groups. At least two of the alkenyl groups may be terminal 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 more than two alkenyl groups, for example, three to six alkenyl groups. The polyalkenyl may include a single type of polyalkenyl, may be a combination of polyalkenyls with the same alkenyl functionality, or may be a combination of polyalkenyls with different alkenyl functionality.

[0044] "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 iodine titration. For prepolymers that are not thiol-terminated, the number average molecular weight is determined by gel permeation chromatography using polystyrene standards. A prepolymer comprises a backbone and a terminal reactive group that can react with another compound, such as a curing agent or crosslinker, to form a cured polymer. A prepolymer comprises multiple repeating moieties linked together, which may be the same or different. The multiple repeating moieties make up the backbone of the prepolymer.

[0045] The polyfunctionalizing agent has the formula (1): B(-V) z (1) wherein B 1 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. In the polyfunctionalizing agent of formula (1), each -V is -R-SH or -R-CH=CH 2 wherein R is 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 other compounds. For example, V may be -R-CH=CH 2 and when reacted with a thiol group, the moiety V 1 -R-CH 2 -CH 2 - and can result from reactions.

[0046] Specific gravity is determined in accordance with ASTM D1475.

[0047] Shore A hardness is measured using a Type A durometer according to ASTM D2240.

[0048] "Substituted" refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituent(s). Substituents include halogen, -S(O) 2 OH, -S(O) 2 , -SH, -SR [wherein R is C 1~6 alkyl], -COOH, -NO 2 , -NR 2 wherein each R is independently selected from hydrogen and C 1~3 alkyl], -CN, =O, C 1~10 Alkyl, -CF 3 , -OH, Phenyl, C 2~6 Heteroalkyl, C 5~6 Heteroaryl, C 1~10 Alkoxy, or -COR, where R is C 1~10 The substituents may include -OH, -NH 2 , or C 1~10 It may be alkyl.

[0049] "Tack-free time" refers to the duration from when the curing reaction of the coreactive composition is first initiated to when a layer prepared from the coreactive composition is no longer tack-free, 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; if the polyethylene sheet easily separates from the layer, the layer is considered to be tack-free. For actinic radiation-curable coreactive compositions, tack-free time refers to the time from when the coreactive composition is exposed to actinic radiation to when a layer prepared from the coreactive composition is no longer tack-free.

[0050] Tensile strength and elongation are measured in accordance with AMS3279.

[0051] "Transmittance" refers to the ability to transmit a portion of the electromagnetic spectrum in the range of 360 nm to 750 nm, such as greater than 20%, greater than 30%, greater than 40%, or greater than 50% of the incident radiation.

[0052] Reference will now be made to certain compounds, compositions, devices, and methods of the present disclosure. The disclosed compounds, compositions, devices, 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.

[0053] Introduction Methods provided by the present disclosure include a method of fabricating a linear sealing component using three-dimensional (3D) printing. Three-dimensional printing includes various robotic manufacturing methods in which processor-controlled robotic methods are used to form three-dimensional articles. The linear sealing component may be fabricated by conveying a first co-reactive component and a second co-reactive component to a mixing chamber, mixing the first co-reactive component and the second co-reactive component to form a reactive mixture, depositing the reactive mixture layer-by-layer to form an elongated body, and curing the deposited reactive mixture via an actinic radiation source. In various examples, the first co-reactive component includes a thiol-terminated polythioether, while the second co-reactive component includes a polyvinyl ether. A linear sealing component fabricated according to the present disclosure may include a first recess and a second recess opposite the first recess, a first volume on a first side of a centerline defined by the first recess and the second recess, a second volume on a second side of the centerline, and a third volume between the first recess and the second recess, such that the centerline passes through the third volume. The first recess may be defined by a first recess opening, a first tip of the first volume, a second tip of the second volume, and a first wall of the third volume. The second recess may be defined by a second recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume. The elongated body may comprise a thermoset polymer formed by mixing at least a first co-reactive component and a second co-reactive component to form a co-reactive mixture, depositing the reactive mixture layer-by-layer to form the elongated body, and curing the deposited reactive mixture via an actinic radiation source.

[0054] A 3D printing apparatus 100 is shown in FIG. 1. FIG. 1 shows the printing apparatus 100 including a mixing chamber 102, a first reactant reservoir 104, a second reactant reservoir 106, an extrusion tip 108, a printing platform 110, and a radiation source 112. The mixing chamber 102 may be fluidly coupled to the first reactant reservoir 104 and the second reactant reservoir 106 such that a first reactant stored in the first reactant reservoir 104 and a second reactant stored in the second reactant reservoir 106 are transported to the mixing chamber 102 to be mixed. Once mixed, the reactant mixture may be deposited on the printing platform 110 via the extrusion tip 108 to form a printed body 114. The printed body 114 may be cured or further cured by a radiation source 112 that may provide actinic radiation during and / or after deposition of the reactant mixture.

[0055] Linear Sealing Components Configuration 1 - Closed core double crescent A linear sealing component is a linear structure that fits into a physical gap between structures. A linear sealing component may fit between a panel gap between two or more panels (e.g., cabin panels of an aircraft). A cross-sectional view of a linear sealing component 200 is shown in Figures 2A and 2B.

[0056] 2A illustrates a linear sealing component 200 having a first volume 202, a second volume 204, a third volume 206, a first crescent shaped recess 208, and a second crescent shaped recess 210. A reference centerline may be defined by the first crescent shaped recess 208 and the second crescent shaped recess 210 as it passes through the third volume 206. As shown, the third volume 206 is centrally positioned and defined by a first inner wall 212, a second inner wall 214, a third inner wall 216, and a fourth inner wall 218. The first volume 202 is positioned on a first side of the reference centerline and is defined by a first outer wall 224, a second inner wall 214, a first tip 220, and a second tip 222. The second volume 204 is positioned on a second side of the reference centerline and is defined by the second outer wall 230, the fourth inner wall 218, the third apex 226, and the fourth apex 228. The first crescent-shaped recess 208 is defined by the first inner wall 212, the first apex 220, and the third apex 226. The second crescent-shaped recess 210 is defined by the third inner wall 216, the second apex 222, and the fourth apex 228. The ability of the linear sealing component to secure a panel with at least three contact points may be attributed to the excellent sound attenuation performance. The crescent-shaped recess may be referred to as a recess.

[0057] FIG. 2B illustrates the linear sealing component 200 of FIG. 2A fitted into a panel gap between a first panel 228 and a second panel 230. Specifically, the first panel 228 is received by the first crescent recess 208 and secured (e.g., via friction and / or pressure) by the first inner wall 212, the first tip 220, and the third tip 226. The second panel 230 is received by the second crescent recess 210 and secured (e.g., via friction and / or pressure) by the third inner wall 216, the second tip 222, and the fourth tip 228. In certain instances, a panel received in a crescent recess does not need to be in contact (e.g., continuous contact) with all three contact points to maintain a seal. The depicted panel 228 may not be in direct contact with the inner core 212, but is secured by the tips 220, 226 to form an effective seal. The first crescent recess 208 and the second crescent recess 210 may each be triangular with an opening narrower than the base near the inner wall. As shown, the opening of the first crescent recess 208 may be configured to receive a panel that is between the linear sealing components of the present disclosure and not in-plane. As depicted, the linear sealing component 200 holds the first panel 228 and the second panel 230 together (e.g., via elastic deformation) when the panels are out-of-plane. The linear sealing component 200 may receive an in-plane panel as well. Additionally, the linear sealing components of the present disclosure may be configured to receive panels spaced apart at various gap sizes, such as 0-1 / 2 inches and / or 0-100% of the recess-to-recess distance of the component 200. As depicted, the linear sealing component 200 can join (e.g., via elastic deformation) a first panel 228 and a second panel 230 when the panel gap is less than the distance from the natural first crescent recess to the second crescent recess of the linear sealing component 200. The linear sealing component 200 can accommodate a panel that is 1 to 1.5 times thicker than its recess opening size.

[0058] Configuration 2 - Open Core Double Crescent 3A illustrates a linear sealing component 300 having an open core (e.g., a third volume having three walls and an opening) and an extended inner wall (e.g., at least two inner walls). As depicted, the linear sealing component 300 has a first volume 302, a second volume 304, a third volume 306, a first crescent-shaped recess 308, and a second crescent-shaped recess 310. A reference centerline may be defined by the first crescent-shaped recess 308 and the second crescent-shaped recess 310 as it passes through the third volume 306. As shown, the third volume 306 is centrally positioned and defined by a first inner wall 312, a second inner wall 314, a third inner wall 316, and an inner opening 318. The first volume 302 is positioned on a first side of the reference centerline and is defined by a first outer wall 324, a second inner wall 314, a first tip 320, and a second tip 322. The second volume 304 is positioned on a second side of the reference centerline and is defined by a second outer wall 330, an inner opening 318, a third tip 326, and a fourth tip 328. The first crescent shaped recess 308 is defined by a first inner wall 312, a first tip 320, and a third tip 326. The second crescent shaped recess 310 is defined by a third inner wall 316, a second tip 322, and a fourth tip 328.

[0059] As shown, the linear sealing component 300 may fit into a panel gap between a first panel 328 and a second panel 330. Specifically, the first panel 328 is received by the first crescent-shaped recess 308 and secured (e.g., via friction and / or pressure) by the first inner wall 312, the first tip 320, and the third tip 326. The second panel 330 is received by the second crescent-shaped recess 310 and secured (e.g., via friction and / or pressure) by the third inner wall 316, the second tip 322, and the fourth tip 328. The first crescent-shaped recess 308 and the second crescent-shaped recess 310 may each be triangular with an opening that is narrower than the base near the inner wall. As depicted in FIG. 3A, the linear sealing component 300 joins a first panel 328 and a second panel 330 through elastic deformation, such as compression of a third volume 306, substantially along a reference centerline. An open core design may improve the compressibility of the third volume 306 such that the linear sealing component 300 may fit into smaller panel gaps, such as the 1 / 8 inch gap shown in FIG. 3A. However, the closed core design of FIG. 2A may have superior sound attenuation performance.

[0060] FIG. 3B illustrates the linear sealing component 300 of FIG. 3A adapted for a panel gap of a longer distance than FIG. 3A. Specifically, the panel gap in FIG. 3B is ½ inch and is between a third panel 336 and a fourth panel 338. The third panel 336 is received by a first crescent recess 308 and secured (e.g., via friction and / or pressure) by a first inner wall 312, a first tip 320, and a third tip 326. The fourth panel 338 is received by a second crescent recess 310 and secured (e.g., via friction and / or pressure) by a third inner wall 316, a second tip 322, and a fourth tip 328. The first crescent recess 308 and the second crescent recess 310 may each be triangular with an opening narrower than the base near the inner wall. As depicted in FIG. 3A, the linear sealing component 300 couples the first panel 328 and the second panel 330 together via elastic deformation, such as compression of the third volume 306 slightly along the reference centerline. Because the panel gap in FIG. 3B is larger than that in FIG. 3A, a smaller degree of compression of the third volume 306 is necessary. As shown, the third panel 336 and the fourth panel 338 are three times thicker than the first panel 328 and the second panel 330 in FIG. 3A, e.g., 3 / 8 inch instead of 1 / 8 inch. Because of the greater length of at least the interior walls 312 and 316, the linear sealing component 300 is configured to receive panels with a larger range of thicknesses (e.g., 1 / 16 inch to 1 / 2 inch). In certain circumstances, the linear sealing component 300 may receive and secure panels with thicknesses 1 to 3 times the size of its recess opening.

[0061] Coreactive Compositions The reactant mixture for fabricating the linear sealing components of the present disclosure may include a prepolymer having any suitable backbone, a prepolymer having any suitable reactive functional group, a co-reactive compound based on any suitable curing chemistry, and any suitable additives. The reactant mixture may be a co-reactive composition including a first compound having a first functional group and a second compound including a second functional group, where the first functional group is reactive to the second functional group. The first and second compounds may independently include a monomer, a combination of monomers, a prepolymer, a combination of prepolymers, or a combination thereof.

[0062] The coreactive composition can include a portion of a coreactive composition in which the reaction between the coreactive compounds is initiated by exposure to energy, such as exposure to actinic radiation (eg, ultraviolet light).

[0063] The coreactive composition can include a coreactive compound that can react without exposure to actinic radiation or after exposure to actinic radiation at a temperature of less than 50° C., e.g., less than 40° C., less than 30° C., less than 20° C., or less than 10° C. For example, the coreactive compound can react at a temperature of 5° C. to 50° C., 10° C. to 40° C., or 15° C. to 25° C., or 20° C. to 30° C.

[0064] The coreactive composition was heated at 25°C and 0.1 s -1 ~100 seconds -1 At shear rates of 200cP~50,000,000cP, 200cP~20,000,000cP, 1,000cP~18,000,000cP, 5,000cP~15,000,000cP, 5,000cP~10,000,000cP, 5,000cP~5,000,000cP, 5,0 The coreactive composition has a viscosity of 200 cP to 1,000,000 cP, 5,000 cP to 100,000 cP, 5,000 cP to 50,000 cP, 5,000 cP to 20,000 cP, 6,000 cP to 15,000 cP, 7,000 cP to 13,000 cP, or 8,000 cP to 12,000 cP. -1 ~100 seconds -1The coreactive composition has a viscosity of greater than 200 cP, greater than 1,000 cP, greater than 10,000 cP, greater than 100,000 cP, greater than 1,000,000 cP, or greater than 10,000,000 cP, etc. at a shear rate of 25° C. and 0.1 s. -1 ~100 seconds -1 At a shear rate of 100,000,000 cP, 10,000,000 cP, 1,000,000 cP, 100,000 cp, 10,000 cP, or 1,000 cP, etc., the viscosity values ​​are measured at a temperature of 25° C. and at a shear rate of 100 seconds. -1 The shear rate is measured using an Anton Paar MCR302 rheometer with a gap of 1 mm.

[0065] The co-reactive compositions may be formulated as sealant compositions that upon curing form a linear sealing component.

[0066] A linear sealing component refers to a material that has the ability to resist atmospheric conditions such as noise, moisture, and temperature, and / or at least partially block the transmission of materials such as water, solvents, fuels, hydraulic fluids, and other liquids and gases. A linear sealing component may exhibit chemical resistance, such as resistance to fuels and hydraulic fluids. A chemically resistant material may exhibit a percent swelling 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. A sealant may exhibit resistance to Jet Reference Fluid (JRF) Type I, or Skydrol® LD-40 hydraulic fluid. For example, a linear sealing component of the present disclosure may exhibit chemical resistance similar to that of the sealant described in U.S. Pat. No. 10,047,259, which is incorporated herein by reference in its entirety for all purposes.

[0067] Prepolymers and Monomers The prepolymer may have a number average molecular weight of 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 2,000 Da, etc. The prepolymer may have a number average molecular weight of 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, etc. 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, etc.

[0068] The prepolymer may be liquid at 25° C. and may have a glass transition temperature Tg of less than −20° C., less than −30° C., or less than −40° C., etc. The prepolymer may exhibit a viscosity in the range of 20 poise to 500 poise (2 Pa-sec to 50 Pa-sec), 20 poise to 200 poise (2 Pa-sec to 20 Pa-sec), or 40 poise to 120 poise (4 Pa-sec to 12 Pa-sec), etc.

[0069] Prepolymer backbone The coreactive composition may include a prepolymer having any suitable polymer backbone. The polymer backbone may be selected 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.

[0070] The prepolymer backbone may be 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, polyethylene The polymers may include, for example, ethylene, syndiotactic or isotactic polypropylene, polylactic acid, polyamide, ethyl-vinyl acetate homopolymer or copolymer, polyurethane, 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.

[0071] 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, and the like), olefin and styrene copolymers, acrylonitrile / styrene copolymers, styrene ... Butadiene / styrene (ABS), styrene / acrylonitrile polymer (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) Homopolymers and copolymers, polyetherimides, fluorinated ethylene 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)),Included may be elastomers, epoxy polymers, polyureas, alkyds, 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.

[0072] The coreactive composition may include a prepolymer that includes an elastomeric backbone.

[0073] Elastomer refers to a material that has "rubber-like" properties and generally has a low Young's modulus and a high tensile strain. Elastomers may have a tensile strain (elongation at break) of 100% to 2,000%. Elastomers may exhibit tear strengths, such as 50 kN / m to 200 kN / m, as determined according to ASTM D624. The Young's modulus of an elastomer may range from 0.5 MPa to 30 MPa, such as 1 MPa to 6 MPa, as determined according to ASTM D412.4893.

[0074] Suitable prepolymers having an elastomeric backbone may 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. The elastomeric prepolymer may include polysiloxanes, such as polymethylhydrosiloxanes, polydimethylsiloxanes, polyhydrodiethylsiloxanes, polydiethylsiloxanes, or combinations of any of the foregoing. The elastomeric prepolymer may include terminal functional groups, such as silanol groups, that are less reactive with amines and isocyanate groups.

[0075] Sulfur-containing prepolymer The coreactive composition may include a sulfur-containing prepolymer or a combination of sulfur-containing prepolymers. The sulfur-containing prepolymer may impart acoustic properties to the cured linear sealing component. The sulfur-containing prepolymer may include a sulfur-containing prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, a monosulfide prepolymer, or a combination of any of the foregoing.

[0076] Sulfur-containing prepolymers are those that contain one or more thioether-S groups in the backbone of the prepolymer. n - groups, where n can be 1-6. Prepolymers that contain only thiols or other sulfur-containing groups as either the end groups 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(-CH 2 -SH)-[-R-(CH 2 ) 2 -S(O) 2 -(CH 2 )-S(O) 2 ]n -CH=CH 2 A prepolymer having the structure: where each R is a moiety that does not contain a sulfur atom is not included as a sulfur-containing prepolymer. 2 -SH)-[-R-(CH 2 ) 2 -S(O) 2 -(CH 2 )-S(O) 2 ]-CH=CH 2 where at least one R is a moiety that contains a sulfur atom, such as a thioether group, is included as a sulfur-containing prepolymer.

[0077] Sulfur-containing prepolymers with high sulfur content can impart chemical resistance to the cured coreactive composition. The sulfur-containing prepolymer backbone can have a sulfur content of greater than 10 wt%, greater than 12 wt%, greater than 15 wt%, greater than 18 wt%, greater than 20 wt%, or greater 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 10 wt% to 25 wt%, 12 wt% to 23 wt%, 13 wt% to 20 wt%, or 14 wt% to 18 wt%, etc., where the weight percent is based on the total weight of the prepolymer backbone.

[0078] Prepolymers having a sulfur-containing backbone can include polythioether prepolymers, polysulfide prepolymers, sulfur-containing polyformal prepolymers, monosulfide prepolymers, and combinations of any of the foregoing.

[0079] The coreactive composition may 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 percent is based on the total weight of the coreactive composition. The coreactive composition may 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 percent is based on the total weight of the coreactive composition. The coreactive composition may 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 percent is based on the total weight of the coreactive composition.

[0080] Co-reactive functional groups The coreactive composition can include a coreactive compound having any suitable coreactive functional group.

[0081] The first co-reactive compound can include one or more first functional groups and the second co-reactive compound can include one or more second functional groups, where the one or more first functional groups are reactive to the one or more second functional groups.

[0082] A functional group or combination of functional groups can be selected to achieve the desired cure rate.

[0083] The first functional group can include a thiol group and the second functional group can include a thiol group, an alkenyl group, an alkynyl group, an epoxy group, a Michael acceptor group, an isocyanate group, or a combination of any of the foregoing.

[0084] The first functional group may include an isocyanate and the second functional group may include a hydroxyl group, an amine group, a thiol group, or a combination of any of the foregoing.

[0085] The first functional group can include an epoxy group and the second functional group can include an epoxy group.

[0086] The first functional group can include a Michael acceptor group and the second functional group can include a Michael donor group.

[0087] The first functional group can include a carboxylic acid group and the second functional group can include an epoxy group.

[0088] The first functional group can include a cyclic carbonate group, an acetoacetate group, or an epoxy group, and the second functional group can include a primary amine group, or a secondary amine group.

[0089] The first functional group can include 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 include a malonate group, acetylacetonate, nitroalkane, or another activated alkenyl group.

[0090] The first functional group may include an amine and the second functional group may include a group selected from an epoxy group, an isocyanate group, an acrylonitrile, a carboxylic acid including esters and anhydrides, an aldehyde, or a ketone.

[0091] Suitable coreactive functional groups are described in Noomen, Proceedings of the XIIIth International Conference in Organic Coatings Science and Technology, Athens, 1987, page 251, and Tillet et al., Progress in Polymer Science, 36 (2011), 191-217.

[0092] The functional groups may be selected to co-react at temperatures 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 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 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.

[0093] 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. The co-reactive composition can be cured at temperatures below 30° 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.

[0094] Curable Coreactive Compositions The coreactive composition may include coreactive compounds capable of coreacting at temperatures below 50° C. without exposure to actinic radiation, and may optionally include a catalyst.

[0095] The coreactive composition can include compounds such as monomers and / or prepolymers that include coreactive functional groups, including any of those disclosed herein.

[0096] The coreactive composition may further include a suitable catalyst or combination of catalysts for catalyzing the reaction between the coreactive compounds.

[0097] Radiation-curable coreactive compositions The co-reactive composition may be an actinic radiation-curable co-reactive composition, in which the curing reaction between the co-reactive compounds in the co-reactive composition is initiated by exposing the co-reactive composition to actinic radiation.

[0098] Actinic radiation includes alpha radiation, gamma radiation, X-rays, ultraviolet (UV) radiation (200 nm to 400 nm), such as UV-A radiation (320 nm to 400 nm), UV-B radiation (280 nm to 320 nm), and UV-C radiation (200 nm to 280 nm); visible radiation (400 nm to 770 nm), radiation in the blue wavelength range (450 nm to 490 nm), infrared radiation (greater than 700 nm), near infrared radiation (0.75 μm to 1.4 μm), and electron beams.

[0099] The radiation-curable coreactive composition may include compounds capable of coreacting by a free radical mechanism. Free radical curing reactions may include thiol / alkenyl and thiol / alkynyl reactions.

[0100] The radiation-curable coreactive composition can include any suitable free radical polymerization initiator or combination of suitable free radical polymerization initiators. The free radical polymerization initiators can include photoinitiators, thermally activated free radical generators, cationic free radical generators, and dark cure free radical generators.

[0101] The radiation-curable coreactive composition may include a photoinitiator, such as a visible light initiator or a UV photoinitiator.

[0102] The radiation-curable coreactive composition may include a thermally activated free radical generator.

[0103] The radiation-curable coreactive composition may include a cationic free-radical generator.

[0104] The radiation-curable coreactive composition may include a dark-cure free-radical generator.

[0105] The free radical photopolymerization reaction can be initiated by exposing the coreactive composition to actinic radiation, such as UV radiation, for less than 180 seconds, less than 120 seconds, less than 90 seconds, less than 60 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The total power of the UV exposure is less than 50 mW / cm. 2 ~500mW / cm 2 , 50mW / cm 2 ~400mW / cm 2 , 50mW / cm 2 ~300mW / cm 2 , 100mW / cm 2 ~300mW / cm 2 , or 150 mW / cm 2 ~250mW / cm 2 It could be.

[0106] The actinic radiation curable coreactive composition is applied at 1 J / cm 2 ~4J / cm 2 The composition can be cured by exposing it to a UV dose of 0.5 J / cm. The UV source is an 8 W lamp with a UVA spectrum. Other doses and / or other UV sources may be used. The UV dose to cure the composition is 0.5 J / cm. 2 ~4J / cm 2 , 0.5J / cm 2 ~3J / cm 2 , 1J / cm 2 ~2J / cm 2 , or 1 J / cm 2 ~1.5J / cm 2 It could be.

[0107] The actinic radiation-curable coreactive compositions can also be cured with radiation in the blue wavelength range, such as using light emitting diodes.

[0108] Actinically curable sealant compositions suitable for use in linear sealing components are disclosed in U.S. Pat. No. 8,729,198, U.S. Pat. No. 8,729,198, U.S. Pat. No. 9,533,798, U.S. Pat. No. 10,233,369, U.S. Application Publication No. 2019 / 0169465, PCT International Publication No. PCT / US2018 / 36746; U.S. Application Publication No. 2018 / 0215974, and U.S. Pat. No. 7,438,974.

[0109] Permeable coreactive compositions The free radically polymerizable coreactive composition can be transparent to actinic radiation to the extent that the incident actinic radiation can generate sufficient free radicals to completely cure the free radically polymerizable coreactive composition.

[0110] A coreactive composition that is transparent to actinic radiation can transmit actinic radiation through a thickness of the coreactive composition of from 1 mm to 30 mm, from 1 mm to 25 mm, from 1 mm to 20 mm, from 1 mm to 15 mm, or from 1 mm to 10 mm, etc.

[0111] A free radically polymerizable coreactive composition can be partially transparent to actinic radiation to the extent that incident actinic radiation can generate sufficient free radicals to initiate free radical polymerization of the coreactive composition in at least a portion of the exposed coreactive composition. The unexposed portions of the coreactive composition can be cured by another free radical mechanism, such as a dark cure mechanism, or can be cured by a non-free radical mechanism.

[0112] The free radical initiation wavelength range can depend on the type of free radical generator in the coreactive composition.

[0113] Curing of the Coreactive Composition A coreactive composition that can be cured without exposure to actinic radiation can be deposited and cured, with the cure rate being determined by one or more of the curing chemistry, catalyst type and amount, temperature, and viscosity of the deposited coreactive composition. After deposition, the coreactive composition can be exposed to heat to accelerate the cure of at least a portion of the coreactive composition.

[0114] Curing of the free radically polymerizable coreactive composition can be initiated by activating the free radical generator, such as by exposing the free radically polymerizable coreactive composition to actinic radiation or heat.

[0115] The free radically polymerizable coreactive composition can be exposed to actinic radiation during deposition of the free radically polymerizable coreactive composition while the free radically polymerizable coreactive composition is in a three dimensional printing apparatus, and / or after the free radically polymerizable coreactive composition is deposited. The deposited free radically polymerizable coreactive composition can be exposed to actinic radiation after the coreactive composition is initially deposited, or after the linear sealing component is fabricated, or after the linear sealing component is installed between the panel gaps, depending on the method of fabrication.

[0116] The linear sealing component can be fabricated by depositing successive layers of the actinic radiation curable co-reactive composition using three-dimensional printing.

[0117] To initiate the chemical reaction, the actinic radiation-curable coreactive composition can be exposed to actinic radiation before being extruded through the nozzle, while being extruded through the nozzle, after being extruded through the nozzle, and / or while or after being deposited on a previously deposited layer.

[0118] When constructing a linear sealing component, the physical properties of the co-reactive composition may be such that the deposited co-reactive composition has sufficient mechanical strength to maintain its intended shape and to support an upper layer of the co-reactive composition before the lower layer is fully cured. The physical properties may be determined, in part, by the amounts of the components in the composition, the type and rate of cure, etc.

[0119] The linear sealing component may be fabricated by printing a coreactive composition that does not require exposure to actinic radiation to initiate the chemical reaction. The linear sealing component may be fabricated using three-dimensional printing to deposit successive layers of the coreactive composition. Similar procedures as described for fabricating actinic radiation curable linear sealing components are applicable, except for exposing the coreactive composition to actinic radiation.

[0120] Photoinitiators Any suitable photoinitiator, such as a thermally activated free radical initiator, or a free radical initiator activated by actinic radiation, or a photoinitiator.

[0121] The photoinitiator may be activated by actinic radiation that, upon irradiation, such as alpha, gamma, x-rays, ultraviolet (UV) radiation including UVA, UVA, and UVC spectrum, visible light, blue light, infrared, near infrared, or electron beam, can apply energy effective to generate an initiating species from the photoinitiator. The photoinitiator may be a UV photoinitiator.

[0122] Suitable UV photoinitiators may include α-hydroxyketones, benzophenone, 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-benzoyl benzoate, 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.

[0123] Thermally activated free radical initiators may be activated at elevated temperatures, such as temperatures above 25°C.

[0124] Suitable thermally activated free radical initiators may include organic peroxy compounds, azobis(organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations of any of the foregoing. Suitable organic peroxy compounds that may 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; diacylperoxides, such as ethylperoxides, ... Peroxyesters 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 suitable thermal polymerization initiators may include 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, and / or 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane. 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 / 1-dimethylvaleronitrile).

[0125] The coreactive compositions may also be cured by means other than using actinic radiation, such as the coreactive compounds listed above, and will typically include two or more modifying compounds.

[0126] For use in three-dimensional printing, a first co-reactive component and a second co-reactive component can be combined in a mixer to form a co-reactive composition that can be extruded and deposited through a nozzle to form a linear sealing component. After deposition, over time, the co-reactive composition hardens to provide a hardened linear sealing component.

[0127] Through the use of co-reactive three-dimensional printing, the range of chemicals and compositions used to fabricate linear sealing components can be expanded beyond the range suitable for use in actinic radiation curable compositions.

[0128] Additionally, a single co-reactive composition can be used to fabricate the linear sealing component, although more than one co-reactive composition may be used, with each co-reactive composition being tailored to optimize the desired properties. The co-reactive composition applied directly to the fastener can be configured to promote adhesion to the fastener surface and be of low density, and the outer co-reactive composition applied over the inner co-reactive composition can be configured to provide enhanced fuel resistance.

[0129] The chemistries of the inner and outer coreactive compositions may be the same or different. Using the same curing chemistry for the inner and outer coreactive compositions may promote adhesion between the two coreactive compositions through the formation of covalent bonds.

[0130] Co-reactive curing chemistries can include thiol / alkenyl, thiol / alkynyl, thiol / thiol, thiol / Michael acceptor, thiol / epoxy, thiol / isocyanate, isocyanate / hydroxyl, isocyanate / amine, and Michael donor / Michael acceptor.

[0131] Polythioether The coreactive composition can include a polythioether prepolymer, or a combination of polythioether prepolymers.

[0132] The polythioether prepolymer can include a polythioether prepolymer comprising at least one moiety having a structure of formula (2), a thiol-terminated polythioether prepolymer of formula (2a), a terminal-modified polythioether of formula (2b), or a combination of any of the foregoing: -SR 1 -[SASR 1 -] n -S- (2) HS-R 1 -[SASR 1 -] n -SH (2a) R 3 -SR 1 -[SASR 1 -] n -SR 3 (2b) During the ceremony, n may be an integer from 1 to 60; Each R 1 are 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 (3) and a polyalkenyl polyfunctionalizing agent of formula (4): CH 2 =CH-O-(R 2 -O) m -CH=CH 2 (3) B(-R 4 -CH=CH 2 ) z (4) During the ceremony, m may be an integer from 0 to 50; Each R 2 are 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 Each R 3 can independently be a moiety that includes a terminal reactive group, B is a z-valent polyalkenyl polyfunctionalizing agent B(-R 7 -CH=CH 2 ) z represents a core of the formula: z can be an integer from 3 to 6; Each R 4 are independently 1~10 Alkanediyl, C 1~10 Heteroalkanediyl, substituted C 1~10 Alkanediyl and substituted C 1~10 Heteroalkanediyl may be selected from the group consisting of heteroalkanediyl.

[0133] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 is C 2~10 It may be an alkanediyl.

[0134] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CHR) p -X-] q (CHR) r --It could be.

[0135] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), X can be selected from O and S, and thus -[(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.

[0136] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 is C 2~6 Alkanediyl and -[(CHR) p -X-] q (CHR) r - may be selected from.

[0137] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CHR) p -X-] q (CHR) r -, X can be O, or X can be S.

[0138] The moiety of formula (2) and the prepolymers of formulas (2a) and (2b) 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.

[0139] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CHR)p -X-] q (CHR) r -, and each R can be hydrogen, or at least one R can be methyl.

[0140] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CH 2 ) p -X-] q (CH 2 ) r -, where each X may be independently selected from O and S.

[0141] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CH 2 ) p -X-] q (CH 2 ) r -, where each X can be O or each X can be S.

[0142] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), R 1 -[(CH 2 ) p -X-] q (CH 2 ) 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.

[0143] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), each R 1 can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2-(ethane-1,2-diylbis(sulfanyl))bis(ethane-1-thiol)), or each R 1can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis(ethane-1-thiol)) and combinations thereof.

[0144] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), 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.

[0145] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), 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.

[0146] In the moiety of formula (2) and the prepolymers of formulas (2a) and (2b), 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.

[0147] In the moiety of formula (2), and the prepolymers of formulas (2a) and (2b), each r can independently be an integer from 2 to 4, from 2 to 6, or from 2 to 8.

[0148] In the divinyl ether of formula (3), 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.

[0149] In the divinyl ether of formula (3), each R 2 are independently 2~10 n-Alkanediyl group, C 3~6 Branched alkanediyl groups, and -[(CH 2 ) p -X-] q (CH 2 ) r - groups.

[0150] In the divinyl ether of formula (3), each R 2 are independently selected from C, such as methanediyl, ethanediyl, n-propanediyl, or n-butanediyl. 2~10 It may be an n-alkanediyl group.

[0151] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p -X-] q (CH 2 ) r - group, where each X can be O or S.

[0152] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p -X-] q (CH 2 ) r - group.

[0153] In the divinyl ether of formula (3), each m can independently be an integer from 1 to 3. Each m can be the same and can be 1, 2, or 3.

[0154] In the divinyl ether of formula (3), each R 2 are independently 2~10 n-Alkanediyl group, C 3~6 Branched alkanediyl groups, and -[(CH 2 ) p -X-] q (CH 2 ) r - groups.

[0155] In the divinyl ether of formula (3), each R 2 are independently 2~10 It may be an n-alkanediyl group.

[0156] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p-X-] q (CH 2 ) r -group, and each X can be O or S.

[0157] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p -X-] q (CH 2 ) r - group, each X can be O or S, and each p can be independently 2, 3, 4, 5, and 6.

[0158] In the divinyl ether of formula (3), each p can be the same and can be 2, 3, 4, 5, or 6.

[0159] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p -X-] q (CH 2 ) r -group, each X can be O or S, and each q can independently be 1, 2, 3, 4, or 5.

[0160] In the divinyl ether of formula (3), each q can be the same and can be 1, 2, 3, 4, or 5.

[0161] In the divinyl ether of formula (3), each R 2 are independently -[(CH 2 ) p -X-] q (CH 2 ) 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.

[0162] In the divinyl ethers of formula (3), 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 (3), each r can independently be an integer from 2 to 4, from 2 to 6, or from 2 to 8.

[0163] Suitable divinyl ethers may 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.

[0164] The divinyl ether may include a sulfur-containing divinyl ether. Suitable sulfur-containing divinyl ethers are disclosed in PCT Publication No. 2018 / 085650.

[0165] In the moiety of formula (3), each A can be independently derived from a polyalkenyl polyfunctionalizing agent. The polyalkenyl polyfunctionalizing agent can have the structure of formula (4), where z can be 3, 4, 5, or 6.

[0166] In the polyalkenyl polyfunctionalizing agent of formula (4), each R 7 are 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 -OH, =O, C 1~4 Alkyl, and C 1~4 The one or more heteroatoms may be selected from O, S, and combinations thereof.

[0167] 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-( 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.

[0168] In the moiety of formula (2) and the prepolymer of formula (2a)-(2b), the molar ratio of the moiety derived from the divinyl ether to the moiety derived from the polyalkenyl polyfunctionalizing agent can be 0.9 mol % to 0.999 mol %, 0.95 mol % to 0.99 mol %, or 0.96 mol % to 0.99 mol %.

[0169] In the moiety of formula (2) and the prepolymer of formulas (2a)-(2b), each R 1 Ha-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 - each R 2 Ha-(CH 2 ) 2 -, and m can be an integer from 1 to 4.

[0170] In the moiety of formula (2) and the prepolymer of formula (2a)-(2b), R 2may be derived from a divinyl ether, such as diethylene glycol divinyl ether, a polyalkenyl polyfunctionalizing agent, such as triallyl cyanurate, or a combination thereof.

[0171] In the moiety of formula (2) and the prepolymer of formula (2a)-(2b), each A may be independently selected from the moiety of formula (3a) and the moiety of formula (4a): -(CH 2 ) 2 -O-(R 2 -O) m -(CH 2 ) 2 - (3a) B{-R 4 -(CH 2 ) 2 -} 2 {-R 4 -(CH 2 ) 2 -S-[-R 1 -SASR 1 -] n -SH} z-2 (4a) In the formula, m, R 1 , R 2 , R 4 , A, B, m, n, and z are as defined in Equation (2), Equation (3), and Equation (4).

[0172] In the moiety of formula (3) and the prepolymer of formula (2a)-(2b), Each R 1 Ha-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 - each R 2 Ha-(CH 2 ) 2 -, m can be an integer from 1 to 4, and the polyfunctionalizing agent B(-R 4 -CH=CH 2 ) z comprises triallyl cyanurate, where z is 3 and each R 4 -O-CH 2 -CH=CH2 It is.

[0173] Methods for synthesizing sulfur-containing polythioethers are disclosed in US Pat. No. 6,172,179.

[0174] The backbone of the thiol-terminated polythioether prepolymer can be modified to improve properties such as adhesion, tensile strength, elongation, UV resistance, hardness, and / or flexibility of sealants and coatings prepared using the polythioether prepolymer. 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. Backbone-modified polythioether prepolymers are disclosed in any one of 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 Publication No. WO 2018 / 085650 (sulfur-containing divinyl ether), and PCT Publication No. WO 2018 / 031532 (urethane-containing). Polythioether prepolymers include those described in U.S. Patent Application Publication Nos. 2017 / 0369737 and 2016 / 0090507.

[0175] Suitable thiol-terminated polythioether prepolymers are disclosed 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 (2), (2a), and (2b). 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.

[0176] Polysulfide The sulfur-containing prepolymer may include a polysulfide prepolymer or a combination of polysulfide prepolymers.

[0177] 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. Polysulfide prepolymers can have two or more than two sulfur-sulfur bonds. Suitable thiol-terminated polysulfide prepolymers are commercially available from AkzoNobel and Toray Industries, Inc. under the trade names Thioplast® and Thiokol-LP®, respectively.

[0178] Suitable polysulfide prepolymers are disclosed in U.S. Patent Nos. 4,623,711, 6,172,179, 6,509,418, 7,009,032, and 7,879,955.

[0179] Suitable thiol-terminated polysulfide prepolymers may 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, commercially available from AkzoNobel. Thioplast® G resins are liquid thiol-terminated polysulfide prepolymers that are blends of difunctional and trifunctional molecules, where the difunctional thiol-terminated polysulfide prepolymers may have the structure of formula (5) and the trifunctional thiol-terminated polysulfide polymers may have the structure of formula (6): HS-(-R 5 -SS-) d -R 5 -SH (5) HS-(-R 5 -SS-) a -CH 2 -CH 2 -(-SSR 5 -) b -SH}{-(-SSR 5 -) c -SH} (6) In the formula, each R 5 Ha-(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 - and d=a+b+c, where the value of d can be 7-38 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%, and a crosslink density of 0% to 2.0%.

[0180] The polysulfide prepolymer may further comprise a terminal-modified polysulfide prepolymer having a structure of formula (5a), a terminal-modified polysulfide prepolymer having a structure of formula (6a), or a combination thereof, R 3 -S-(-R 5 -SS-) d -R 5 -SR 3 (5a) R 3 -S-(-R 5 -SS-) a -CH 2 -CH 2 -(-SSR 5 -) b -S-}{-(-SSR 5 -) c -SR 3} (6a) In the formula, d, a, b, c, and R 5 is as defined for equations (6) and (7), and R 3 is the moiety that contains the terminal reactive group.

[0181] Suitable thiol-terminated polysulfide prepolymers may also include Thiokol® LP polysulfides available from Toray Industries, Inc., such as Thiokol® LP2, Thiokol® LP3, Thiokol™ LP12, Thiokol® LP23, Thiokol® LP33, and Thiokol® LP55. Thiokol® LP polysulfides have 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 may have a structure of formula (7) and the end-modified polysulfide prepolymer may have a structure of formula (7a): HS-[(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -SS-] e-(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -SH (7) R 3 -S-[(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -SS-] e -(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -SR 3 (7a) where e can be an integer between 8 and 80, such as a number average molecular weight between 1,000 Da and 7,500 Da, and each R 6 is a moiety that contains a terminal reactive functional group.

[0182] The thiol-terminated sulfur-containing prepolymer may include Thiokol-LP® polysulfide, Thioplast® G polysulfide, or a combination thereof.

[0183] 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; y may have an average value in the range of 1.0 to 1.5; Each R is independently selected from branched alkanediyl, branched arenediyl, and the structure -(CH 2 ) p -O-(CH 2 ) q -O-(CH 2 ) 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; Each R 3 is a moiety that contains a terminal reactive functional group.

[0184] 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 -(CH 2 ) p -O-(CH 2 ) q -O-(CH 2 ) r --It could be.

[0185] In the moiety of formula (7) and the prepolymer of formula (7a) to (7b), the branched alkanediyl or branched arenediyl is -R(-A) f -, where R is a hydrocarbon group, f is 1 or 2, and A is a branch point. A branched alkanediyl can have the structure -CH 2 (-CH(-CH 2 -)-)-.

[0186] Exemplary thiol-terminated polysulfide prepolymers of formula (7a) and (7b) are disclosed in U.S. Application Publication No. 2016 / 0152775, U.S. Pat. No. 9,079,833, and U.S. Pat. No. 9,663,619.

[0187] 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 in U.S. Patent No. 8,729,216 and U.S. Patent No. 8,541,513.

[0188] 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-CH 2 -OR 7 -S s -) g-1 -R 7 -O-CH 2 -OR 7 - (8) HS-(R 7 -O-CH 2 -ORS s -) g-1 -R 7 -O-CH 2 -OR 7 -SH (8a) R 3 -S-(R 7 -O-CH 2 -OR 7 -S s -) g-1 -R 7 -O-CH 2 -OR 7 -SR 3 (8b) In the formula, R 7 is C 2~4 alkanediyl, s is an integer of 1 to 8, g is an integer of 2 to 370, and each R 3 is independently a moiety that contains a terminal reactive functional group.

[0189] Moieties of formula (8) and prepolymers of formula (8a)-(8b) are disclosed in JP62-53354.

[0190] Sulfur-containing polyformal 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) v -R 8 -] h - (9) R 10 -R 8 -(S) p -R 8 -[OC(R 9 ) 2 -OR 8 -(S) v -R 8 -] h -R 10 (9a) R 3 -R 8 -(S) p -R 8 -[OC(R 9 ) 2 -OR 8 -(S) v -R 8 -] h -R 3 (9b) {R 10 -R 8 -(S) p -R 8 -[OC(R 9 ) 2 -OR 8 -(S) v -R 8 -] h -OC(R 9 ) 2 -O-} m Z (9c) {R3 -R 8 -(S) p -R 8 -[OC(R 9 ) 2 -OR 8 -(S) v -R 8 -] h -OC(R 9 ) 2 -O-} m Z (9d) wherein h can be an integer from 1 to 50; each v 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

[0191] Monosulfide The sulfur-containing prepolymer may include a monosulfide prepolymer or a combination of monosulfide prepolymers.

[0192] The monosulfide prepolymer may comprise 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) w -(R 12 -X) u -R 13 -] x -S- (10) HS-R 13 -[-S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -SH (10a) {HS-R 13 -[-S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-V'-} z B (10b) R 3 -SR 13 -[-S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -SR 3 (10c) {R 3 -SR 13 -[-S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-V'-} z B (10d) During the ceremony, Each R 11 are independently 2~10 Alkanediyl, e.g., C 2~6 Alkanediyl;C 2~10 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 6~8Cycloalkanediyl;C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 alkylarenediyl; Each R 12 are independently hydrogen, C 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 are independently hydrogen, C 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; w can be an integer from 1 to 5; u may be an integer from 0 to 5; x 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 are 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.

[0193] Methods for synthesizing thiol-terminated monosulfide containing moieties of formula (10) or prepolymers of formulas (10b)-(10c) are disclosed in US Pat. No. 7,875,666.

[0194] The monosulfide prepolymer may 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) w -C(R 15 ) 2 -(XR 14 ) q -] x -S- (11) H-[-S-(R 14 -X) w -C(R 15 ) 2 -(XR 14 ) u -] x -SH (11a) R 3 -[-S-(R 14 -X) w -C(R 15 ) 2 -(XR 14 ) u -] x -SR 3 (11b) {H-[-S-(R 14 -X) w -C(R 15 ) 2 -(XR 14 ) u -] x -S-V'-} zB (11c) {R 3 -[-S-(R 14 -X) w -C(R 15 ) 2 -(XR 14 ) u -] x -S-V'-} z B (11d) During the ceremony, Each R 14 are 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 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; w can be an integer from 1 to 5; u may be an integer from 1 to 5; x 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.

[0195] Methods for synthesizing the monosulfides of formulae (11)-(11d) are disclosed in US Pat. No. 8,466,220.

[0196] Coreactive Groups The coreactive composition may have a tack-free time of less than 8 hours, less than 6 hours, less than 4 hours, less than 2 hours, less than 1 hour, or less than 30 minutes at 25C / 50% relative humidity, where the tack-free time is determined in accordance with AS5127 / 1(5.8) (Aerospace Standard Test Methods for Aerospace Sealants).

[0197] Co-reactive compositions for forming linear sealing components exhibiting fast time to Shore 10A hardness can include co-reactive agents having fast cure chemistry, systems curable by actinic radiation, catalysts, and combinations of any of the foregoing.

[0198] The cured composition may 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.

[0199] Co-reactive compositions for forming linear sealing components that exhibit electrical conductivity, EMI / RFI shielding, and / or static dissipative properties may include a conductive filler or combination of conductive fillers.

[0200] Additives The coreactive composition may include one or more additives such as catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, fillers, colorants, photochromic agents, rheology modifiers, reactive diluents, cure activators and accelerators, corrosion inhibitors, fire retardants, UV stabilizers, rain erosion inhibitors, or any combination of the foregoing.

[0201] catalyst The coreactive composition may include a catalyst or combination of catalysts, where one or more catalysts are selected to catalyze a reaction between co-reactants in the coreactive composition, such as a first co-reactive compound and a second co-reactive compound.

[0202] 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 compound with a second compound. Suitable catalysts can include amine catalysts, depending on the curing chemistry, such as thiol-ene or thiol-epoxy.

[0203] The coreactive composition may comprise 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.

[0204] 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 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.

[0205] 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.

[0206] Dark cure catalysts include combinations of metal complexes and organic peroxides, trialkylborane complexes and peroxide-amine redox initiators. Dark cure catalysts can be used in conjunction with a photoinitiator or independently of a photoinitiator.

[0207] Curing Activator Coreactive compositions based on thiol / thiol curing chemistry can include a cure activator or combination of cure activators to initiate the thiol / thiol polymerization reaction. The cure activators can be used in coreactive compositions where both the first compound and the second compound include a thiol-terminated sulfur-containing prepolymer, such as a thiol-terminated polysulfide prepolymer.

[0208] The cure activator may include an oxidizing agent capable of oxidizing terminal mercaptan groups to form disulfide bonds. Suitable oxidizing agents may include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, and dichromates.

[0209] The cure activator may include an inorganic activator, an organic activator, or a combination thereof.

[0210] Suitable inorganic activators may include metal oxides. Suitable metal oxide activators include zinc oxide (ZnO), lead oxide (PbO), lead peroxide (PbO 3 ), manganese dioxide (MnO 2 ), sodium perborate (NaBO 3 H 2 O), potassium permanganate (KMnO 4 ), calcium peroxide (CaCO 3 ), barium peroxide (BaO 3), cumene hydroperoxide, and combinations of any of the foregoing. Cure activators include MnO 2 It could be.

[0211] The coreactive composition based on the thiol / thiol curing chemistry may comprise 1 wt% to 10 wt% of the curing activator or combination of curing activators, where the wt% is based on the total weight of the composition. The coreactive composition may comprise 1 wt% to 9 wt%, 2 wt% to 8 wt%, 3 wt% to 7 wt%, or 4 wt% to 6 wt% of the activator or combination of curing activators, where the wt% is based on the total weight of the composition. 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 the curing activator or combination of curing activators, where the wt% is based on the total weight of the composition.

[0212] Co-reactive compositions based on thiol / thiol curing chemistry can include a cure accelerator or a combination of cure accelerators.

[0213] The cure accelerator can act as a sulfur donor and generate active sulfur fragments that can react with the terminal thiol groups of the thiol-terminated polysulfide prepolymer.

[0214] Suitable cure accelerators may include thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldehyde amines, and combinations of any of the foregoing.

[0215] The cure accelerator may be a thiuram polysulfide, a thiuram disulfide, or a combination thereof.

[0216] Other suitable 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. Non-sulfur-containing cure accelerators include tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water, and base.

[0217] The coreactive composition may comprise 0.01 wt% to 2 wt% of the cure accelerator or combination of cure accelerators, 0.05 wt% to 1.8 wt%, 0.1 wt% to 1.6 wt%, or 0.5 wt% to 1.5 wt% of the cure accelerator or combination of cure accelerators, where the weight percentages are based on the total weight of the composition. The coreactive composition may comprise less than 2 wt%, less than 1.8 wt%, less than 1.6 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or less than 0.05 wt% of the cure accelerator or combination of cure accelerators, where the weight percentages are based on the total weight of the composition.

[0218] Adhesion promoter The coreactive composition may include an adhesion promoter or combination of adhesion promoters. The adhesion promoter may enhance adhesion of the coreactive composition 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 cabin panels.

[0219] The adhesion promoter may include a phenolic adhesion promoter, a combination of phenolic adhesion promoters, an organofunctional silane, a combination of organofunctional silanes, or a combination of any of the foregoing. The organofunctional alkoxysilane may be an amine-functional alkoxysilane. The organo group may be selected from a thiol group, an amine group, a hydroxyl group, a silanol group, an epoxy group, an alkynyl group, an alkenyl group, an isocyanate group, or a Michael acceptor group.

[0220] The phenolic adhesion promoter may include heat treated phenolic resins, unheat treated phenolic resins, or combinations thereof. Suitable adhesion promoters may 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 monomers, oligomers, and / or prepolymers.

[0221] 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.

[0222] Suitable phenolic resins may 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 combinations of any of the foregoing. Suitable phenolic resins may be synthesized by base-catalyzed reaction of phenol with formaldehyde. Phenolic adhesion promoters may include the 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. Methylon® resins may include Methylon® 75108 (allyl ether of methylol phenol, see U.S. Pat. No. 3,517,082) and Methylon® 75202. Varcum® resins can 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. The S Durez® resin can be Durez® 34071.

[0223] 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 have the structure R a -(CH 2 ) n -Si(-OR) 3-n R n and R a is an organofunctional group, n is 0, 1, or 2, and R is an alkyl, such as methyl or ethyl. The organofunctional group may include an epoxy, amino, methacryloxy, or sulfide group. The organofunctional alkoxysilane may be a dipodal alkoxysilane having two or more than two alkoxysilane groups, a functional dipodal alkoxysilane, a non-functional dipodal alkoxysilane, or a combination of any of the foregoing. The organofunctional alkoxysilane may be a combination of a monoalkoxysilane and a dipodal alkoxysilane.

[0224] Suitable amino-functional alkoxysilanes under the Silquest® trade name include Silquest® A-1100 (γ-aminopropyltriethoxysilane), Silquest® A-1108 (γ-aminopropylsilsesquioxane), Silquest® A-1110 (γ-aminopropyltrimethoxysilane), Silquest® 1120 (N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane), Silquest® 1128 (benzylaminosilane), Silquest® 1130 (β-aminopropyltrimethoxysilane), Silquest® 1132 (β-aminopropyltrimethoxysilane), Silquest® 1134 (β-aminopropyltrimethoxysilane), Silquest® 1136 (β-aminopropyltrimethoxysilane), Silquest® 1138 ... Examples of suitable amine-functional alkoxysilanes include Silquest® A-1130 (triamino-functional silane), Silquest® Y-11699 (bis(γ-triethoxysilylpropyl)amine), Silquest® A-1170 (bis(γ-trimethoxysilylpropyl)amine), Silquest® A-1387 (polyazamide), Silquest® Y-19139 (ethoxy-based polyazamide), and Silquest® A-2120 (N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane). Suitable amine-functional alkoxysilanes are commercially available from Gelest Inc., Dow Corning Corporation, and Momentive Performance Materials, Inc.

[0225] filling material The coreactive composition may include a filler or a combination of fillers. The fillers may include inorganic fillers, organic fillers, low density fillers, conductive fillers, or a combination of any of the foregoing.

[0226] The co-reactive composition for forming the linear sealing component may include an inorganic filler or a combination of inorganic fillers.

[0227] Inorganic fillers may be included to provide mechanical reinforcement and to control the rheological properties of the composition, such as viscosity. Inorganic fillers may be added to the composition to impart desired physical properties, such as to increase impact strength, control viscosity, and / or modify the electrical properties of the cured composition.

[0228] Inorganic fillers useful in the coreactive 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.

[0229] Suitable calcium carbonate fillers 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.

[0230] 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 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.

[0231] The coreactive composition may include an organic filler or a combination of organic fillers.

[0232] 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 sealant 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.

[0233] The organic filler may have 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, etc. The organic filler may have a specific gravity in the range of 0.85-1.15, in the range of 0.9-1.1, in the range of 0.9-1.05, or in the range of 0.85-1.05, etc.

[0234] The organic filler may include thermoplastics, thermosets, or combinations thereof.Suitable thermoplastics and thermosets may include epoxy, epoxy-amide, ETFE copolymer, nylon, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylidene chloride, polyvinyl fluoride, TFE, polyamide, polyimide, ethylene propylene, perfluorohydrocarbons, fluoroethylene, polycarbonate, polyetheretherketone, polyetherketone, polyphenylene oxide, polyphenylene sulfide, polystyrene, polyvinyl chloride, melamine, polyester, phenolics, epichlorohydrin, fluorinated hydrocarbons, polycyclics, polybutadiene, polychloroprene, polyisoprene, polysulfide, polyurethane, isobutylene isoprene, silicone, styrene butadiene, liquid crystal polymer, or any combination of the foregoing.

[0235] Suitable polyamide 6 and polyamide 12 particles may be 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®.

[0236] The organic filler may have any suitable shape. The organic filler may comprise a fraction of ground polymer that has been filtered to select a desired size range. The organic filler may comprise substantially spherical particles. The particles may be solid or porous.

[0237] The organic filler may have an average particle size in the range of 1 μm to 100 μm, 2 μm to 40 μm, 2 μm to 30 μm, 4 μm to 25 μm, 4 μm to 20 μm, 2 μm to 12 μm, or 5 μm to 15 μm, etc. The organic filler may have an average particle size less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm, or less than 20 μm, etc. The particle size distribution may be determined by using a Fisher subsieve sizer or by optical inspection.

[0238] low density filler Co-reactive compositions for forming linear sealing components exhibiting low density may include low density fillers, such as low density organic fillers, hollow particulates, coated particulates, or combinations of any of the foregoing. Low density fillers may also be referred to as lightweight fillers.

[0239] The linear sealing component may 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, etc., where the specific gravity is determined according to ISO 2781 at 23° C. / 55% RH.

[0240] The organic filler may include low density, such as modified expanded thermoplastic microcapsules. Suitable modified expanded thermoplastic microcapsules may include an outer coating of melamine or urea / formaldehyde resin. The coreactive composition may include low density microcapsules. The low density microcapsules may include thermally expandable microcapsules.

[0241] 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.

[0242] Suitable materials for forming the walls of the thermally expandable microcapsules may 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 crosslinker may be included with the material that forms the walls of the thermally expandable microcapsules.

[0243] Suitable thermoplastic microcapsules may include Expancel™ microcapsules, such as Expancel® DE microparticles available from AkzoNobel. Suitable Expancel™ DE microparticles may include Expancel® 920DE40 and Expancel® 920DE80. Suitable low density microcapsules are also available from Kureha Corporation.

[0244] Low density fillers, such as low density microcapsules, can be characterized by a specific gravity in the range of 0.01-0.09, in the range of 0.04-0.09, in the range of 0.04-0.08, in the range of 0.01-0.07, in the range of 0.02-0.06, in the range of 0.03-0.05, in the range of 0.05-0.09, in the range of 0.06-0.09, or in the range of 0.07-0.09, the specific gravity being determined in accordance with ASTM D1475. Low density fillers, such as low density microcapsules, can 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, the specific gravity being determined in accordance with ASTM D1475.

[0245] Low density fillers, such as low density microcapsules, may be characterized by an average particle diameter of 1 μm to 100 μm and may have a substantially spherical shape. Low density fillers, such as low density microcapsules, may be characterized by an average particle size of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm, as determined according to ASTM D1475.

[0246] 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 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.

[0247] Depending on the coating of the aminoplast resin, the aminoplast coated microcapsules may be characterized by a specific gravity in the range of 0.02-0.08, in the range of 0.02-0.07, in the range of 0.02-0.06, in the range of 0.03-0.07, in the range of 0.03-0.065, in the range of 0.04-0.065, in the range of 0.045-0.06, or in the range of 0.05-0.06, the specific gravity being determined according to ASTM D1475.

[0248] The coreactive composition may include micronized polyethylene oxide homopolymer. The organic filler may include polyethylene, such as polyethylene oxide powder. Suitable polyethylenes may be available 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®.

[0249] The coreactive composition may comprise from 1 wt% to 90 wt% of the low density filler, from 1 wt% to 60 wt%, from 1 wt% to 40 wt%, from 1 wt% to 20 wt%, from 1 wt% to 10 wt%, or from 1 wt% to 5 wt% of the low density filler, the weight percentages being based on the total weight of the composition.

[0250] 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 1 wt.%, or greater than 10 wt.% low density filler, where the wt.% is based on the total weight of the composition.

[0251] 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.

[0252] The co-reactive composition can comprise greater than 0.5 vol.% low density filler, greater than 1 vol.%, 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.%, greater than 70 vol.%, or greater than 80 vol.% low density filler, where the vol.% is based on the total volume of the co-reactive composition.

[0253] Conductive Filler The coreactive composition may include a conductive filler or a combination of conductive fillers, which 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.

[0254] Suitable conductive fillers, such as conductive fillers, may include metals, metal alloys, conductive oxides, semiconductors, carbon, carbon fibers, and combinations of any of the foregoing.

[0255] Other conductive fillers may 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, silver-plated aluminum core particles or platinum-plated copper particles; precious metal-plated glass, plastic, or ceramics such as silver-plated glass particulates, precious metal-plated aluminum, or precious metal-plated plastic particulates; precious metal-plated mica; and other such precious metal conductive fillers. Non-precious metal-based materials may also be used, including non-precious metal-plated non-precious metals such as copper-coated iron particles or nickel-plated copper; non-precious metals, e.g., copper, aluminum, nickel, cobalt; non-precious metal-plated non-metals, e.g., nickel-plated graphite, and non-metallic materials such as carbon black and graphite. Combinations of conductive fillers and shapes of conductive fillers may be used to achieve the desired conductivity, EMI / RFI shielding effectiveness, hardness, and other properties suitable for a particular application.

[0256] The amount and type of conductive filler shall be 0.50 Ω / cm when cured. 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 coreactive composition.

[0257] Organic fillers, inorganic fillers, and low density fillers can be coated with metals to provide conductive fillers.

[0258] The conductive filler may include graphene, which is a nanotube with a thickness equal to the atomic size of one carbon atom, i.e., sp 2 It comprises a close-packed honeycomb crystal lattice made of carbon atoms with a single wall of hybridized carbon atoms.

[0259] The conductive fillers may include magnetic fillers or a combination of magnetic fillers.

[0260] The magnetic filler may include a soft magnetic metal. This can enhance 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. As the soft magnetic metal, the at least one magnetic material selected may be Fe, FeCo, FeNi, FeAl, and FeSi, and may be used as permalloy (FeNi alloy), super permalloy (FeNiMo alloy), sendust (FeSiAl alloy), FeSi alloy, FeCo alloy, FeCr alloy, FeCrSi alloy, FeNiCo alloy, and Fe, etc. Other magnetic fillers include iron-based powder, iron-nickel-based powder, iron powder, ferrite powder, alnico powder, Sm 2 Co 17 Powder, Nd-B-Fe powder, barium ferrite BaFe 2 O4 , bismuth ferrite BiFeO 3 , chromium dioxide CrO 2 , SmFeN, NdFeB, and SmCo.

[0261] Reactive Diluents The coreactive composition may include a hydroxyl-functional vinyl ether or a combination of hydroxyl-functional vinyl ethers. A reactive diluent may be used to reduce the viscosity of the composition. A reactive diluent is a low molecular weight compound, such as one with a molecular weight of less than 400 Da, that has at least one functional group that can react with at least one of the primary reactants of the composition and become part of a crosslinked network. The reactive diluent may have one or two functional groups. A reactive diluent may be used to control the viscosity of the composition or to improve the wetting of fillers in the coreactive composition.

[0262] The hydroxyl functional vinyl ether can have the formula (12): CH 2 =CH-O-(CH 2 ) t -OH (12) In the formula, t is an integer from 2 to 10. In the hydroxyl functional vinyl ether of formula (12), t can be 1, 2, 3, 4, 5, or t can be 6. Suitable hydroxyl functional vinyl ethers can 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.

[0263] The coreactive composition can comprise 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 curable composition.

[0264] The coreactive composition may include an amino-functional vinyl ether or a combination of amino-functional vinyl ethers as a reactive diluent.

[0265] The amino-functional vinyl ether can have the structure of formula (13): CH 2 =CH-O-(CH 2 ) w -NH 2 (13) In the formula, w is an integer from 2 to 10. In the amino-functional vinyl ether of formula (13), w can be 1, 2, 3, 4, 5, or t can be 6. Suitable amino-functional vinyl ethers can include 1-methyl-3-aminopropyl vinyl ether, 4-aminobutyl vinyl ether, and any combination of the foregoing. The amino-functional vinyl ether can be 4-aminobutyl vinyl ether as a reactive diluent. The coreactive composition may comprise 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.

[0266] The coreactive composition may include as reactive diluents vinyl diluents such as styrene, alpha-methylstyrene, and para-vinyltoluene; vinyl acetate; and / or n-vinylpyrrolidone.

[0267] Plasticizer The coreactive composition may contain a plasticizer or combination of plasticizers. Plasticizers may be included to adjust the viscosity of the composition and to facilitate application.

[0268] Suitable plasticizers may 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, epoxy esters of isooctyl thalate, benzophenones, and combinations of any of the foregoing.

[0269] The coreactive composition may comprise 0.5% to 7% by weight of the plasticizer or combination of plasticizers, 1% to 6% by weight, 2% to 5% by weight, or 2% to 4% by weight of the plasticizer or combination of plasticizers, where the weight percentages are based on the total weight of the coreactive composition.

[0270] The coreactive composition may include less than 8 wt. % plasticizer, less than 6 wt. %, less than 4 wt. %, or less than 2 wt. % plasticizer or combination of plasticizers, where the weight percentages are based on the total weight of the coreactive composition.

[0271] Photochromic Agent 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.

[0272] Corrosion Inhibitors The co-reactive compositions provided by the present disclosure may include a corrosion inhibitor or a combination of corrosion inhibitors.

[0273] Suitable corrosion inhibitors include zinc phosphate corrosion inhibitors, lithium orthosilicate (Li 4 SiO 4 ) and lithium metasilicate (Li 2 SiO 3 ), lithium silicate corrosion inhibitors such as 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 (zinc oxide (ZnO), magnesium oxide (MgO), cerium oxide (CeO 2 ), molybdenum oxide (MoO 3 ), and / or silicon dioxide (SiO 2 ), as well as combinations of any of the foregoing.

[0274] 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.

[0275] Fire retardant The coreactive composition may include a fire retardant or combination of fire retardants.

[0276] The fire retardant may include inorganic fire retardants, organic fire retardants, or combinations thereof.

[0277] Suitable inorganic fire retardants may 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.

[0278] Suitable organic fire 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. The fire retardants can be in solid (e.g., powder) or liquid form.

[0279] The coreactive composition may comprise from 1 wt% to 30 wt%, e.g., from 1 wt% to 20 wt% or from 1 wt% to 10 wt% of the flame retardant or combination of flame retardants based on the total weight of the coreactive composition. 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 the flame retardant or combination of flame retardants based on the total weight of the coreactive composition.

[0280] Moisture Control Additive The co-reactive composition may include a moisture control additive or a combination of moisture control additives.

[0281] Suitable moisture control additives may 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.

[0282] 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.

[0283] UV stabilizers 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. Suitable UV stabilizers may include Cyasorb® (Solvay), Uvinul® (BASF), and Tinuvin® (BASF) brand name products.

[0284] Additive Manufacturing of Linear Sealing Components FIG. 4 is a simplified diagram illustrating a method 400 for additively manufacturing a linear sealing component. The method 400 includes a process 402 of conveying a first co-reactive component and a second co-reactive component to a mixing chamber, a process 404 of mixing the first co-reactive component and the second co-reactive component to form a reactive mixture, a process 406 of depositing the reactive mixture layer by layer to form an elongated body, and a process 408 of curing the deposited reactive mixture via an actinic radiation source. Although the above content is illustrated using a selected group of processes for the method, there may be many alternatives, modifications, and variations. Some of the processes may be expanded and / or combined. Other processes may be inserted into those listed above. Some processes may be deleted or replaced. Depending on the embodiment, the order of the processes may be interchanged.

[0285] The process 402 of transporting the first and second co-reactive components to the mixing chamber may include transporting (e.g., pumping) the first co-reactive component from a first reservoir and transporting (e.g., pumping) the second co-reactive component from a second reservoir to the mixing chamber. The first co-reactive component may include a sulfur-containing prepolymer, which may include a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing. The first co-reactive component may include a thiol-terminated polythioether. The second co-reactive component includes a polyene prepolymer, which may be a polyvinyl ether. The first and / or second co-reactive components may further include flame-retardant filler particles, rheology-modifying filler particles (e.g., organic and / or inorganic), lightweight filler particles, and / or sound-damping filler particles.

[0286] The process 404 of mixing the first and second co-reactive components to form a reactive mixture may include actively (e.g., via a propeller) and / or passively (e.g., via static structures in the chamber) mixing the co-reactive components to form a homogenous reactive mixture. The reactive mixture may be partially cured in the mixing chamber prior to deposition to obtain desired rheological characteristics and / or self-supporting strength (e.g., to enable overhang printing and / or to prevent gravity-induced deformations such as sagging). In some circumstances, air bubbles may be removed from the reactive mixture prior to deposition such that printing defects that may result in acoustically weak points (e.g., acoustically leaky points) may be minimized.

[0287] The process 406 of depositing the reactive mixture layer by layer to form the elongated body may include directing the extrusion nozzle using a controller (e.g., in a computer) to apply pressure(s) to the mixing chamber (e.g., via pressurizing a reservoir connected thereto) to extrude the reactive mixture to form the elongated body of the linear sealing component.

[0288] The process 408 of curing the deposited reactive mixture via an actinic radiation source may include exposing the extruded reactive mixture from the elongated body and / or extrusion nozzle to actinic radiation (e.g., ultraviolet light) during and / or after deposition. The mixing chamber may be actinic radiation transparent so that actinic radiation can be applied while the reactive mixture is in the mixing chamber to partially cure the reactive mixture before deposition. The actinic radiation source may be spaced 20-30 inches, for example 23 inches, from the extrusion nozzle and / or mixing chamber. The actinic radiation source may be covered with a layer of polarizing film toward the direction of the extrusion nozzle. The actinic radiation source may have a luminance of 230 mW / cm. 2 The lamp may be a 395 nm UV lamp having a baseline intensity of 100 nm. Once the linear sealing components are printed, deposition may be stopped and a secondary curing step may be implemented, such as with the same 395 nm UV lamp in an aluminum foil lined chamber for at least 30 minutes. Upon curing, the elongated body may have a porous structure, such as a closed porous structure, within its walls.

[0289] The linear sealing components can be fabricated using co-reactive three-dimensional printing.

[0290] Co-reactive three-dimensional printing refers to a robotic manufacturing method in which a co-reactive composition is extruded through a nozzle and deposited using automated control. In co-reactive three-dimensional printing, a portion of the co-reactive composition can be pumped into a three-dimensional printing device and the curing reaction can be initiated by applying energy, such as by exposing the co-reactive composition to ultraviolet light. Alternatively, at least two co-reactive components can be combined and mixed to form a co-reactive composition, which can then be extruded through a nozzle and deposited. Upon mixing, the co-reactive compounds can react and initiate curing at temperatures below 30° C., such as 20° C. to 25° C., to form a thermoset polymer matrix. Alternatively, after mixing, the co-reactive compounds are initially unreactive when first combined and the reaction can be initiated by exposing the co-reactive composition to energy, such as ultraviolet light.

[0291] A three dimensional printing equipment for fabricating a part may include one or more pumps, one or more mixers, and one or more nozzles. One or more coreactive compositions can be pumped into one or more mixers and forced under pressure through one or more nozzles directed at a surface or previously applied layer.

[0292] The three dimensional printing equipment can include pressure control, extrusion dies, co-extrusion dies, coating applicators, temperature control elements, elements for applying energy to the co-reactive composition, or any combination of the foregoing.

[0293] The three dimensional printing facility may include a build device for moving the nozzle in three dimensions relative to the surface. The movement of the three dimensional printing device may be controlled by a processor.

[0294] A linear sealing component can be fabricated by depositing a coreactive composition comprising at least two coreactive components, followed by depositing additional portions or layers of the coreactive composition on the underlying deposited portion or layer and / or on adjacent already deposited portions or layers to form successive portions or layers of the article. The layers can be deposited successively on top of and / or adjacent to previously deposited layers to build an acoustically resistant portion. The coreactive composition can be mixed and then deposited, or the coreactive components can be deposited separately. If deposited separately, the coreactive components can be deposited simultaneously, successively, or both simultaneously and successively.

[0295] The coreactive composition can be deposited using any suitable coreactive three-dimensional printing device. The selection of a suitable coreactive three-dimensional printing device can depend on several factors, including the deposition volume, the viscosity of the coreactive composition, the deposition rate, the reaction rate of the coreactive compound, and the complexity and size of the chemically resistant part to be fabricated. Each of the two or more coreactive components can be introduced into an independent pump and injected into a mixer to combine and mix the two coreactive components to form the coreactive composition. A nozzle can be coupled to the mixer, and the mixed coreactive composition can be forced through or extruded through the nozzle under pressure.

[0296] The pump may be a positive displacement pump, a syringe pump, a piston pump, or a progressive cavity pump. The two pumps delivering the two co-reactive components may be arranged in parallel or in series. A suitable pump may be capable of pushing a liquid or viscous liquid through a nozzle orifice. This process may also be referred to as extrusion. The co-reactive components may also be introduced into the mixer using two pumps in series.

[0297] Two or more than two coreactive components may be deposited by dispensing the material through a disposable nozzle attached to a progressive cavity two-component system where the coreactive components are mixed in-line. The two-component system may include two progressive cavity pumps that separately dose the coreactive components to a disposable static mixer dispenser or dynamic mixer. Other suitable pumps include positive displacement pumps, syringe pumps, piston pumps, and progressive cavity pumps. After mixing to form the coreactive composition, the coreactive composition forms an extrudate as it is passed under pressure through one or more dies and / or one or nozzles to deposit on a base to provide an initial layer of a chemically resistant part, and successive layers may be deposited on and / or adjacent to a previously deposited layer. The deposition system may be positioned perpendicular to the base, but may also be set at any suitable angle to form an extrudate, such that the extrudate and deposition system form an obtuse angle with the extrudate parallel to the base. Extrudate refers to the coreactive composition after mixing the coreactive components in a static mixer or a dynamic mixer. The extrudate may be shaped as it passes through a die and / or nozzle.

[0298] The base, the deposition system, or both the base and the deposition system can be coupled to build a three-dimensional chemically resistant part. The movements can be performed in a predetermined manner, which can be accomplished using any suitable CAD / CAM methods and equipment, such as robotics and / or computerized machine tool interfaces.

[0299] The extrudate formed by extruding the coreactive composition through the nozzle of the three-dimensional printing device can be deposited in any orientation. The nozzle can be oriented downward, upward, sideways, or at any angle in between. In this manner, the coreactive composition can be deposited as a vertical wall or as an overhang. The extrudate can be deposited on a vertical wall, on the underside of a sloping wall, or on the bottom of a horizontal surface. The use of an 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.

[0300] The extrudate may be dispensed continuously or intermittently to form the initial and subsequent layers. For intermittent deposition, the deposition system may be interfaced with a switch to shut off a pump, such as a progressive cavity pump, thereby interrupting the flow of the coreactive composition.

[0301] The three-dimensional printing system may include an in-line static mixer and / or dynamic mixer, and a separate pressurized pumping section for holding at least two co-reactive components and feeding the co-reactive components to the static mixer and / or dynamic mixer. The mixer, such as an active mixer, may include a variable speed central impeller with a high shear blade in the nozzle. A range of nozzles may be used having minimum dimensions such as 0.2 mm to 100 mm, 0.5 mm to 75 mm, 1 mm to 50 mm, or 5 mm to 25 mm. The nozzles may have minimum dimensions such as greater than 1 mm, greater than 2 mm, greater than 5 mm, greater than 10 mm, greater than 20 mm, greater than 30 mm, greater than 40 mm, greater than 50 mm, greater than 60 mm, greater than 70 mm, greater than 80 mm, or greater than 90 mm. The nozzle may have a minimum dimension such as less than 100 mm, less than 90 mm, less than 80 mm, less than 70 mm, less than 60 mm, less than 50 mm, less than 40 mm, less than 30 mm, less than 20 mm, less than 10 mm, or less than 5 mm. The nozzle may have any suitable cross-sectional dimension such as circular, spherical, elliptical, rectangular, square, trapezoidal, triangular, planar, or other suitable shape. The aspect ratio or ratio of the orthogonal dimensions may be any suitable dimension suitable for fabricating a chemically resistant part such as 1:1, greater than 1:2, greater than 1:3, greater than 1:5, or greater than 1:10.

[0302] 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. The exit orifice diameters 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 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 co-reactive materials. The distribution section may be a straight tube having any of the preceding orifice diameters. The length of the distribution section may be configured to provide an area where the co-reactive components can begin to react and build viscosity before being deposited into the article. The length of the distribution section can be selected based on the deposition rate, the reaction rate of the co-reactant, and the viscosity of the co-reactant composition.

[0303] The coreactive composition may have a residence time in the static and / or dynamic mixing nozzle of 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 desired, based on the cure chemistry and cure rate.

[0304] Generally, a suitable residence time is less than the gel time of the coreactive composition.

[0305] The coreactive composition can have a volumetric flow rate of 0.1 mL / min to 20,000 mL / min, such as 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 volumetric flow rate can depend on the viscosity of the coreactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the coreactive compound.

[0306] The coreactive composition may be used at a deposition rate of 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 deposition rate may depend on the viscosity of the coreactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the coreactive compound. The deposition rate 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 being deposited.

[0307] The static and / or dynamic mixing nozzles can be heated or cooled to control the rate of reaction between the co-reactive compounds and / or the viscosity of the co-reactive components. 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 co-reactive compounds.

[0308] The rate at which the coreactive composition reacts to form the thermosetting polymer matrix can be determined and / or controlled by the selection of the reactive functional groups of the coreactive compound. The reaction rate can also be determined by factors that lower the activation energy of the reaction, such as heat and / or catalysts.

[0309] The reaction rate may be reflected in the gel time of the co-reactive composition. A fast curing chemical reaction refers to a chemical reaction in which the co-reactive compound has a gel time of less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds, etc. The co-reactive composition may have a gel time of 0.1 seconds to 5 minutes, 0.2 seconds to 3 minutes, 0.5 seconds to 2 minutes, 1 second to 1 minute, or 2 seconds to 40 seconds, etc. The gel time is the time when the co-reactive composition can no longer be stirred by hand after mixing the co-reactive components. The gel time of a latent co-reactive composition refers to the time from when the curing reaction is first initiated to when the co-reactive composition can no longer be stirred by hand.

[0310] Since the coreactive components can be combined and mixed uniformly, the coreactive composition can begin to cure immediately upon mixing, and the size of the coreactive composition and extrudate passed through the nozzle is not particularly limited. Thus, coreactive additive manufacturing facilitates the use of large size extrudates, thereby facilitating the ability to rapidly fabricate both small and large seal caps.

[0311] Using the coreactive three-dimensional printing method, the coreactive composition can be deposited at a speed of 1 mm / sec to 400 mm / sec and / or a flow rate of 0.1 mL / min to 20,000 mL / min.

[0312] Aspects of the invention The present disclosure may be further defined by one or more of the following aspects.

[0313] Aspect 1. An additively manufactured sealing component comprising an elongate body having a first crescent shaped recess and a second crescent shaped recess opposite the first crescent shaped recess, the first crescent shaped recess and the second crescent shaped recess opposite the first crescent shaped recess, the first crescent shaped recess and the second crescent shaped recess defining a centerline, a first volume on a first side of the centerline, a second volume on a second side of the centerline, and a third volume between the first crescent shaped recess and the second crescent shaped recess, such that the centerline passes through the third volume, the first crescent shaped recess having a first crescent shaped recess opening, a first tip of the first volume, a second tip of the second volume ... third volume between the first crescent shaped recess and the second crescent shaped recess, such that the centerline passes through the third volume, an additively manufactured sealing component, wherein the second crescent shaped recess is defined by a second tip of the first volume and a first wall of the third volume, the second crescent shaped recess is defined by a second crescent shaped recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume, and the elongated body comprises a thermosetting polymer formed by at least mixing at least a first co-reactive component and a second co-reactive component to form a co-reactive mixture, depositing the reactive mixture layer-by-layer to form the elongated body, and curing the deposited reactive mixture via an actinic radiation source.

[0314] Embodiment 2. The additively manufactured sealing component of embodiment 1, wherein the first crescent-shaped recess and the second crescent-shaped recess are each configured to receive a panel having a thickness 1 to 10 times the size of the recess opening of the crescent-shaped recess.

[0315] Embodiment 3. The additively manufactured sealing component of embodiment 1 or 2, wherein the first crescent-shaped recess and the second crescent-shaped recess extend the entire length of the elongated body.

[0316] Embodiment 4. An additively manufactured sealing component according to any one of embodiments 1-3, wherein a substantial portion of the elongated body has a uniform cross-sectional shape.

[0317] Embodiment 5. An additively manufactured sealing component according to any one of embodiments 1-4, wherein the elongated body has a porous structure.

[0318] Embodiment 6. The additively manufactured sealing component of any one of embodiments 1-5, wherein the first crescent-shaped recess and the second crescent-shaped recess are triangular.

[0319] Embodiment 7. The additively manufactured sealing component of any one of embodiments 1-6, wherein the first crescent shaped recess is configured such that upon receipt of a panel having a thickness greater than the first crescent shaped recess opening, the first tip, the second tip, and the first wall secure the panel via three-point contact, and the second crescent shaped recess is configured such that upon receipt of a panel having a thickness greater than the second crescent shaped recess opening, the third tip, the fourth tip, and the second wall secure the panel via three-point contact.

[0320] Embodiment 8. The additively manufactured sealing component of any one of embodiments 1-7, wherein the first crescent shaped recess is configured such that upon receipt of a panel having a thickness greater than the first crescent shaped recess opening, the first tip and the second tip elastically deform to widen the first crescent shaped recess opening, and the second crescent shaped recess is configured such that upon receipt of a panel having a thickness greater than the second crescent shaped recess opening, the third tip and the fourth tip elastically deform to widen the second crescent shaped recess opening.

[0321] Embodiment 9. The additively manufactured sealing component of any one of embodiments 1-8, wherein the third volume is compressible at least along the centerline such that when the third volume is compressed, the distance between the first crescent-shaped recess and the second crescent-shaped recess decreases.

[0322] Embodiment 10. An additively manufactured sealing component according to any one of embodiments 1-9, wherein the elongated body is configured to receive a first panel in the first crescent-shaped recess and a second panel in the second crescent-shaped recess, and a distance between the first crescent-shaped recess and the second crescent-shaped recess is variable by at least a minimum of twice the wall thickness of the sealing component.

[0323] Embodiment 11. The additively manufactured sealing component of any one of embodiments 1-10, wherein the first co-reactive component comprises a sulfur-containing prepolymer.

[0324] Example 12. The additively manufactured sealing component of example 11, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.

[0325] Example 13. The additively manufactured sealing component of example 12, wherein the polythioether is a thiol-terminated polythioether.

[0326] Embodiment 14. The additively manufactured sealing component of any one of embodiments 1-13, wherein the second co-reactive component comprises a polyene prepolymer.

[0327] Example 15. The additively manufactured sealing component of example 14, wherein the polyene prepolymer is a polyvinyl ether.

[0328] Example 16. The additively manufactured sealing component of any one of Examples 1-15, wherein at least one of the first co-reactive component and the second co-reactive component further comprises flame-retardant filler particles.

[0329] Example 17. The additively manufactured sealing component of any one of Examples 1-16, wherein at least one of the first co-reactive component and the second co-reactive component further comprises rheology modifying filler particles.

[0330] Example 18. The additively manufactured sealing component of example 17, wherein the rheology modifying filler particles comprise organic filler particles or inorganic filler particles.

[0331] Example 19. The additively manufactured sealing component of any one of Examples 1-18, wherein at least one of the first co-reactive component and the second co-reactive component further comprises lightweight filler particles.

[0332] Embodiment 20. The additively manufactured sealing component of any one of embodiments 1-19, wherein at least one of the first co-reactive component and the second co-reactive component further comprises sound-damping filler particles.

[0333] Embodiment 21. An aircraft component, comprising: a first panel; a second panel; and an elongated seal component having a first crescent shaped recess and a second crescent shaped recess opposite the first crescent shaped recess, the first crescent shaped recess and the second crescent shaped recess defining a centerline, the first crescent shaped recess being fixedly secured to the first panel and the second crescent shaped recess being fixedly secured to the second panel, the first crescent shaped recess and the second crescent shaped recess opposite the first crescent shaped recess, a first volume on a first side of the centerline, a second volume on a second side of the centerline, and a third volume between the first crescent shaped recess and the second crescent shaped recess, such that the centerline passes through the third volume, the first crescent shaped recess having a first crescent shaped recess opening, a first tip of the first volume, 13. An aircraft component comprising: a first volume having a first recess, a second tip of the second volume, and a first wall of the third volume; a second crescent shaped recess defined by a second crescent shaped recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume; and an elongated seal component comprising a thermoset polymer formed by: forming a reactive mixture by at least mixing at least a first co-reactive component and a second co-reactive component, wherein the first co-reactive component comprises a thiol-terminated polythioether and the second co-reactive component comprises a polyvinyl ether; depositing the reactive mixture layer-by-layer to form the elongated seal component; and curing the deposited reactive mixture via an actinic radiation source.

[0334] Aspect 22. The aircraft component of aspect 21, wherein the first crescent-shaped recess and the second crescent-shaped recess are each configured to receive a panel having a thickness 1 to 10 times the size of the recess opening of the crescent-shaped recess.

[0335] Embodiment 23. The aircraft component of embodiment 21 or 22, wherein the first crescent-shaped recess and the second crescent-shaped recess extend the entire length of the elongated body.

[0336] Embodiment 24. The aircraft component of any one of embodiments 21-23, wherein a substantial portion of the elongated body has a uniform cross-sectional shape.

[0337] Embodiment 25. The aircraft component of any one of embodiments 21 to 24, wherein the elongated body has a porous structure.

[0338] Embodiment 26. The aircraft of any one of embodiments 21 to 25, wherein the first crescent-shaped recess and the second crescent-shaped recess are triangular.

[0339] Aspect 27. An aircraft as described in any one of aspects 21 to 26, wherein the first recess is configured such that, upon receipt of a panel having a thickness greater than the first crescent recess opening, the first tip, the second tip, and the first wall secure the panel via three-point contact, and the second crescent recess is configured such that, upon receipt of a panel having a thickness greater than the second crescent recess opening, the third tip, the fourth tip, and the second wall secure the panel via three-point contact.

[0340] Aspect 28. An aircraft as described in any one of aspects 21 to 27, wherein the first recess is configured such that, upon receipt of a panel having a thickness greater than the first crescent-shaped recess opening, the first tip and the second tip elastically deform to widen the first crescent-shaped recess opening, and the second crescent-shaped recess is configured such that, upon receipt of a panel having a thickness greater than the second crescent-shaped recess opening, the third tip and the fourth tip elastically deform to widen the second crescent-shaped recess opening.

[0341] Embodiment 29. The aircraft component of any one of embodiments 21 to 28, wherein the third volume is compressible at least along the centerline such that when the third volume is compressed, a distance between the first crescent-shaped recess and the second crescent-shaped recess decreases.

[0342] Embodiment 30. The aircraft component of any one of embodiments 21-29, wherein a distance between the first crescent-shaped recess and the second crescent-shaped recess is at least a minimum of twice the wall thickness of the sealing component.

[0343] Embodiment 31 The aircraft component of any one of embodiments 21-30, wherein the first coreactive component comprises a sulfur-containing prepolymer.

[0344] Example 32. The aircraft component of example 31, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.

[0345] Embodiment 33. The aircraft component according to embodiment 32, wherein the polythioether is a thiol-terminated polythioether.

[0346] Example 34. The aircraft component of any one of Examples 21-33, wherein the second coreactive component comprises a polyene prepolymer.

[0347] Aspect 35. The aircraft component of aspect 34, wherein the polyene prepolymer is a polyvinyl ether.

[0348] Example 36 The aircraft component of any one of Examples 21 to 35, wherein at least one of the first and second co-reactive components further comprises flame-retardant filler particles.

[0349] Example 37. The aircraft component of any one of Examples 21 to 36, wherein at least one of the first and second co-reactive components further comprises rheology modifying filler particles.

[0350] Example 38. The aircraft component of Example 37, wherein the rheology modifying filler particles comprise organic filler particles or inorganic filler particles.

[0351] Example 39. The aircraft component of any one of Examples 21-38, wherein at least one of the first co-reactive component and the second co-reactive component further comprises lightweight filler particles.

[0352] Embodiment 40. The aircraft component of any one of embodiments 21 to 39, wherein at least one of the first co-reactive component and the second co-reactive component further comprises sound-damping filler particles.

[0353] Embodiment 41. A method of additively manufacturing a sealing component, comprising: delivering a first co-reactive component and a second co-reactive component to a mixing chamber, wherein the first co-reactive component comprises a thiol-terminated polythioether and the second co-reactive component comprises a polyvinyl ether; mixing the first co-reactive component and the second co-reactive component to form a reactive mixture; depositing the reactive mixture layer-by-layer to form an elongated body; and curing the deposited reactive mixture via an actinic radiation source, wherein the elongated body has a first crescent-shaped recess and a second crescent-shaped recess opposite the first crescent-shaped recess. 13. A method of forming a mold recess comprising: a first crescent shaped recess defining a centerline; a second crescent shaped recess opposite the first crescent shaped recess; a first volume on a first side of the centerline; a second volume on a second side of the centerline; and a third volume between the first crescent shaped recess and the second crescent shaped recess, such that the centerline passes through the third volume; the first crescent shaped recess is bounded by a first crescent shaped recess opening, a first tip of the first volume, a second tip of the second volume, and a first wall of the third volume; and the second crescent shaped recess is bounded by a second crescent shaped recess opening, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume.

[0354] Aspect 42. The method of aspect 41, wherein the first crescent-shaped recess and the second crescent-shaped recess are each configured to receive a panel having a thickness 1 to 10 times the size of the recess opening of the crescent-shaped recess.

[0355] Embodiment 43. The method of embodiment 41 or 42, wherein the first crescent-shaped recess and the second crescent-shaped recess extend the entire length of the elongate body.

[0356] Embodiment 44. The method of any one of embodiments 41 to 43, wherein a substantial portion of the elongate body has a uniform cross-sectional shape.

[0357] Embodiment 45. The method of any one of embodiments 41 to 44, wherein the elongate body has a porous structure.

[0358] Embodiment 46. The method of any one of embodiments 41 to 45, wherein the first crescent-shaped recess and the second crescent-shaped recess are triangular.

[0359] Embodiment 47. The method of any one of embodiments 41 to 46, wherein the first recess is configured such that, upon receipt of a panel having a thickness greater than the first crescent recess opening, the first tip, the second tip, and the first wall secure the panel via three-point contact, and the second crescent recess is configured such that, upon receipt of a panel having a thickness greater than the second crescent recess opening, the third tip, the fourth tip, and the second wall secure the panel via three-point contact.

[0360] Aspect 48. The method of any one of aspects 41 to 47, wherein the first recess is configured such that, upon receipt of a panel having a thickness greater than the first crescent-shaped recess opening, the first tip and the second tip elastically deform to widen the first crescent-shaped recess opening, and the second crescent-shaped recess is configured such that, upon receipt of a panel having a thickness greater than the second crescent-shaped recess opening, the third tip and the fourth tip elastically deform to widen the second crescent-shaped recess opening.

[0361] Embodiment 49. The method of any one of embodiments 41 to 48, wherein the third volume is compressible at least along the centerline such that when the third volume is compressed, the distance between the first crescent-shaped recess and the second crescent-shaped recess decreases.

[0362] Embodiment 50. The method of any one of embodiments 41 to 49, wherein the elongated body is configured to receive a first panel in the first crescent-shaped recess and a second panel in the second crescent-shaped recess, and a distance between the first crescent-shaped recess and the second crescent-shaped recess is variable from at least a minimum of twice the wall thickness of the sealing component.

[0363] Embodiment 51 The method of any one of embodiments 41-50, wherein the first coreactive component comprises a sulfur-containing prepolymer.

[0364] Embodiment 52. The method of embodiment 51, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.

[0365] Embodiment 53. The method of embodiment 52, wherein the polythioether is a thiol-terminated polythioether.

[0366] Embodiment 54 The method of any one of embodiments 41 to 53, wherein the second coreactive component comprises a polyene prepolymer.

[0367] Aspect 55. The method of aspect 54, wherein the polyene prepolymer is a polyvinyl ether.

[0368] Embodiment 56 The method of any one of embodiments 41 to 55, wherein at least one of the first co-reactive component and the second co-reactive component further comprises flame-retardant filler particles.

[0369] Embodiment 57. The method of any one of embodiments 41 to 56, wherein at least one of the first co-reactive component and the second co-reactive component further comprises rheology modifying filler particles.

[0370] Embodiment 58. The method of embodiment 57, wherein the rheology modifying filler particles comprise organic filler particles or inorganic filler particles.

[0371] Embodiment 59 The method of any one of embodiments 41-58, wherein at least one of the first co-reactive component and the second co-reactive component further comprises lightweight filler particles.

[0372] Embodiment 60. The method of any one of embodiments 41 to 59, wherein at least one of the first co-reactive component and the second co-reactive component further comprises sound attenuating filler particles.

[0373] Aspect 61. A composition of matter comprising: a first co-reactive component comprising a sulfur-containing prepolymer; a second co-reactive component comprising a polyene prepolymer, the second co-reactive component being reactive to the first co-reactive component upon mixing and exposure to a source of actinic radiation; and flame retardant filler particles dispersed in the composition of matter.

[0374] Embodiment 62. The composition of embodiment 61, when cast at a thickness of 0.125 inches and cured, has a tensile strength of 310-360 psi. EXAMPLES

[0375]

[0023] Embodiments provided by the present disclosure are further illustrated by reference to the following examples that describe additively manufactured linear sealing components, methods of additively manufacturing linear sealing components, and co-reactive compositions for additively manufacturing linear sealing components. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be implemented without departing from the scope of the present disclosure.

[0376] Example 1 UV-cured polythioether linear sealing components The linear sealing component was 3D printed using an actinic radiation curable thiol-ene based resin formulation. Specifically, the linear sealing component according to Example 1 was manufactured using the formulation described in Example 5 and has the same structural design as the linear sealing component 200 in FIG. 2A.

[0377] The thiol-ene formulations contained a mixture of thiol- and alkenyl-terminated resins, rheology modifiers and fillers, and photoinitiators. The formulations were stored in UV-opaque tubes at -40°C and thawed to 23°C before use. The thiol-ene formulations were 3D printed using a custom-built 3D printer consisting of a LulzBot Taz 3D printing gantry and a ViscoTec preeflow® Eco-DUO dual extruder with integrated print bed. A UV source (UltraFire® WF-501B UV LED flashlight with a nominal peak wavelength of 395 nm) was attached to the ViscoTec extruder and aimed from the extruder to the point of application at a distance of 23 inches from the extruder.

[0378] The thiol and alkenyl components were loaded into opaque Nordson cartridges and connected to a ViscoTec extruder using polytetrafluoroethylene tubing wrapped in aluminum foil to prevent the transmission of ambient light. The loaded cartridges were pressurized under nitrogen at 80 psi (0.551 N / mm 2 ) and printed using custom written G-code that simultaneously directed the print head and print bed while switching the flow of the co-reactive composition formed by mixing the thiol and alkenyl components through a ViscoTec extruder.

[0379] After extrusion began, the UV LED light was switched on. The liquid thiol-ene formulation was extruded onto the print bed through a static mix nozzle with an inner diameter of 0.6 mm. The linear sealing components were printed using a print head speed of 120 mm / sec and a flow rate of 1.2 mL / min. Under these conditions, the extruded coreactive composition cured within 5 seconds after exiting the extruder.

[0380] Example 2 Acoustic Testing FIG. 5 illustrates an acoustic test apparatus 500 used to perform sound attenuation performance testing on linear sealing components. As shown, the acoustic test apparatus 500 includes a sound chamber 502 having a first panel 504 and a second panel 506 on a first side of the sound chamber. The first panel 504 and the second panel are configured to be adjusted to form a panel gap of various gap sizes therebetween. The gap size can be adjusted by turning an adjustment knob 516 coupled to a linear slide 510. Specifically, the first panel 504 can be coupled to the linear slide 510 via a first slider 512 to which the first panel is coupled. The second panel 506 can be coupled to the linear slide 510 via a second slider 514 to which the second panel is coupled. The sound chamber 502 further has a sound source opening 518 and a microphone opening 520. The sound source opening 518 may allow a sound source (e.g., a speaker) to be positioned at the sound source opening to deliver sound into the sound chamber 502. The microphone opening 520 may allow a microphone to be positioned inside the sound chamber 502 to measure the sound pressure level(s) inside the sound chamber. A sound intensity probe is then placed outside the sound chamber near the panel gap.

[0381] The chamber including the adjustable panel is assembled with aluminum panels so that the panel gap simulates a noise leakage area such as an aircraft cabin environment, and acoustic insertion loss performance can be measured by inserting a linear sealing component into the panel gap. To perform the acoustic attenuation test, the linear sealing component is installed between the panels, a sound source is activated to deliver sound pressure into the acoustic chamber, and then a first microphone makes a first measurement(s) corresponding to the sound level inside the chamber while a sound intensity probe makes a second measurement(s) corresponding to the sound level outside the chamber. The test conditions for Example 2 include an 18" x 12" x 12" sound chamber with an adjustable gap of 1 / 8" between two 1 / 8" aluminum panels. The sound source was set to generate noise up to 25.6 kHz at random and constant levels. The sound intensity probe was centrally positioned next to the linear sealing component within the sound chamber. The sound intensity probe was centrally positioned next to the linear sealing component on the outside of the sound chamber, approximately 2" away from the panel gap. The sound intensity probe may include two microphones configured to detect measured pressure levels at frequencies between 50 Hz and 12.5 kHz (1 / 3 octave band). The sound intensity probe may be measured at an average of 16 seconds per point. The sound test environment was at room temperature and in an anechoic chamber.

[0382] Example 3 Sound Pressure Level Frequency Spectrum 6 shows the sound pressure level frequency spectrum from 50 Hz to 12.5 kHz, 1 / 3 octave band, for the open gap configuration and for the gap sealed with the linear sealing component according to Example 1. As shown, a high insertion loss, which can be determined by calculating the difference between the sound pressure levels measured in the open gap configuration and the sealed gap configuration, was observed for the linear sealing component of Example 1 across the frequency spectrum.

[0383] Example 4 Overall Sound Pressure Level with and without Sealer FIG. 7 shows a comparative histogram showing the reduction in overall sound pressure level with and without a sealer. The sound pressure level from the source reference was measured by a microphone in the sound chamber. As shown, the overall sound pressure level outside the sound chamber with a 1 / 8 inch wide open gap was 90.6 dB(A). After installing a typical foam sealer, the overall sound pressure level outside the sound chamber is reduced to 79.7 dB(A). When the linear sealing components described in Example 1 are installed, the overall sound pressure level outside the sound chamber is reduced to 75.1 dB(A).

[0384] UV-curable polythioether chemistry An actinic radiation-curable thiol-ene based coreactive composition was prepared by combining the first component (ie, Part A) and the second component (ie, Part B).

[0385] The thiol-ene based coreactive composition can be at least partially cured under ambient conditions without actinic radiation, which can help the extruded composition to withstand its weight during layer-by-layer extrusion and / or subsequent actinic radiation. Such multi-cure properties of the thiol-ene based coreactive composition can help achieve covalent bonding throughout the 3D printed part.

[0386] The thiol-ene formulations contained a mixture of thiol- and alkenyl-terminated resins, rheology modifiers and fillers, and photoinitiators. [Table 1]

[0387] The thiol-ene formulation of Example 5 was made with a mix ratio of Part B to Part A of 100 to 8.37. [Table 2]

[0388] The thiol-ene formulation of Example 6 was made with a mix ratio of Part B to Part A of 100 to 8.05. [Table 3]

[0389] The thiol-ene formulation of Example 7 was made with a mix ratio of Part B to Part A of 100 to 8.05. [Table 4]

[0390] The thiol-ene formulation of Example 8 was made with a mix ratio of Part B to Part A of 100 to 7.57. [Table 5]

[0391] The thiol-ene formulation of Example 9 was made with a mix ratio of Part B to Part A of 100 to 7.57.

[0392] Example 10 Rheological Properties of Uncured Coreactive Compositions from Examples 5-9 The uncured sealant formulations were measured using a 25 mm parallel plate geometry at room temperature without light exposure. Viscosity was measured from shear rates of 0.1 1 / s to 200 1 / s. Viscosity recovery was measured by holding the shear rate at 0.1 1 / s for 200 seconds.

[0393] FIG. 8A shows the viscosity of the uncured coreactive compositions from Examples 5-9 over a range of shear rates.

[0394] FIG. 8B shows the post-shear viscosity of the uncured coreactive compositions from Examples 5-9 over time.

[0395] Example 11 Table 6 Physical Properties of Coreactive Compositions from Examples 5-9 The sealant formulation was applied to the substrate at a thickness of 0.125 in. (3.175 mm). The sealant was exposed to 1 J / cm2 to 2 J / cm2 of UVA radiation. Shore A hardness was measured using a Type A durometer according to ASTM D220. Tensile strength and elongation were measured according to ASTM D412 Die C. Depth of cure was measured by applying the sealant formulation in a 0.4 in. deep groove. Depth of cure is obtained by determining the depth to which the sample was fully cured after exposure. [Table 6] [Table 7]

[0396] Data sets marked with an asterisk include samples with a value of zero, indicating a self-extinguishing condition. Results obtained in accordance with CFR14 §25.853(a) Appendix F Part I(a)1(iv) specification. Average burn rate not to exceed 2.5 in / min.

[0397] Example 13 Linear Sealing Component Dimensions 9 is a diagram illustrating dimensions of a linear sealing component according to various embodiments of the present disclosure. It should be understood that the linear sealing components of the present disclosure may be scaled to fit between panels of different thicknesses and panel gaps of different sizes. In one particular example, the relationships between panel thickness (t), gap size (w), component wall thickness (z), recess opening size (x), recess depth (y), and recess inner wall width (v) may be described by one or more of equations (14), (15), (16), (17): y=4x (14) v=10x (15) 2z≦w (16) x≦t≦v (17) In various examples, each crescent recess of the linear sealing component of the present disclosure may form two wing recesses when the corresponding crescent recess is bonded to a panel. The dimensions of the wing recesses may be described by one or more of equations (18), (19), (20): a=5x-(t / 2) (18) c 2 =(4x) 2 +(4.5x) 2 (19) b 2 =c 2 -(5x-(t / 2)) 2 (20)

[0398] 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

1. 1. An additively manufactured sealing component, comprising: a first recess and a second recess opposite the first recess, the first recess and the second recess defining a centerline; a first volume on a first side of the centerline; a second volume on a second side of the centerline; and an elongate body having a third volume between the first recess and the second recess, the centerline passing through the third volume; the first recess is bounded by a first recess opening, a first apex of the first volume, a second apex of the second volume, and a first wall of the third volume; the second recess is bounded by a second recess opening, a third apex of the first volume, a fourth apex of the second volume, and a second wall of the third volume; The elongated body comprises: forming a co-reactive mixture by at least mixing at least a first co-reactive component and a second co-reactive component; depositing the reactive mixture layer-by-layer to form the elongated body; and curing the deposited reactive mixture via an actinic radiation source to form a thermoset polymer.

2. 2. The additively manufactured sealing component of claim 1 , wherein the first recess and the second recess are each configured to receive a panel having a thickness between 1 and 10 times a size of the recess opening of the recess.

3. 3. The additively manufactured sealing component of claim 1 or 2, wherein the first recess and the second recess extend an entire length of the elongate body.

4. 4. The additively manufactured sealing component of any one of claims 1 to 3, wherein a substantial portion of the elongate body has a uniform cross-sectional shape.

5. The additively manufactured sealing component of any one of claims 1 to 4, wherein the elongate body has a porous structure.

6. 6. The additively manufactured sealing component of any one of claims 1 to 5, wherein the first recess and the second recess are triangular.

7. the first recess is configured such that upon receipt of a panel having a thickness greater than the first recess opening, the first apex, the second apex, and the first wall secure the panel via three-point contact; 7. The additively manufactured sealing component of any one of claims 1 to 6, wherein the second recess is configured such that upon receipt of a panel having a thickness greater than the second recess opening, the third apex, the fourth apex and the second wall secure the panel via three-point contact.

8. the first recess is configured such that upon receipt of a panel having a thickness greater than the first recess opening, the first apex and the second apex elastically deform to widen the first recess opening; 8. The additively manufactured sealing component of any one of claims 1 to 7, wherein the second recess is configured such that upon receipt of a panel having a thickness greater than the second recess opening, the third apex and the fourth apex elastically deform to widen the second recess opening.

9. 9. The additively manufactured sealing component of any one of claims 1 to 8, wherein the third volume is compressible at least along the centre line such that when the third volume is compressed, a distance between the first recess and the second recess decreases.

10. The elongated body comprises: a first recess configured to receive a first panel and a second recess configured to receive a second panel; 10. The additively manufactured sealing component of any one of claims 1 to 9, wherein the distance between the first recess and the second recess is variable by at least a minimum of twice the wall thickness of the sealing component.

11. 11. The additively manufactured sealing component of any one of claims 1 to 10, wherein the first co-reactive component comprises a sulfur-containing prepolymer.

12. 12. The additively manufactured sealing component of claim 11, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.

13. 13. The additively manufactured sealing component of claim 12, wherein the polythioether is a thiol-terminated polythioether.

14. 14. The additively manufactured sealing component of any one of claims 1 to 13, wherein the second co-reactive component comprises a polyene prepolymer.

15. 15. The additively manufactured sealing component of claim 14, wherein the polyene prepolymer is a polyvinyl ether.

16. 16. The additively manufactured sealing component of any one of claims 1 to 15, wherein at least one of the first and second co-reactive components further comprises flame retardant filler particles.

17. 17. The additively manufactured sealing component of any one of claims 1 to 16, wherein at least one of the first and second co-reactive components further comprises rheology modifying filler particles.

18. 20. The additively manufactured sealing component of claim 17, wherein the rheology modifying filler particles comprise organic filler particles or inorganic filler particles.

19. 19. The additively manufactured sealing component of any one of claims 1 to 18, wherein at least one of the first co-reactive component and the second co-reactive component further comprises lightweight filler particles.

20. 20. The additively manufactured sealing component of any one of claims 1 to 19, wherein at least one of the first and second co-reactive components further comprises sound attenuating filler particles.

21. A first panel; A second panel; a first recess and a second recess opposite the first recess, the first recess and the second recess defining a centerline, the first recess being rigidly coupled to the first panel and the second recess being rigidly coupled to the second panel; a first volume on a first side of the centerline; a second volume on a second side of the centerline; and an elongated seal component having a third volume between the first recess and the second recess, the centerline passing through the third volume; the first recess is bounded by a first recess opening, a first apex of the first volume, a second apex of the second volume, and a first wall of the third volume; the second recess is bounded by a second recess opening, a third apex of the first volume, a fourth apex of the second volume, and a second wall of the third volume; The elongated seal component comprises: forming a reactive mixture by at least mixing at least a first co-reactive component and a second co-reactive component, the first co-reactive component comprising a thiol-terminated polythioether and the second co-reactive component comprising a polyvinyl ether; depositing the reactive mixture layer-by-layer to form the elongated seal component; and curing the deposited reactive mixture via a source of actinic radiation to form a thermoset polymer.

22. 1. A method for additively manufacturing a sealing component, comprising: conveying a first co-reactive component and a second co-reactive component to a mixing chamber, the first co-reactive component comprising a thiol-terminated polythioether and the second co-reactive component comprising a polyvinyl ether; mixing the first co-reactive component and the second co-reactive component to form a reactive mixture; depositing the reactive mixture layer-by-layer to form an elongated body; and curing the deposited reactive mixture via a source of actinic radiation; The elongated body comprises: a first recess and a second recess opposite the first recess, the first recess and the second recess defining a centerline; a first volume on a first side of the centerline; a second volume on a second side of the centerline; and a third volume between the first recess and the second recess, the centerline passing through the third volume; the first recess is bounded by a first recess opening, a first apex of the first volume, a second apex of the second volume, and a first wall of the third volume; the second recess is bounded by a second recess opening, a third apex of the first volume, a fourth apex of the second volume, and a second wall of the third volume.

23. 1. A composition of matter comprising: a first co-reactive component comprising a sulfur-containing prepolymer; a second co-reactive component comprising a polyene prepolymer, said second co-reactive component being reactive to said first co-reactive component upon mixing and exposure to a source of actinic radiation; and flame retardant filler particles dispersed in the composition of matter, When the composition was cast at a thickness of 0.125 inches and cured, A tensile strength between 310 and 360 psi, or The composition has an elongation of 420% to 480%.

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