Linear sealing component and method for additive manufacturing of linear sealing component
Additively manufactured sealing components with contoured recesses and volumes address the issue of ineffective acoustic attenuation in aircraft by enhancing sealing and acoustic performance across varying gap sizes.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- PPG INDUSTRIES OHIO INC
- Filing Date
- 2022-11-08
- Publication Date
- 2026-04-10
AI Technical Summary
Aircraft structural components often have slight mismatches leading to gaps that result in ineffective acoustic attenuation between the cabin and other areas, with current insulating methods like tapes and foams being inadequate due to poor sealer properties and varying gap sizes.
An additively manufactured sealing component with contoured recesses and volumes, formed by a coreactive mixture deposited layer by layer and cured via a chemical source, to fit into varying panel gaps and enhance acoustic attenuation.
The sealing component effectively reduces noise pollution by providing superior acoustic attenuation and sealing performance across different gap sizes, improving the fit and precision of aircraft components.
Smart Images

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Abstract
Description
[Technical Field]
[0001] Cross-reference of related applications This application claims the benefit under § 119(e) of U.S. Provisional Application No. 63 / 277,646, filed November 10, 2021, which is incorporated in its entirety by reference.
[0002] This disclosure relates to linear sealing components, as well as methods and compositions for additive manufacturing thereof. The disclosure further relates to sealing components that may have flame-retardant and / or acoustic-attenuating properties, as well as methods and compositions for additive manufacturing thereof. Linear sealing components may be used in aerospace applications. [Background technology]
[0003] Aircraft require high-precision construction and fit of their structural components. Even slight mismatches can result in physical gaps between components. Even slightly mismatched aircraft internal structural components can lead to poor acoustic attenuation between the cabin and other areas such as the aircraft avionics bay, baggage compartment, and landing gear wheel wells. In particular, noise can travel from noisy areas of the aircraft through physical gaps to the cabin area, thus causing noise pollution. Currently, insulating tapes and foams are typically inserted manually into physical gaps to improve barrier properties, but these are only slightly effective and not satisfactory. The ineffectiveness can be at least in part due to poor sealer properties, inadequate sealer-component interfaces, and varying gap sizes.
[0004] What is needed is an improvement that surpasses what has been mentioned above. [Overview of the Initiative]
[0005] This 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, the first recess and the second recess opposite the first recess defining a centerline, a first volume on the first side of the centerline, a second volume on the second side of the centerline, and a third volume between the first recess and the second recess, the third volume through which the centerline passes. The first recess includes the opening of the first recess, the first tip of the first volume, The third tip of the second volume , and the first wall of the third volume may be contoured. The second recess is the opening of the second recess, Second tip of the first volume The contour may be formed by a fourth tip of a second volume and a second wall of a third volume. The elongated body may include a thermosetting polymer formed by forming a coreactive mixture by mixing at least a first coreactive component and a second coreactive component, depositing the reactive mixture layer by layer to form an elongated body, and curing the deposited reactive mixture via a chemical source.
[0006] The drawings described herein are for illustrative purposes only. They are not intended to limit the scope of this disclosure. [Brief explanation of the drawing]
[0007] [Figure 1] This figure shows an apparatus for additive manufacturing of linear sealing components.
[0008] [Figure 2A] This is an image showing a linear sealing component according to the first embodiment.
[0009] [Figure 2B] Figure 2A shows an image illustrating how the linear sealing component fits into a 1 / 2-inch panel gap between 1 / 8-inch panels.
[0010] [Figure 3A]This image shows that the linear sealing component of the second embodiment fits into a 1 / 8-inch panel gap between 1 / 8-inch panels.
[0011] [Figure 3B] Figure 3A shows an image illustrating how the linear sealing component fits into a 1 / 2-inch panel gap between 3 / 8-inch panels.
[0012] [Figure 4] This figure shows a method for additive manufacturing linear sealing components.
[0013] [Figure 5] This is a diagram showing an acoustic testing apparatus.
[0014] [Figure 6] This graph shows the frequency spectrum data of sound pressure levels with and without the installation of linear ceiling components.
[0015] [Figure 7] This graph shows the overall sound pressure level with and without the installation of linear ceiling components.
[0016] [Figure 8A] This graph shows the viscosity of a co-reactive mixture within a given shear rate range.
[0017] [Figure 8B] This graph shows the shear viscosity of a co-reactive mixture over time.
[0018] [Figure 9] This diagram shows the dimensions of a linear sealing component. [Modes for carrying out the invention]
[0019] definition For the purposes of the following detailed description, it should be understood that the present invention may take various alternative modifications and sequences of steps, unless expressly otherwise specified. Furthermore, except for any example of operation, or where otherwise shown, all numbers representing the quantities of components used in the specification and claims should be understood in all examples as being modified by the term “approximately.” Thus, unless shown to be contrary, the numerical parameters described in the following specification and appended claims are approximations that may vary depending on the desired properties obtained by this disclosure. At the very least, and without attempting to limit the application of the equivalent view to the claims, each numerical parameter should be interpreted in light of at least the reported significant number of digits and by applying the usual rounding technique.
[0020] While the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values shown in specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that inevitably arise from the standard variations observed in their respective test measurements.
[0021] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges contained therein. For example, the range "1 to 10" is intended to have all subranges between (and including) the stated minimum value of 1 and the stated maximum value of 10, i.e., the minimum value equal to or greater than 1 and the maximum value equal to or less than 10.
[0022] The use of the singular form includes the plural form unless otherwise specified, and the plural form includes the singular form. Furthermore, while "and / or" may be explicitly used in certain examples, the use of "or" means "and / or" unless otherwise specified.
[0023] "Alkanediyl" refers to a group of 1 to 18 carbon atoms (C 1~18 ), 1 to 14 carbon atoms (C 1~14), a diradical of a saturated, branched, or linear acyclic hydrocarbon group having 1 to 6 carbon atoms (C 1~6 ), a diradical of a saturated, branched, or linear acyclic hydrocarbon group having 1 to 4 carbon atoms (C 1~4 ), or a diradical of a saturated, branched, or linear acyclic hydrocarbon group having 1 to 3 carbon atoms (C 1~3 ). Alkanediyl refers to C 2~14 alkanediyl, C 2~10 alkanediyl, C 2~8 alkanediyl, C 2~6 alkanediyl, C 2~4 alkanediyl, or C 2~3 alkanediyl. Examples of the alkanediyl group include methane-diyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl and isopropane-1,2-diyl (e.g., -CH2CH2CH2- and -CH(CH3)CH2-), butane-1,4-diyl (-CH2CH2CH2CH2-), pentane-1,5-diyl (-CH2CH2CH2CH2CH2-), hexane-1,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, and dodecane-1,12-diyl.
[0024] "Alkancycloalkane" 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 can be C 3~6 , C 5~6 , cyclohexyl, or cyclohexanediyl. 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. The alkancycloalkane group is C 4~18 [[ID=3�]]alkancycloalkane, C 4~16 alkancycloalkane, C4~12 Alkanes and cycloalkanes, C 4~8 Alkanes and cycloalkanes, C 6~12 Alkanes and cycloalkanes, C 6~10 Alkanes, cycloalkanes, or C 6~9 They may be alkanecycloalkanes. The alkanecycloalkane group may include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.
[0025] "Alkanecycloalkanediyl" refers to the diradical of the 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 may be an alkanecycloalkanediyl. Examples of alkanecycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.
[0026] The "alkenyl" group refers to the structure -CR=C(R)2, where the alkenyl group is a terminal group and is bonded to a larger molecule. In such cases, each R is independently a hydrogen and a C 1~3 It may contain alkyl groups. Each R can be a hydrogen atom, and the alkenyl group may have the structure -CH=CH2.
[0027] "Alkoxy" refers to an -OR group in which R is alkyl, as defined herein. Exemplary alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. Alkoxy groups are C 1~8 Alkoxy, C 1~6 Alkoxy, C 1~4 Alkoxy, or C 1~3 It could be an 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. Alkyl groups are C 1~6 Alkyl, C 1~4 Alkyl, or C 1~3 It can be an alkyl group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, and tetradecyl. Alkyl groups are C 1~6 Alkyl, C 1~4 Alkyl, and C 1~3 It can be alkyl.
[0029] "Arenediyl" refers to a diradical monocyclic or polycyclic aromatic group. Examples of arenediyl groups include benzene-diyl and naphthalene-diyl. The arenediyl group is C 6~12 Arrenziil, C 6~10 Arrenziil, C 6~9 It may be allenediyl or benzenediyl.
[0030] "Cycloalkanediyl" refers to a diradical saturated monocyclic or polycyclic hydrocarbon group. The cycloalkanediyl group is C 3~12 Cycloalkanediyl, C 3~8 Cycloalkanediyl, C 3~6 Cycloalkanediyl, or C 5~6 It may be a cycloalkanediyl. Examples of cycloalkanediyl groups 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. Cycloalkyl groups are C 3~12 Cycloalkyl, C 3~8 Cycloalkyl, C 3~6 Cycloalkyl, or C5~6 It may be a cycloalkyl group.
[0032] A "heteroalkanediyl" refers to an alkanediyl group in which one or more of the carbon atoms are replaced by heteroatoms such as N, O, S, or P. In heteroalkanediyls, one or more heteroatoms can be N or O.
[0033] A "heterocycloalkanediyl" refers to a cycloalkanediyl group in which one or more of the carbon atoms are replaced by heteroatoms such as N, O, S, or P. In a heterocycloalkanediyl, one or more heteroatoms can be N or O.
[0034] The "backbone" of a prepolymer refers to the segment between reactive end groups. The prepolymer backbone is typically polythiol HS-[R] n - Includes repeating subunits such as the SH skeleton.
[0035] A “coreactive composition” refers to a composition containing two or more coreactive compounds that can react at temperatures such as below 50°C, below 40°C, below 30°C, or below 20°C. Reactions between two or more compounds can be initiated by combining and mixing two or more coreactive compounds, and / or by exposing a coreactive composition containing two or more coreactive compounds to chemical radiation. A coreactive composition can be formed by combining and mixing a first reactive component containing a first reactive compound and a second reactive component containing a second reactive compound, where the first reactive compound can react with the second reactive compound.
[0036] Polyfunctionalizing agent B(-V) zThe "core" in this context refers to part B. The "core" of a compound or polymer refers to the segment between reactive end groups, such as the core of the polythiol HS-R-SH. The core of a compound or prepolymer may also be called the backbone of the compound or the backbone of the prepolymer. The core of a polyfunctionalizer 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 a part having a reactive functional group is bonded.
[0037] "Curing rate" and / or "curing time" may refer to the period from when the curing reaction of a co-reactive composition is first initiated by combining and mixing the co-reactive components to form the co-reactive composition, and / or by exposing the co-reactive composition to chemical radiation, until the layer prepared from the co-reactive composition exhibits a Shore hardness of 30A at 25°C and 50% relative humidity. In the case of chemical radiation-curable compositions, curing time refers to the period from when the co-reactive composition is first exposed to chemical radiation until the layer prepared from the exposed co-reactive composition exhibits a Shore hardness of 30A at 25°C and 50% relative humidity.
[0038] A dash ("-") between two letters or symbols is used to indicate a substituent bond or a bond between two atoms, such as -CONH2, that is bonded through a carbon atom.
[0039] The term "derived from" in the phrase "part derived from the compound" refers to a part that was formed during the reaction between the parent compound and the reactant. For example, the bis(alkenyl) compound CH2=CH-R-CH=CH2 can react with another compound, such as a compound having a thiol group, to produce a part -(CH2)2-R-(CH2)2- derived from the reaction between the alkenyl group and the thiol group. As another example, in the case of a parent diisocyanate with the structure O=C=NRN=C=O, the part 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 -V'- part is formed from the reaction of a thiol group with a part containing a terminal group that is reactive to the thiol group. For example, the group V- may contain CH2=CH-CH2-O-, and the terminal alkenyl group CH2=CH- is reactive to the thiol group -SH. When it reacts with the thiol group, the -V'- part becomes -CH2-CH2-CH 2- It is O-.
[0041] Glass transition temperature T g This 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 of -80°C to 25°C. g This is identified as the peak of the tanδ curve.
[0042] A monomer can refer to a low molecular weight compound 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. A monomer 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. A monomer may have a molecular weight greater than 100 Da, greater than 200 Da, greater than 300 Da, greater than 400 Da, greater than 500 Da, greater than 600 Da, or greater than 800 Da. A monomer may have two or more reaction functionalities, such as 2 to 6, 2 to 5, or 2 to 4. A monomer may have functionalities of 2, 3, 4, 5, 6, or any combination of the above. Monomers may have average reaction functionalities such as 2-6, 2-5, 2-4, 2-3, 2.1-2.8, or 2.2-2.6.
[0043] A "polyalkenyl" refers to a compound having at least two alkenyl groups. At least two of these alkenyl groups may be terminal alkenyl groups, and such polyalkenyl compounds may be called alkenyl-terminal compounds. Alkenyl groups may also be pendant alkenyl groups. A polyalkenyl can be a dialkenyl having two alkenyl groups. A polyalkenyl may have more than two alkenyl groups, for example, three to six. A polyalkenyl may consist of a single type of polyalkenyl, a combination of polyalkenyls having the same alkenyl functional group, or a combination of polyalkenyls having different alkenyl functional groups.
[0044] "Prepolymer" refers to homopolymers and copolymers. In the case of thiol-terminated prepolymers, the molecular weight is the number-average molecular weight "Mn" determined by end-group analysis using iodine titration. In the case of non-thiol-terminated prepolymers, the number-average molecular weight is determined by gel permeation chromatography using a polystyrene standard. A prepolymer consists of a backbone and end-reactive groups that can react with other compounds, such as curing agents or crosslinking agents, to form a cured polymer. A prepolymer contains multiple repeating partial units that are bonded together, which may be the same or different. These multiple repeating partial units constitute the backbone of the prepolymer.
[0045] The polyfunctionalizing agent is given by formula (1): B(-V) z (1) It may have a structure in formula B 1 -V is the core of the polyfunctional agent, and each V is a moiety terminated with a reactive functional group such as a thiol group, alkenyl group, epoxy group, isocyanate group, or Michael acceptor group, and z is an integer from 3 to 6, for example, 3, 4, 5, or 6. In the polyfunctional agent of formula (1), each -V may have a structure such as -R-SH or -R-CH=CH2, where R is C 2~10 Alkandiil, C 2~10 Heteroalkanediyl, substituted C 2~10 Alkanediyl or substitution C 2~10It can be a heteroalkanediyl. When partial V is reacted with another compound, partial V 1 - is obtained, which is said to be due to the reaction with other compounds. For example, if V is -R-CH=CH2 and reacts with a thiol group, partial V 1 It is -R-CH2-CH2- and may originate from the reaction.
[0046] The specific gravity is determined according to 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 independently substituted with the same or different substituent(s). Substituents include halogens, -S(O)2OH, -S(O)2, -SH, -SR [where R is C]. 1~6 [Alkyl], -COOH, -NO2, -NR2 [wherein each R is independently hydrogen and C] 1~3 [Containing alkyl], -CN, =O,C 1~10 Alkyl, -CF3, -OH, phenyl, C 2~6 Heteroalkyl, C 5~6 Heteroaryl, C 1~10 Alkoxy, or -COR [wherein R is C] 1~10 It may include alkyl groups. Substituents may be -OH, -NH2, or C 1~10 It can be alkyl.
[0049] "Tack-free time" refers to the duration from the initial commencement of the curing reaction of a co-reactive composition until the layer prepared from the co-reactive composition is no longer tack-free. Tack-free status is determined by applying a polyethylene sheet to the surface of the layer with manual 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 tack-free. In the case of chemically beam-curable co-reactive compositions, tack-free time refers to the time from exposure of the co-reactive composition to chemical radiation until the layer prepared from the co-reactive composition is no longer tack-free.
[0050] Tensile strength and elongation are measured according to AMS3279.
[0051] "Transmission" refers to the ability to transmit more than 20%, 30%, 40%, or 50% of the electromagnetic spectrum of incident radiation in the range of 360 nm to 750 nm.
[0052] Herein, we refer to certain compounds, compositions, apparatuses, and methods of the present disclosure. The disclosed compounds, compositions, apparatuses, and methods are not intended to limit the scope of the claims. On the contrary, the claims are intended to encompass all alternatives, modifications, and equivalents.
[0053] Introduction The methods provided by this disclosure include methods for fabricating linear sealing components 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. Linear sealing components may be fabricated by transporting a first co-reactive component and a second co-reactive component into a mixing chamber; mixing the first and second co-reactive components 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 chemical source. In various examples, the first co-reactive component comprises a thiol-terminated polythioether, while the second co-reactive component comprises a polyvinyl ether. A linear sealing component fabricated by this disclosure may include a first recess and a second recess opposite the first recess, a first volume on the first side of the centerline defined by the first and second recesses, a second volume on the second side of the centerline, and a third volume between the first and second recesses such that the centerline passes through the third volume. The first recess may be contoured 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 contoured 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 include a thermosetting polymer formed by: forming a coreactive mixture by mixing at least a first coreactive component and a second coreactive component; depositing the reactive mixture layer by layer to form an elongated body; and curing the deposited reactive mixture via a chemical source.
[0054] A 3D printing apparatus 100 is shown in Figure 1. Figure 1 shows the printing apparatus 100, which includes 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 can be fluidly coupled to the first reactant reservoir 104 and the second reactant reservoir 106 so that the first reactant stored in the first reactant reservoir 104 and the second reactant stored in the second reactant reservoir 106 are transported to the mixing chamber 102 and mixed. Once mixed, the reactant mixture can be deposited onto the printing platform 110 via the extrusion tip 108 to form a printed body 114. The printed body 114 can be cured or further cured by a radiation source 112 which can provide chemical radiation during and / or after the deposition of the reactant mixture.
[0055] Linear Ceiling Components Configuration 1 - Closed-core double crescent type A linear sealing component is a linear structure that fits into a physical gap between structures. A linear sealing component can fit between panel gaps between two or more panels (e.g., aircraft cabin panels). Cross-sectional views of a linear sealing component 200 are shown in Figures 2A and 2B.
[0056] Figure 2A shows 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 can be defined by the first crescent-shaped recess 208 and the second crescent-shaped recess 210 such that it passes through the third volume 206. As shown, the third volume 206 is centrally located 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 located on the 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 the second side of the reference centerline and is defined by the second outer wall 230, the fourth inner wall 218, the third tip 226, and the fourth tip 228. The first crescent-shaped recess 208 is defined by the first inner wall 212, the first tip 220, and the third tip 226. The second crescent-shaped recess 210 is defined by the third inner wall 216, the second tip 222, and the fourth tip 228. The ability of the linear sealing component to fix the panel having at least three contact points may be due to its excellent sound attenuation performance. The crescent-shaped recess may be called a recess.
[0057] Figure 2B shows the linear sealing component 200 of Figure 2A fitted into the panel gap between the first panel 228 and the second panel 230. Specifically, the first panel 228 is received by the first crescent recess 208 and secured by the first inner wall 212, the first tip 220, and the third tip 226 (e.g., via friction and / or pressure). The second panel 230 is received by the second crescent recess 210 and secured by the third inner wall 216, the second tip 222, and the fourth tip 228 (e.g., via friction and / or pressure). In certain examples, the panel received in the crescent recess does not need to be in contact with all three contact points (e.g., continuous contact) to maintain the seal. The depicted panel 228 does not need to be in direct contact with the inner recess 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, having 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 located between the linear sealing components of this disclosure and is not in the plane. As depicted, the linear sealing component 200 connects the first panel 228 and the second panel 230 (e.g., via elastic deformation) when the panel is out of the plane. The linear sealing component 200 may similarly receive a panel that is in the plane. Furthermore, the linear sealing components of this disclosure may be configured to receive panels spaced at various gap sizes, such as 0 to 1 / 2 inches and / or 0 to 100% of the distance between recesses of component 200. As depicted, the linear sealing component 200 can join the first panel 228 and the second panel 230 (e.g., via elastic deformation) when the panel gap is smaller 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 panels with a thickness of 1 to 1.5 times the size of its recess opening.
[0058] Configuration 2 - Open-core double crescent type Figure 3A shows a linear sealing component 300 having an open core (e.g., a third volume having three walls and one opening) and extended inner walls (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 recess 308, and a second crescent recess 310. A reference centerline can be defined by the first crescent recess 308 and the second crescent recess 310 such that it passes through the third volume 306. As shown, the third volume 306 is centrally located 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 located on the 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 located on the 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 can be fitted into the panel gap between the first panel 328 and the second panel 330. Specifically, the first panel 328 is received by a first crescent recess 308 and secured by a first inner wall 312, a first tip 320, and a third tip 326 (e.g., via friction and / or pressure). The second panel 330 is received by a second crescent recess 310 and secured by a third inner wall 316, a second tip 322, and a fourth tip 328 (e.g., via friction and / or pressure). 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 shown in Figure 3A, the linear sealing component 300 connects the first panel 328 and the second panel 330 via elastic deformation, such as compression of the third volume 306, substantially along the reference centerline. An open core design may improve the compressibility of the third volume 306 so that the linear sealing component 300 can fit into smaller panel gaps, such as the 1 / 8-inch gap shown in Figure 3A. However, the closed core design in Figure 2A may have superior sound attenuation performance.
[0060] Figure 3B shows the linear sealing component 300 of Figure 3A fitted to a panel gap of a longer distance than that in Figure 3A. Specifically, the panel gap in Figure 3B is 1 / 2 inch and is between the third panel 336 and the fourth panel 338. The third panel 336 is received by the first crescent recess 308 and secured (e.g., by friction and / or pressure) by the first inner wall 312, the first tip 320, and the third tip 326. The fourth panel 338 is received by the second crescent recess 310 and secured (e.g., by friction and / or pressure) by the third inner wall 316, the second tip 322, and the 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 Figure 3A, the linear sealing component 300 joins the first panel 328 and the second panel 330 via elastic deformation, such as compression of a third volume 306, slightly along the reference centerline. Because the panel gap in Figure 3B is larger than that in Figure 3A, a smaller degree of compression of the third volume 306 is required. 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 Figure 3A, for example, 3 / 8 inch instead of 1 / 8 inch. Because at least the inner walls 312 and 316 are longer, the linear sealing component 300 is configured to accommodate panels of a wider range of thicknesses (e.g., 1 / 16 inch to 1 / 2 inch). In certain circumstances, the linear sealing component 300 may accommodate and secure panels of 1 to 3 times the thickness of its recessed opening size.
[0061] Co-reactive composition The reactant mixture for producing the linear sealing components of this disclosure may comprise a prepolymer having any suitable backbone, a prepolymer having any suitable reactive functional group, a coreactive compound based on any suitable curing chemical, and any suitable additive. The reactant mixture may be a coreactive composition comprising a first compound having a first functional group and a second compound having a second functional group, wherein the first functional group is reactive to the second functional group. The first and second compounds may independently comprise monomers, combinations of monomers, prepolymers, combinations of prepolymers, or combinations thereof.
[0062] Coreactive compositions may include partially coreactive compositions in which the reaction between coreactive compounds is initiated by exposure to energy, such as exposure to chemical rays (e.g., ultraviolet light).
[0063] Coreactive compositions may include coreactive compounds that can react at temperatures below 50°C, for example, below 40°C, below 30°C, below 20°C, or below 10°C, either without or after exposure to chemical radiation. For example, coreactive compounds may react at temperatures of 5°C to 50°C, 10°C to 40°C, 15°C to 25°C, or 20°C to 30°C.
[0064] The coreactive composition was tested at 25°C for 0.1 seconds. -1 ~100 seconds -1 At the shear rate, 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 viscosities are such as 00 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. The coreactive compositions are exposed to temperatures of 25°C and 0.1 seconds. -1 ~100 seconds -1At shear rates, the viscosities are 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. The coreactive composition is subjected to 25°C and 0.1 seconds. -1 ~100 seconds -1 At a shear rate, it has viscosities such as less than 100,000,000 cP, less than 10,000,000 cP, less than 1,000,000 cP, less than 100,000 cP, less than 10,000 cP, or less than 1,000 cP. Viscosity values are measured at a temperature of 25°C and 100 seconds. -1 The shear rate is measured using an Anton Paar MCR302 rheometer with a gap of 1 mm.
[0065] The co-reactive composition can be formulated as a sealant composition that forms a linear sealing component upon curing.
[0066] Linear sealing components refer to materials that have the ability to resist atmospheric conditions such as noise, moisture, and temperature, and / or to at least partially block the transmission of materials such as water, solvents, fuels, hydraulic fluids, and other liquids and gases. Linear sealing components may exhibit chemical resistance, such as resistance to fuels and hydraulic fluids. Chemical-resistant materials may exhibit a percentage swelling rate of less than 25%, less than 20%, less than 15%, or less than 10% after immersion in a chemical at 70°C for 7 days, as determined in accordance with EN ISO 10563. Sealants may exhibit resistance to jet reference fluids (JRF) type I, or Skydrol® LD-40 hydraulic fluids. For example, the linear sealing components of this disclosure may exhibit chemical resistance similar to that of the sealant described in U.S. Patent No. 10,047,259, which is incorporated herein by reference in whole for all purposes.
[0067] Prepolymers and monomers The prepolymer may have a number-average molecular weight such as 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. The prepolymer may have a number-average molecular weight such as greater than 2,000 Da, greater than 4,000 Da, greater than 6,000 Da, greater than 8,000 Da, greater than 10,000 Da, or greater than 15,000 Da. The prepolymer may have a number-average molecular weight such as, 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.
[0068] The prepolymer may be liquid at 25°C and may have a glass transition temperature (Tg) such as below -20°C, below -30°C, or below -40°C. The prepolymer may exhibit viscosities 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).
[0069] Prepolymer skeleton The co-reactive composition may include a prepolymer having any suitable polymer backbone. The polymer backbone may be selected to impart desired physical properties such as tensile strength, % elongation, Young's modulus, impact resistance, or other properties relevant to the application, in order to impart solvent resistance to the co-reactive composition to be cured. The prepolymer backbone may be terminated with one or more suitable functional groups, depending on the specific curing chemical reaction.
[0070] The prepolymer skeleton consists of 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, and polyethylene. This may include polystyrene, syndiotactic or isotactic polypropylene, polylactic acid, polyamide, ethyl vinyl acetate homopolymer or copolymer, polyurethane, ethylene copolymer, propylene copolymer, propylene impact copolymer, polyether ether ketone, polyoxymethylene, syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), butene homopolymer and copolymer, hexene homopolymer and copolymer, and any combination of the foregoing.
[0071] Other suitable prepolymer skeletons 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, one or more acrylates, methacrylates, methyl acrylate, ethyl methacrylate, butyl acrylate, and methyl polymers derived from butyl methacrylate, etc.), olefin and styrene copolymers, acrylonitrile / 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), polyether ketone (PEK), polyether ether ketone (PEEK), polyimide, polyoxymethylene (POM) Homopolymers and copolymers, polyetherimides, fluoroethylene propylene polymers (FEP), poly(vinyl fluoride), poly(vinylidene fluoride), poly(vinylidene chloride) and poly(vinyl chloride), polyurethanes (thermoplastic and thermosetting), aramids (such as Kevlar® and Nomex®), polytetrafluoroethylene (PTFE), polysiloxanes (including polydimethylenesiloxane, dimethylsiloxane / vinylmethylsiloxane copolymer, and vinyldimethylsiloxane-terminated poly(dimethylsiloxane)),Examples include elastomers, epoxy polymers, polyureas, alkyds, cellulose polymers (such as ethylcellulose, ethyl hydroxyethylcellulose, carboxymethylcellulose, cellulose acetate, cellulose acetic acid propionate, and cellulose acetate butyrate), polyethers, and glycols such as poly(ethylene oxide) (also known as poly(ethylene glycol)) and poly(propylene oxide) (also known as poly(propylene glycol)), as well as ethylene oxide / propylene oxide copolymers, acrylic latex polymers, polyester acrylate oligomers and polymers, polyester diol diacrylate polymers, and UV-curable resins.
[0072] The co-reactive composition may include a prepolymer containing an elastomer skeleton.
[0073] An elastomer is a material that possesses "rubber-like" properties and generally has a low Young's modulus and high tensile strain. Elastomers can have a tensile strain (elongation at break) of 100% to 2,000%. Elastomers can exhibit tear strengths of 50 kN / m to 200 kN / m, as determined according to ASTM D624. The Young's modulus of an elastomer can range from 0.5 MPa to 30 MPa, for example, 1 MPa to 6 MPa, as determined according to ASTM D412.4893.
[0074] Suitable prepolymers having an elastomer backbone include polyethers, polybutadienes, fluoroelastomers, perfluoroelastomers, ethylene / acrylic copolymers, ethylene propylene dienterpolymers, nitriles, polythiolamines, polysiloxanes, chlorosulfonated polyethylene rubber, isoprene, neoprene, polysulfide, polythioethers, silicones, styrene butadiene, and any combination of the aforementioned. Elastomerous prepolymers may include polysiloxanes such as polymethylhydrosiloxane, polydimethylsiloxane, polyhydrodiethylsiloxane, polydiethylsiloxane, or any combination of the aforementioned. Elastomerous prepolymers may include terminal functional groups that have low reactivity with amines and isocyanate groups, such as silanol groups.
[0075] Sulfur-containing prepolymer The co-reactive composition may include a sulfur-containing prepolymer or a combination of sulfur-containing prepolymers. The sulfur-containing prepolymer can impart sound resistance to the linear sealing component to be cured. The sulfur-containing prepolymer may include a sulfur-containing prepolymer, a polysulfide prepolymer, a sulfur-containing polyformal prepolymer, a monosulfide prepolymer, or any combination of the aforementioned.
[0076] A sulfur-containing prepolymer is a prepolymer with one or more thioether-S molecules in its backbone. n - Refers to a prepolymer having a group [wherein n can be 1 to 6]. Prepolymers containing only thiols or other sulfur-containing groups as either terminal or pendant groups are not included in sulfur-containing prepolymers. The prepolymer backbone refers to a portion of the prepolymer having repeating segments. Therefore, HS-RR(-CH2-SH)-[-R-(CH2)2-S(O)2-(CH2)-S(O)2] nA prepolymer having the structure -CH=CH2, in which each R is a part that does not contain a sulfur atom, is not included in the sulfur-containing prepolymers. A prepolymer having the structure HS-RR(-CH2-SH)-[-R-(CH2)2-S(O)2-(CH2)-S(O)2]-CH=CH2, in which at least one R is a part that contains a sulfur atom, such as a thioether group, is included in the sulfur-containing prepolymers.
[0077] Sulfur-containing prepolymers with high sulfur content can impart chemical resistance to the co-reactive composition to be cured. The sulfur-containing prepolymer skeleton may have a sulfur content of more than 10% by weight, more than 12% by weight, more than 15% by weight, more than 18% by weight, more than 20% by weight, or more than 25% by weight, where the weight percentage is based on the total weight of the prepolymer skeleton. Chemical-resistant prepolymer skeletons may have sulfur content of 10% to 25% by weight, 12% to 23% by weight, 13% to 20% by weight, or 14% to 18% by weight, where the weight percentage is based on the total weight of the prepolymer skeleton.
[0078] Examples of prepolymers having a sulfur-containing skeleton include polythioether prepolymers, polysulfide prepolymers, sulfur-containing polyformal prepolymers, monosulfide prepolymers, and any combination of the aforementioned.
[0079] The co-reactive composition may contain 40% to 80% by weight, 40% to 75% by weight, 45% to 70% by weight, or 50% to 70% by weight of a sulfur-containing prepolymer or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the co-reactive composition. The co-reactive composition may contain more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the co-reactive composition. The co-reactive composition may contain less than 90% by weight, less than 80% by weight, less than 70% by weight, less than 60% by weight, less than 50% by weight, or combination of sulfur-containing prepolymers, where the weight percentage is based on the total weight of the co-reactive composition.
[0080] Co-reactive functional groups The coreactive composition may contain a coreactive compound having any suitable coreactive functional group.
[0081] The first co-reactive compound may contain one or more first functional groups, the second co-reactive compound may contain one or more second functional groups, and one or more first functional groups are reactive to one or more second functional groups.
[0082] By selecting one functional group or a combination of functional groups, the desired curing rate can be achieved.
[0083] The first functional group may include a thiol group, and the second functional group may include a thiol group, an alkenyl group, an alkynyl group, an epoxy group, a Michael acceptor group, an isocyanate group, or any combination of the above.
[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 any combination of the aforementioned.
[0085] The first functional group may include an epoxy group, and the second functional group may include an epoxy group.
[0086] The first functional group may include a Michael acceptor group, and the second functional group may include a Michael donor group.
[0087] The first functional group may include a carboxylic acid group, and the second functional group may include an epoxy group.
[0088] The first functional group may include a cyclic carbonate group, an acetacetate group, or an epoxy group, and the second functional group may include a primary amine group or a secondary amine group.
[0089] The first functional group may include a Michael acceptor group such as a (meth)acrylate group, cyanoacrylate, vinyl ether, vinylpyridine, or α,β-unsaturated carbonyl group, and the second functional group may include a malonate group, acetylacetonate, nitroalkane, or another active alkenyl group.
[0090] The first functional group may include an amine, and the second functional group may include a carboxylic acid, aldehyde, or ketone selected from epoxy groups, isocyanate groups, acrylonitriles, esters, and anhydrides.
[0091] Suitable co-reactive 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] 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. 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. 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 curing rate of any of these co-reactive chemical reactions can be altered by including a suitable catalyst or combination of catalysts in the co-reactive composition. The curing rate of any of these co-reactive chemical reactions can also be altered by increasing or decreasing the temperature of the co-reactive composition. While the co-reactive composition can cure at temperatures below 30°C, heating the co-reactive composition can accelerate the reaction rate, which may be desirable in certain circumstances, such as to accommodate increased printing speeds. Increasing the temperature of the co-reactive components and / or the co-reactive composition may also serve to adjust viscosity, thereby facilitating the mixing of the co-reactive components and / or the deposition of the co-reactive composition.
[0094] Curable Co-reactive Composition The coreactive composition may contain a coreactive compound that can co-react at temperatures below 50°C without exposure to chemical radiation, and may optionally contain a catalyst.
[0095] The coreactive composition may include compounds such as monomers and / or prepolymers containing a coreactive functional group, which may include 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-hardening co-reactive composition The co-reactive composition may be a chemically beam-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 a chemical beam.
[0098] Examples of actinic rays include α-rays, γ-rays, X-rays, ultraviolet (UV) rays (200 nm to 400 nm), for example, 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 (above 700 nm), near-infrared radiation (0.75 μm to 1.4 μm), and electron beams.
[0099] The radiation-curable co-reactive composition may contain a compound capable of co-reacting by a free radical mechanism. Examples of free radical curing reactions may include thiol / alkenyl reactions and thiol / alkynyl reactions.
[0100] The radiation-curable co-reactive composition may contain any suitable free radical polymerization initiator or a combination of suitable free radical polymerization initiators. Free radical polymerization initiators may include photoinitiators, thermally activated free radical generators, cationic free radical generators, and dark curing free radical generators.
[0101] The radiation-curable co-reactive composition may contain a photoinitiator such as a visible light initiator or a UV light initiator.
[0102] The radiation-curable co-reactive composition may contain a thermally activated free radical generator.
[0103] The radiation-curable co-reactive composition may contain a cationic free radical generator.
[0104] The radiation-curable co-reactive composition may contain a dark curing free radical generator.
[0105] The free radical photopolymerization reaction can be initiated by exposing the co-reactive 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 output of the UV exposure is 50 mW / cm 2 ~500 mW / cm 2 、50 mW / cm 2 ~400 mW / cm 2 、50 mW / cm 2 ~300 mW / cm 2 、100 mW / cm 2 ~300 mW / cm 2 、または150 mW / cm 2 ~250 mW / cm 2 and can be.
[0106] The actinic radiation curable co-reactive composition can be exposed to a UV dose of 1 J / cm 2 ~4 J / cm 2 to cure the composition. The UV source is an 8W lamp having a UVA spectrum. Other doses and / or other UV sources may be used. The UV dose for curing the composition can be 0.5 J / cm 2 ~4 J / cm 2 、0.5 J / cm 2 ~3 J / cm 2 、1 J / cm 2 ~2 J / cm 2 、または1 J / cm 2 ~1.5 J / cm 2 and can be.
[0107] The actinic radiation curable co-reactive composition can also be cured with radiation in the blue wavelength range, such as by using light emitting diodes.
[0108] Chemically curable sealant compositions suitable for use in linear sealing components are disclosed in U.S. Patent Nos. 8,729,198, 9,533,798, 10,233,369, U.S. Publication No. 2019 / 0169465, PCT International Publication No. PCT / US2018 / 36746; U.S. Publication No. 2018 / 0215974, and U.S. Patent No. 7,438,974.
[0109] Permeable co-reactive composition The free radical polymerizable coreactive composition may be permeable to a chemical beam to such an extent that the incident chemical beam can generate enough free radicals to completely cure the free radical polymerizable coreactive composition.
[0110] Co-reactive compositions that are permeable to chemical rays can allow chemical rays to pass through them through thicknesses such as 1 mm to 30 mm, 1 mm to 25 mm, 1 mm to 20 mm, 1 mm to 15 mm, or 1 mm to 10 mm.
[0111] A free radical polymerizable coreactive composition may be partially permeable to a chemical beam to such an extent that the incident chemical beam can generate enough free radicals to initiate free radical polymerization of the coreactive composition in at least a portion of the exposed coreactive composition. The unexposed portion of the coreactive composition can be cured by another free radical mechanism, such as a dark curing mechanism, or by a non-free radical mechanism.
[0112] The free radical initiation wavelength range may depend on the type of free radical generator in the co-reactive composition.
[0113] Curing of co-reactive composition Co-reactive compositions can be deposited and cured without exposure to chemical radiation, and the curing rate is determined by one or more of the curing chemicals, type and amount of catalyst, temperature, and viscosity of the deposited co-reactive composition. After deposition, the co-reactive composition can be exposed to heat to accelerate the curing of at least a portion of the co-reactive composition.
[0114] The curing of a free radical polymerizable coreactive composition can be initiated by activating the free radical generator, such as by exposing the free radical polymerizable coreactive composition to chemical radiation or heat.
[0115] Free radical polymerizable coreactive compositions may be exposed to chemical radiation while they are in a three-dimensional printing apparatus, during deposition of the free radical polymerizable coreactive compositions, and / or after deposition of the free radical polymerizable coreactive compositions. The deposited free radical polymerizable coreactive compositions may be exposed to chemical radiation after the coreactive compositions are initially deposited, or, depending on the manufacturing method, after the linear sealing components are manufactured, or after the linear sealing components are installed between panel gaps.
[0116] Linear sealing components can be fabricated by depositing continuous layers of chemically laser-curable coreactive compositions using three-dimensional printing.
[0117] To initiate a chemical reaction, the chemically beam-curable coreactive composition may be exposed to chemical radiation before being extruded from the nozzle, while being extruded from the nozzle, after being extruded from the nozzle, and / or while or after being deposited on a pre-deposited layer.
[0118] When constructing a linear sealing component, the physical properties of the co-reactive composition can be such that the deposited co-reactive composition has sufficient mechanical strength to maintain its intended shape and support the upper layer of the co-reactive composition before the underlying layer is fully cured. The physical properties can be determined, in part, by the amounts of the components in the composition, the type and rate of curing, and the like.
[0119] A linear sealing component can be fabricated by printing a co-reactive composition that does not require exposure to actinic radiation to initiate a chemical reaction. The linear sealing component can be fabricated using three-dimensional printing to deposit successive layers of the co-reactive composition. Procedures similar to those described for fabricating a chemically curable linear sealing component are applicable, except that the co-reactive composition is not exposed to actinic radiation.
[0120] Photoinitiator 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 can be activated by actinic radiation that can apply energy effective to generate initiating species from the photoinitiator upon irradiation with, for example, alpha rays, gamma rays, X-rays, ultraviolet (UV) rays including the UVA, UVA, and UVC spectra, visible light, blue light, infrared light, near infrared light, or an electron beam. The photoinitiator can be a UV photoinitiator.
[0122] Suitable UV photoinitiators include α-hydroxyketones, benzophenone, α,α-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2-hydroxy-2-propyl ketone, 1-hydroxycyclohexylphenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, O-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosverone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-acyclophosphine oxide, benzophenone photoinitiators, oxime photoinitiators, phosphine oxide photoinitiators, and any combination of the above.
[0123] Thermally activated free radical initiators can be activated at high temperatures, such as above 25°C.
[0124] Suitable thermally activated free radical initiators include organic peroxy compounds, azobis(organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and any combination of the aforementioned. Suitable organic peroxy compounds that can be used as thermal polymerization initiators include peroxy monocarbonate esters, e.g., tertiary butyl peroxy 2-ethylhexyl carbonate and tertiary butyl peroxyisopropyl carbonate; peroxy ketals, e.g., 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane; peroxy dicarbonate esters, e.g., di(2-ethylhexyl) peroxy dicarbonate, di(sec-butyl) peroxy dicarbonate and diisopropyl peroxy dicarbonate; diacyl peroxide Examples include 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauryl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide; peroxyesters, such as tert-butyl peroxypivalate, tert-butyl peroxyoctylate, and tert-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, acetylcyclohexanesulfonyl peroxide, and any combination of the aforementioned. 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] Coreactive compositions may also be cured by means other than chemical radiation, such as the coreactive compounds mentioned above, and would typically contain two or more modification 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 from 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] The use of co-reactive three-dimensional printing can extend the range of chemicals and compositions used to fabricate linear sealing components beyond those suitable for use in chemically wire-curable compositions.
[0128] Furthermore, linear sealing components can be fabricated using a single co-reactive composition, but more than one co-reactive composition may be used, each co-reactive composition being adjusted to optimize the desired properties. A co-reactive composition applied directly to the fastener may be configured to promote adhesion to the fastener surface and to be low density, while an outer co-reactive composition applied on top of the inner co-reactive composition may be configured to provide enhanced fuel resistance.
[0129] The chemicals of the inner and outer coreactive compositions may be the same or different. By using the same curing chemical for both the inner and outer coreactive compositions, adhesion between the two coreactive compositions by covalent bond formation can be promoted.
[0130] Co-reactive curing chemicals may include thiol / alkenyl, thiol / alkynyl, thiol / thiol, thiol / Michael receptor, thiol / epoxy, thiol / isocyanate, isocyanate / hydroxyl, isocyanate / amine, and Michael donor / Michael receptor.
[0131] polythioether The co-reactive composition may include a polythioether prepolymer or a combination of polythioether prepolymers.
[0132] The polythioether prepolymer may include a polythioether prepolymer comprising at least one moiety having the structure of formula (2), a thiol-terminated polythioether prepolymer of formula (2a), a terminally modified polythioether of formula (2b), or any combination thereof. -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 can be an integer from 1 to 60. Each R 1 Independently, C 2~10 Alkandiil, C 6~8 Cycloalkanediyl, C 6~14 Alkanecycloalkanediyl, C 5~8 Heterocycloalkanediyl, and -[(CHR) p -X-] q (CHR) r - can be selected from, in the formula, p can be an integer between 2 and 6. q can be an integer from 1 to 5. r can be an integer between 2 and 10. Each R can be independently selected from hydrogen and methyl. Each X can be independently selected from O, S, and SS. Each A can independently be a portion derived from the polyvinyl ether of formula (3) and the polyalkenyl polyfunctionalizer of formula (4), CH2=CH-O-(R 2 -O) m -CH=CH2(3) B(-R 4-CH=CH2) z (4) During the ceremony, m can be an integer between 0 and 50. Each R 2 Independently, C 1~10 Alkandiil, C 6~8 Cycloalkanediyl, C 6~14 Alkanecycloalkanediyl and -[(CHR) p -X-] q (CHR) r - may be selected from, where p, q, r, R, and X are R 1 As defined in relation to, Each R 3 These can independently be moieties containing terminal reactive groups, B is a z-valent polyalkenyl polyfunctionalizer B(-R 7 -CH=CH2) z It represents the core, and in the formula, z can be an integer between 3 and 6. Each R 4 Independently, C 1~10 Alkandiil, C 1~10 Heteroalkanediyl, substituted C 1~10 Alkanediyl and substituted C 1~10 They can be selected from heteroalkanediyl groups.
[0133] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 C 2~10 It could be Arcandil.
[0134] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CHR) p -X-] q (CHR) r - It is possible.
[0135] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), X may be selected from O and S, and therefore -[(CHR) p -X-] q(CHR) r -ha-[(CHR) p -O-] q (CHR) r -or-[(CHR) p -S-] q (CHR) r - is possible. p and r can be equal, for example, when both p and r can be 2.
[0136] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 C 2~6 Alkanedils and -[(CHR)] p -X-] q (CHR) r - can be selected from these options.
[0137] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CHR) p -X-] q (CHR) r - can be O, or X can be S.
[0138] The portion of formula (2), and the prepolymers of formulas (2a) and (2b) [wherein R 1 ha-[(CHR) p -X-] q (CHR) r In [possibly], p can be 2, r can be 2, q can be 1, and X can be S, or p can be 2, q can be 2, r can be 2, and X can be O, or p can be 2, r can be 2, q can be 1, and X can be O.
[0139] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CHR) p -X-] q (CHR) r - and each R can be a hydrogen atom, or at least one R can be a methyl atom.
[0140] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CH2) p -X-] q (CH2) r -This is possible, and in the formula, each X can be independently selected from O and S.
[0141] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CH2) p -X-] q (CH2) r - is possible, and in the expression, each X can be O or each X can be S.
[0142] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), R 1 ha-[(CH2) p -X-] q (CH2) r - is possible, in the equation p can be 2, X can be 0, q can be 2, r can be 2, R 2 m can be ethane, m can be 2, and n can be 9.
[0143] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), each R 1 It may be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2-(ethane-1,2-diylbis(sulfanyl))bis(ethane-1-thiol)), or each R 1 These may be derived from dimercaptodiethyl sulfide (DMDS; 2,2'-thiobis(ethane-1-thiol)), or from combinations thereof.
[0144] In the part of formula (2), and in 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 be 2, 3, 4, 5, or 6.
[0145] In the portion of formula (2), and in the prepolymers of formulas (2a) and (2b), each q may independently be 1, 2, 3, 4, or 5. Each q may be the same and may be 1, 2, 3, 4, or 5.
[0146] In the portion of formula (2), and in the prepolymers of formulas (2a) and (2b), each r may independently be 2, 3, 4, 5, 6, 7, 8, 9, or 10. Each r may be the same and may be 2, 3, 4, 5, 6, 7, 8, 9, or 10.
[0147] In the part of formula (2), and in the prepolymers of formulas (2a) and (2b), each r can independently be an integer between 2 and 4, 2 and 6, or 2 and 8.
[0148] In the divinyl ether of formula (3), m can be an integer between 0 and 50, for example, 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 Independently, C 2~10 n-alkanediyl group, C 3~6 Branched alkanediyl group, and -[(CH2) p -X-] q (CH2) r -Can be selected from the base.
[0150] In the divinyl ether of formula (3), each R 2 These are independently C such as methanediyl, ethanediyl, n-propanediyl, or n-butanediyl. 2~10 It can be an n-alkanediyl group.
[0151] In the divinyl ether of formula (3), each R 2 Independently, -[(CH2) p -X-] q (CH2) r - May include a base, where each X can be O or S.
[0152] In the divinyl ether of formula (3), each R 2 Independently, -[(CH2) p -X-] q (CH2) r - May include a base.
[0153] In the divinyl ether of formula (3), each m can be an integer from 1 to 3 independently. Each m can be the same and be 1, 2, or 3.
[0154] In the divinyl ether of formula (3), each R 2 Independently, C 2~10 n-alkanediyl group, C 3~6 Branched alkanediyl group, and -[(CH2) p -X-] q (CH2) r -Can be selected from the base.
[0155] In the divinyl ether of formula (3), each R 2 Independently, C 2~10 It can be an n-alkanediyl group.
[0156] In the divinyl ether of formula (3), each R 2 Independently, -[(CH2) p -X-] q (CH2) r -It can be a base, and each X can be either O or S.
[0157] In the divinyl ether of formula (3), each R 2 Independently, -[(CH2) p -X-] q (CH2) r - can be a base, each X can be O or S, and each p can independently be 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 Independently, -[(CH2) p -X-] q (CH2) r - can be a base, 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 Independently, -[(CH2) p -X-] q (CH2) r - can be a base, 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 ether of formula (3), each r can be the same and be 2, 3, 4, 5, 6, 7, 8, 9, or 10. In the divinyl ether of formula (3), each r can independently be an integer between 2 and 4, 2 and 6, or 2 and 8.
[0163] Suitable divinyl ethers include ethylene glycol divinyl ether (EG-DVE), butanediol divinyl ether (BD-DVE), hexanediol divinyl ether (HD-DVE), diethylene glycol divinyl ether (DEG-DVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polytetrahydrofuryl divinyl ether, cyclohexanedimethanol divinyl ether, and any combination of the aforementioned.
[0164] Divinyl ethers may include sulfur-containing divinyl ethers. Suitable sulfur-containing divinyl ethers are disclosed in PCT Publication 2018 / 085650.
[0165] In part (3), each A may independently be derived from a polyalkenyl polyfunctionalizer. The polyalkenyl polyfunctionalizer may have the structure of formula (4), where z may be 3, 4, 5, or 6.
[0166] In the polyalkenyl polyfunctional agent of formula (4), each R 7 Independently, C 1~10 Alkandiil, C 1~10 Heteroalkanediyl, substituted C 1~10 Alkanediyl or substitution C 1~10 A heteroalkanediyl can be selected. One or more substituents may be -OH, =O, C. 1~4 Alkyl, and C 1~4 Alkoxy atoms may be selected. 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-trialyl-1,3,5-triazinan-2,4,6-trione), 1,3,5-trialyl-1,3,5-triazinan-2,4,6-trione), 1,3-bis(2-methylallyl)-6-methylene-5-(2-oxopropyl)-1,3,5-triazinon-2,4-dione, tris(allyloxy)methane, pentaerythritol trialyl ether, 1-( Examples include allyloxy)-2,2-bis((allyloxy)methyl)butane, 2-propa-2-ethoxy-1,3,5-tris(propa-2-enyl)benzene, 1,3,5-tris(propa-2-enyl)-1,3,5-triazinan-2,4-dione, and 1,3,5-tris(2-methylallyl)-1,3,5-triazinan-2,4,6-trione, 1,2,4-trivinylcyclohexane, trimethylolpropanetrivinyl ether, and any combination of the above.
[0168] In the portion of formula (2) and the prepolymers of formulas (2a) to (2b), the molar ratio of the portion derived from the divinyl ether to the portion derived from the polyalkenyl polyfunctionalizer may 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 part of formula (2) and the prepolymers of formulas (2a) to (2b), each R 1 It can be -(CH2)2-O-(CH2)2-O-(CH2)2-, and each R 2 m can be -(CH2)2-, and m can be an integer from 1 to 4.
[0170] In the part of formula (2) and the prepolymers of formulas (2a) to (2b), R 2 These may be derived from divinyl ethers such as diethylene glycol divinyl ether, polyalkenyl polyfunctionalizers such as triallyl cyanurate, or combinations thereof.
[0171] In the portion of formula (2) and the prepolymers of formulas (2a) to (2b), each A can be independently selected from the portion of formula (3a) and the portion of formula (4a). -(CH2)2-O-(R 2 -O) m -(CH2)2- (3a) B {-R 4 -(CH2)2-}2{-R 4 -(CH2)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 defined in equations (2), (3), and (4).
[0172] In the portion of formula (3) and the prepolymers of formulas (2a) to (2b), Each R 1It can be -(CH2)2-O-(CH2)2-O-(CH2)2-, and each R 2 is possible as -(CH2)2-, m can be an integer from 1 to 4, and polyfunctional agent B(-R 4 -CH=CH2) z It contains triallyl cyanurate, where z is 3 and each R 4 The equation is -O-CH2-CH=CH2.
[0173] A method for synthesizing sulfur-containing polythioethers is disclosed in U.S. Patent No. 6,172,179.
[0174] The thiol-terminated polythioether prepolymer backbone 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. To improve one or more performance attributes, adhesion promoters, antioxidants, metal ligands, and / or urethane bonds may be incorporated into the polythioether prepolymer backbone. The skeletal-modified polythioether prepolymers are disclosed in any one of the following U.S. Patents: 8,138,273 (containing urethane), 9,540,540 (containing sulfone), 8,952,124 (containing bis(sulfonyl) alkanol), 9,382,642 (containing metal ligand), U.S. Publication 2017 / 0114208 (containing antioxidant), PCT International Publication 2018 / 085650 (sulfur-containing divinyl ether), and PCT International Publication 2018 / 031532 (containing urethane). Examples of polythioether prepolymers include those described in U.S. Publications 2017 / 0369737 and 2016 / 0090507.
[0175] Suitable thiol-terminated polythioether prepolymers are disclosed in U.S. Patent No. 6,172,179. These thiol-terminated polythioether prepolymers may include Permapol® P3.1E, Permapol® P3.1E-2.8, Permapol® L56086, or any combination thereof, 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). Examples of 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 Publication Nos. 2017 / 0369757 and 2016 / 0090507.
[0176] Polysulfide Sulfur-containing prepolymers may include polysulfide prepolymers or combinations of polysulfide prepolymers.
[0177] A polysulfide prepolymer is a prepolymer backbone containing one or more polysulfide bonds, i.e., -S x - Refers to a prepolymer containing a sulfur-sulfur bond [wherein x is 2 to 4]. Polysulfide prepolymers may have two or more sulfur-sulfur bonds. Suitable thiol-terminated polysulfide prepolymers are commercially available from AkzoNobel and Toray Industries, Inc. under the trademark names Thioplast® and Thiokol-LP®, respectively.
[0178] Suitable polysulfide prepolymers are disclosed in U.S. Patents No. 4,623,711, No. 6,172,179, No. 6,509,418, No. 7,009,032, and No. 7,879,955.
[0179] Suitable thiol-terminated polysulfide prepolymers include Thioplast® G polysulfides such as Thioplast® G1, Thioplast® G4, Thioplast® G10, Thioplast® G12, Thioplast® G21, Thioplast® G22, Thioplast® G44, Thioplast® G122, and Thioplast® G131, which are commercially available from AkzoNobel. Thioplast® G resin is a liquid thiol-terminated polysulfide prepolymer that is a blend of bifunctional and trifunctional molecules, in which the bifunctional thiol-terminated polysulfide prepolymer may have the structure of formula (5) and the trifunctional thiol-terminated polysulfide polymer may have the structure of formula (6). HS-(-R 5 -SS-) d -R 5 -SH (5) HS-(-R 5 -SS-) a -CH2-CH{-CH2-(-SSR 5 -) b -SH}{-(-SSR 5 -) c -SH} (6) In the formula, each R 5 The compound is -(CH2)2-O-CH2-O-(CH2)2-, where d = a + b + c, and the value of d can be 7 to 38 depending on the amount of trifunctional crosslinking agent (1,2,3-trichloropropane; TCP) used in the synthesis of the polysulfide prepolymer. Thioplast® G polysulfides may have a number average molecular weight of less than 1,000 Da to 6,500 Da, an SH content of 1% to over 5.5%, and a crosslinking density of 0% to 2.0%.
[0180] The polysulfide prepolymer may further include a terminally modified polysulfide prepolymer having the structure of formula (5a), a terminally modified polysulfide prepolymer having the 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 -CH2-CH{-CH2-(-SSR 5 -) b -S-}{-(-SSR 5 -) c -SR 3 (6a) In the formula, d, a, b, c, and R 5 This is defined for equations (6) and (7), and R 3 This is the portion containing the terminal reactive group.
[0181] Suitable thiol-terminated polysulfide prepolymers may 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, a -SH content of 0.8% to 7.7%, and a crosslinking density of 0% to 2%. Thiokol® LP polysulfide prepolymers have the structure of formula (7), and terminally modified polysulfide prepolymers may have the structure of formula (7a). HS-[(CH2)2-O-CH2-O-(CH2)2-SS-] e -(CH2)2-O-CH2-O-(CH2)2-SH (7) R 3 -S-[(CH2)2-O-CH2-O-(CH2)2-SS-] e -(CH2)2-O-CH2-O-(CH2)2-SR 3 (7a) In the formula, e can be an integer from 8 to 80, such as a number-average molecular weight from 1,000 Da to 7,500 Da, and each R 6 This is the part containing the terminally reactive functional group.
[0182] Thiol-terminated sulfur-containing prepolymers may include Thiokol-LP® polysulfide, Thioplast® G polysulfide, or a combination thereof.
[0183] The polysulfide prepolymer may include a polysulfide prepolymer containing the portion of formula (7), a thiol-terminated polysulfide prepolymer of formula (7a), a terminally modified polysulfide prepolymer of formula (7b), or any combination thereof. -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 can 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 a branched alkanediyl, a branched arenediyl, and structure-(CH2) p -O-(CH2) q -O-(CH2) r - can be selected from the parts having -, in the formula, q can 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 This is the part containing the terminally reactive functional group.
[0184] In the portion of formula (7) and the prepolymers of formulas (7a) to (7b), R 6 0% to 20% of the group may include branched alkanediyl or branched arenediyl, R 6 80% to 100% of the original is -(CH2) p -O-(CH2) q -O-(CH2) r - It is possible.
[0185] In the portion of formula (7) and the prepolymers of formulas (7a) to (7b), branched alkanediyl or branched arenediyl is -R(-A) f -This can be the case, where R is a hydrocarbon group, f is 1 or 2, and A is a branching point. Branched alkanediyls may have the structure -CH2(-CH(-CH2-)-).
[0186] Exemplary thiol-terminated polysulfide prepolymers of formulas (7a) and (7b) are disclosed in U.S. Patent Publication No. 2016 / 0152775, U.S. Patent No. 9,079,833, and U.S. Patent No. 9,663,619.
[0187] Sulfur-containing prepolymers may include sulfur-containing polyformal prepolymers or combinations thereof. Sulfur-containing polyformal prepolymers useful for sealant applications are disclosed in U.S. Patents 8,729,216 and 8,541,513.
[0188] The polysulfide prepolymer may include a polysulfide prepolymer containing the portion of formula (8), a thiol-terminated polysulfide prepolymer of formula (8a), a terminally modified polysulfide prepolymer of formula (8b), or any combination thereof. -(R 7 -O-CH2-OR 7 -S s -) g-1 -R 7 -O-CH2-OR 7 - (8) HS-(R7 -O-CH2-ORS s -) g-1 -R 7 -O-CH2-OR 7 -SH (8a) R 3 -S-(R 7 -O-CH2-OR 7 -S s -) g-1 -R 7 -O-CH2-OR 7 -SR 3 (8b) In the formula, R 7 is C 2~4 It is an alkanediyl, where s is an integer from 1 to 8, g is an integer from 2 to 370, and each R 3 This is a portion that independently contains terminally reactive functional groups.
[0189] The portion of formula (8) and the prepolymers of formulas (8a) to (8b) are disclosed in JP62-53354.
[0190] Sulfur-containing polyformal The sulfur-containing polyformal prepolymer may include the portion of formula (9), the thiol-terminated sulfur-containing polyformal prepolymer of formula (9a), the terminally modified sulfur-containing polyformal prepolymer of formula (9b), the thiol-terminated sulfur-containing polyformal prepolymer of formula (9c), the terminally modified sulfur-containing polyformal prepolymer of formula (9d), or any combination 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) {R 3 -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) In the formula, h can be an integer from 1 to 50, and each v can be independently selected from 1 and 2, and each R 8 C 2~6 It can be an alkandiyl, each R 9 These are, independently, hydrogen and 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 A selection may be made from the aryl, each R 10 This is the part containing the terminal thiol group, and each R3 This is a molar containing terminally reactive functional groups other than thiol groups, and Z is the m-valent parent polyol Z(OH) m It may originate from the core.
[0191] monosulfide Sulfur-containing prepolymers may include monosulfide prepolymers or combinations of monosulfide prepolymers.
[0192] The monosulfide prepolymer may include the portion of formula (10), the thiol-terminated monosulfide prepolymer of formula (10a), the thiol-terminated monosulfide prepolymer of formula (10b), the terminally modified monosulfide prepolymer of formula (10c), the terminally modified monosulfide prepolymer of formula (10d), or any combination thereof. -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 Independently, C 2~10 Alkanedyl, for example, C 2~6 Arcandil; C 2~10 Branched alkanedyls, 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 Selected from alkylarenediyl, Each R 12 These are, independently, hydrogen and C 1~10 n-alkanediyl, for example, C 1~6 n-alkanediyl, C 2~10 Branched alkanediyl, for example, 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 Selected from alkylarenediyl, Each R 13 These are, independently, hydrogen and C 1~10 n-alkanediyl, for example, C 1~6 n-alkanediyl, C 2~10 Branched alkanediyl, for example, C having one or more pendant groups which may be alkyl groups such as methyl or ethyl groups. 3~6Branched alkanediyl; C 6~8 Cycloalkanediyl group; C 6~14 Alkylcycloalkanediyl, for example, C 6~10 Alkylcycloalkanediyl; and C 8~10 Selected from alkylarenediyl, Each X can be independently selected from O and S. w can be an integer from 1 to 5. u can be an integer between 0 and 5. x can be an integer from 1 to 60, for example, 2 to 60, 3 to 60, or 25 to 35. Each R 3 These are independently selected from reactive functional groups, B is a z-valent polyfunctionalizing agent B(-V). z It represents the core, and in the formula, z can be an integer between 3 and 6. Each V may be a moiety containing a reactive terminal group to the thiol group, Each -V'- can originate from a reaction between -V and a thiol.
[0193] A method for synthesizing thiol-terminated monosulfides containing a portion of formula (10) or prepolymers of formulas (10b) to (10c) is disclosed in U.S. Patent No. 7,875,666.
[0194] The monosulfide prepolymer may include a thiol-terminated monosulfide prepolymer containing the portion of formula (11) or the portion 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 any combination 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'-} z B (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 Independently, C 2~10 Alkanedyl, for example, C 2~6 Arcandil; C 3~10 Branched alkanedyls, 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 Selected from alkylarenediyl, Each R 15 These are, independently, hydrogen and C 1~10 n-alkanediyl, for example, C 1~6 n-alkanediyl, C 3~10Branched alkanediyl, for example, 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 Selected from alkylarenediyl, Each X can be independently selected from O and S. w can be an integer from 1 to 5. u can be an integer from 1 to 5. x can be an integer from 1 to 60, for example, 2 to 60, 3 to 60, or 25 to 35. Each R 3 This is the part containing the terminal functional group, B is a z-valent polyfunctionalizing agent B(-V). z It represents the core, and in the formula, z can be an integer between 3 and 6. Each V may be a moiety containing a reactive terminal group to the thiol group, Each -V'- can originate from a reaction between -V and a thiol.
[0195] A method for synthesizing the monosulfides of formulas (11) to (11d) is disclosed in U.S. Patent No. 8,466,220.
[0196] Co-reactive groups The co-reactive 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, the tack-free time being determined according to AS5127 / 1(5.8) (Aerospace Standard Test Methods for Aerospace Sealants).
[0197] A coreactive composition for forming a linear sealing component exhibiting a fast hardening time to Shore 10A may comprise a coreactive agent having a fast-curing chemical, a system curable by chemical radiation, a catalyst, and any combination thereof.
[0198] The cured composition can achieve a Shore hardness of 10A in less than 10 minutes, and the hardness is determined according to ISO 868 at 23°C / 55% relative humidity.
[0199] Coreactive compositions for forming linear sealing components that exhibit conductivity, EMI / RFI shielding, and / or electrostatic dissipation may include conductive fillers or combinations of conductive fillers.
[0200] additives Co-reactive compositions may contain one or more additives, such as catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, fillers, colorants, photochromic agents, rheology modifiers, reactive diluents, curing activators and accelerators, corrosion inhibitors, fire retardants, UV stabilizers, rain erosion inhibitors, or any combination of the above.
[0201] catalyst The coreactive composition may include a catalyst or a combination of catalysts, one or more catalysts selected to catalyze a reaction between coreactants in the coreactive composition, such as a first coreactive compound and a second coreactive compound.
[0202] A catalyst or combination of catalysts may be selected to catalyze the reaction of coreactants in a coreactive composition, such as the reaction of a first compound and a second compound. Suitable catalysts may include amine catalysts, depending on the curing chemical, such as thiol-ene or thiol epoxy.
[0203] The co-reactive composition may contain 0.1% to 1% by weight, 0.2% to 0.9% by weight, 0.3% to 0.7% by weight, or 0.4% to 0.6% by weight of a catalyst or combination of catalysts, where the weight percentage is based on the total weight of the co-reactive composition.
[0204] The catalyst may include a latent catalyst or a combination of latent catalysts. Latent catalysts include catalysts that are little to no activity until released or activated by physical and / or chemical mechanisms. Latent catalysts may be contained within the structure or chemically blocked. Controlled-release catalysts may release catalyst upon exposure to ultraviolet light, heat, ultrasound, or moisture. Latent catalysts may be sequestered within a core-shell structure or trapped within a matrix of crystalline or semi-crystalline polymers, and the catalyst may diffuse from the inclusion over time or upon activation, such as by the application of thermal or mechanical energy.
[0205] Co-reactive compositions may include dark-curing catalysts or combinations of dark-curing catalysts. A dark-curing catalyst refers to a catalyst that can generate free radicals without exposure to electromagnetic energy.
[0206] Examples of dark-curing catalysts include combinations of metal complexes and organic peroxides, trialkylborane complexes and peroxide-amine redox initiators. Dark-curing catalysts may be used in combination with photopolymerization initiators or independently of them.
[0207] curing agent Co-reactive compositions based on thiol / thiol curing chemical reactions may include a curing activator or a combination of curing activators to initiate the thiol / thiol polymerization reaction. The curing activator may be used in a co-reactive composition in which both the first and second compounds include a thiol-terminated sulfur-containing prepolymer, such as a thiol-terminated polysulfide prepolymer.
[0208] The curing agent may include an oxidizing agent capable of oxidizing terminal mercaptan groups to form disulfide bonds. Suitable oxidizing agents include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, and dichromate.
[0209] The curing agent 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 (PbO3), manganese dioxide (MnO2), sodium perborate (NaBO3·H2O), potassium permanganate (KMnO4), calcium peroxide (CaCO3), barium peroxide (BaO3), cumene hydroperoxide, and any combination of the above. The curing activator may be MnO2.
[0211] Co-reactive compositions based on thiol / thiol curing chemical reactions may contain 1% to 10% by weight of a curing activator or combination of curing activators, where the weight percentage is based on the total weight of the composition. Co-reactive compositions may contain 1% to 9% by weight, 2% to 8% by weight, 3% to 7% by weight, or 4% to 6% by weight of an activator or combination of curing activators, where the weight percentage is based on the total weight of the composition. Co-reactive compositions may contain more than 1% by weight, more than 2% by weight, more than 3% by weight, more than 4% by weight, more than 5% by weight, or more than 6% by weight of a curing activator or combination of curing activators, where the weight percentage is based on the total weight of the composition.
[0212] Co-reactive compositions based on thiol / thiol curing chemical reactions may include curing accelerators or combinations of curing accelerators.
[0213] The curing accelerator can act as a sulfur donor, generating active sulfur fragments that can react with the terminal thiol groups of the thiol-terminated polysulfide prepolymer.
[0214] Suitable curing accelerators may include thiazoles, thirams, sulfenamides, guanidines, dithiocarbamates, xanthetes, thioureas, aldehyde amines, and any combination thereof.
[0215] The curing accelerator may be thiuram polysulfide, thiuram disulfide, or a combination thereof.
[0216] Other suitable curing accelerators include triazines, as well as sulfides or metal salts and amine salts of dialkyldithiophosphates and dithiophosphates, for example, triazines, as well as sulfides or metal salts and amine salts of dialkyldithiophosphates, and any combination of the above. Non-sulfur-containing curing accelerators include tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water, and bases.
[0217] Co-reactive compositions may contain 0.01% to 2% by weight of a curing accelerator or combination of curing accelerators, 0.05% to 1.8% by weight, 0.1% to 1.6% by weight, or 0.5% to 1.5% by weight of a curing accelerator or combination of curing accelerators, where the weight percentage is based on the total weight of the composition. Co-reactive compositions may contain less than 2% by weight, less than 1.8% by weight, less than 1.6% by weight, less than 1.4% by weight, less than 1.2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or less than 0.05% by weight of a curing accelerator or combination of curing accelerators, where the weight percentage is based on the total weight of the composition.
[0218] Adhesion promoter Co-reactive compositions may include adhesion promoters or combinations of adhesion promoters. Adhesion promoters can enhance the adhesion of the co-reactive composition to substrates such as metals, composites, polymers, or ceramic surfaces, or to coatings such as primer coatings or other coating layers. Adhesion promoters can enhance adhesion to cabin panels.
[0219] Adhesion promoters may include phenolic adhesion promoters, combinations of phenolic adhesion promoters, organic functional silanes, combinations of organic functional silanes, or any combination of the above. Organic functional alkoxysilanes may be amine functional alkoxysilanes. The organo group may be selected from thiol groups, amine groups, hydroxyl groups, silanol groups, epoxy groups, alkynyl groups, alkenyl groups, isocyanate groups, or Michael acceptor groups.
[0220] Phenolic adhesion promoters may include heat-treated phenolic resins, unheat-treated phenolic resins, or combinations thereof. Suitable adhesion promoters include phenolic resins such as Methylon® phenolic resins, and organosilanes such as epoxy, mercapto, or amine-functionalized silanes, such as Silquest® organosilanes. Heat-treated phenolic resins refer to phenolic resins that have been co-reacted with monomers, oligomers, and / or prepolymers.
[0221] Phenolic adhesion promoters may contain reaction products from the condensation reaction of a phenolic resin with one or more thiol-terminated polysulfides. Phenolic adhesion promoters may be thiol-terminated.
[0222] Suitable phenolic resins include 2-(hydroxymethyl)phenol, (4-hydroxy-1,3-phenylene)dimethanol, (2-hydroxybenzene-1,3,4-triyl)trimethanol, 2-benzyl-6-(hydroxymethyl)phenol, (4-hydroxy-5-((2-hydroxy-5-(hydroxymethyl)cyclohexa-2,4-dien-1-yl)methyl)-1,3-phenylene)dimethanol, (4-hydroxy-5-((2-hydroxy-3,5-bis(hydroxymethyl)cyclohexa-2,4-dien-1-yl)methyl)-1,3-phenylene)dimethanol, and any combination of the above. Suitable phenolic resins can be synthesized by a base-catalyzed reaction of phenol and formaldehyde. Phenolic adhesion promoters may include reaction products of condensation reactions between Methylon® resin, Varcum® resin, or Durez® resin available from Durez Corporation and thiol-terminated polysulfides such as Thioplast® resin. Examples of Methylon® resins include Methylon® 75108 (allyl ether of methylrollphenol, see U.S. Patent No. 3,517,082) and Methylon® 75202. Examples of Varcum® resins include Varcum® 29101, Varcum® 29108, Varcum® 29112, Varcum® 29116, Varcum® 29008, Varcum® 29202, Varcum® 29401, Varcum® 29159, Varcum® 29181, Varcum® 92600, Varcum® 94635, Varcum® 94879, and Varcum® 94917. S Durez® resin may be Durez® 34071.
[0223] The co-reactive composition may contain an organic functional alkoxysilane adhesion promoter, such as an organic functional alkoxysilane. The organic functional alkoxysilane may contain a hydrolyzable group bonded to a silicon atom and at least one organic functional group. The organic functional alkoxysilane has structure R a -(CH2) n -Si(-OR) 3-n R n It may have R a is an organic functional group, where n is 0, 1, or 2, and R is an alkyl group such as methyl or ethyl. The organic functional group may include epoxy, amino, methacrylate, or sulfide groups. An organically functional alkoxysilane may be a dipodal alkoxysilane having two or more alkoxysilane groups, a functional dipodal alkoxysilane, a non-functional dipodal alkoxysilane, or any combination of the aforementioned. An organically functional alkoxysilane may be a combination of a monoalkoxysilane and a dipodal alkoxysilane.
[0224] Suitable amino-functional alkoxysilanes under the trademark name Silquest® 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), Si Examples 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 Co-reactive compositions may include fillers or combinations of fillers. Fillers may include inorganic fillers, organic fillers, low-density fillers, conductive fillers, or any combination of the aforementioned.
[0226] Coreactive compositions for forming linear sealing components may include inorganic fillers or combinations of inorganic fillers.
[0227] Inorganic fillers may be included to provide mechanical strengthening 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 increasing impact strength, controlling viscosity, and / or modifying the electrical properties of the cured composition.
[0228] Useful inorganic fillers in co-reactive compositions include carbon black, calcium carbonate, precipitated calcium carbonate, calcium hydroxide, hydrated alumina (aluminum hydroxide), talc, mica, titanium dioxide, alumina silicate, carbonate, chalk, silicate, glass, metal oxides, graphite, and any combination of the above.
[0229] Suitable calcium carbonate fillers include products available from Solvay Special Chemicals such as Socal® 31, Socal® 312, Socal® U1S1, Socal® UaS2, Socal® N2R, Winnofil® SPM, and Winnofil® SPT. Calcium carbonate fillers may include combinations of precipitated calcium carbonate.
[0230] Inorganic fillers can be surface-treated to provide hydrophobic or hydrophilic surfaces that promote the dispersion of the inorganic filler and its compatibility with other components of the co-reactive composition. The inorganic filler may include surface-modified particles, such as surface-modified silica. The surface of the silica particles may be modified to adjust the hydrophobicity or hydrophilicity of the silica particle surface. Surface modification may affect the dispersibility, viscosity, curing rate, and / or adhesion of the particles.
[0231] Co-reactive compositions may include organic fillers or combinations of organic fillers.
[0232] Organic fillers may be selected to have a low specific gravity, be resistant to solvents such as JRF type I, and / or reduce the density of the sealant layer. Suitable organic fillers may also have acceptable adhesion to sulfur-containing polymer matrices. Organic fillers may include solid powders or particles, hollow powders or particles, or combinations thereof.
[0233] Organic fillers may have specific gravities 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. Organic fillers may have specific gravities in the range of 0.85 to 1.15, 0.9 to 1.1, 0.9 to 1.05, or 0.85 to 1.05.
[0234] Organic fillers may include thermoplastics, thermosettings, or combinations thereof. Suitable thermoplastics and thermosettings include epoxy, epoxyamides, ETFE copolymers, nylon, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylidene chloride, polyvinyl fluoride, TFE, polyamides, polyimides, ethylene propylene, perfluorohydrocarbons, fluoroethylene, polycarbonates, polyether ether ketones, polyether ketones, polyphenylene oxide, polyphenylene sulfide, polystyrene, polyvinyl chloride, melamine, polyesters, phenolic compounds, epichlorohydrins, fluorinated hydrocarbons, polycyclic compounds, polybutadiene, polychloroprene, polyisoprene, polysulfide, polyurethanes, isobutylene isoprene, silicones, styrene butadiene, liquid crystal polymers, or any combination of the above.
[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 trademark name Orgasol® and from Evonik Industries under the trademark name Vestosin®.
[0236] The organic filler may have any preferred shape. The organic filler may contain a fraction of filtered, pulverized polymer to select a desired size range. The organic filler may contain substantially spherical particles. The particles may be solid or porous.
[0237] Organic fillers may have average particle sizes in the ranges 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. Organic fillers may also have average particle sizes less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm, or less than 20 μm. The particle size distribution can be determined by using a Fischer subsieve sizer or by optical inspection.
[0238] low density filler Coreactive compositions for forming low-density linear sealing components may include low-density fillers such as low-density organic fillers, hollow microparticles, coated microparticles, or any combination thereof. Low-density fillers may also be called lightweight fillers.
[0239] Linear sealing components may exhibit specific gravities such as less than 1.1, less than 1.0, less than 0.9, less than 0.8, or less than 0.7, and the specific gravity is determined according to ISO 2781 at 23°C / 55%RH.
[0240] The organic filler may include low-density microcapsules such as modified expandable thermoplastic microcapsules. Preferred modified expandable thermoplastic microcapsules may include an outer coating of melamine or urea / formaldehyde resin. The co-reactive composition may include low-density microcapsules. Low-density microcapsules may include thermally expandable microcapsules.
[0241] A thermally expandable microcapsule refers to a hollow shell 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, and in some cases 10 μm to 24 μm, or 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 any microcapsule before expansion. The particle size distribution can be determined by using a Fischer subsieve sizer or by optical inspection.
[0242] Suitable materials for forming the walls of thermally expandable microcapsules include polymers of vinylidene chloride, acrylonitrile, styrene, polycarbonate, methyl methacrylate, ethyl acrylate, and vinyl acetate, copolymers of these monomers, and combinations of these polymers and copolymers. Crosslinking agents may be included together with the materials forming the walls of the thermally expandable microcapsules.
[0243] Suitable thermoplastic microcapsules include ExpanseL® microcapsules, such as ExpanseL® DE nanoparticles available from AkzoNobel. Suitable ExpanseL® DE nanoparticles include ExpanseL® 920DE40 and ExpanseL® 920DE80. Suitable low-density microcapsules are also available from Kureha Corporation.
[0244] Low-density fillers, such as low-density microcapsules, can be characterized by specific gravities within the ranges of 0.01 to 0.09, 0.04 to 0.09, 0.04 to 0.08, 0.01 to 0.07, 0.02 to 0.06, 0.03 to 0.05, 0.05 to 0.09, 0.06 to 0.09, or 0.07 to 0.09, with the specific gravity determined according to ASTM D1475. Low-density fillers, such as low-density microcapsules, can also be characterized by specific gravities 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, with the specific gravity determined according to ASTM D1475.
[0245] Low-density fillers, such as low microcapsules, can 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 microcapsules, can be characterized by an average particle diameter of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm when determined according to ASTM D1475.
[0246] Low-density fillers, such as low-density microcapsules, may include inflatable microcapsules or microballoons having a coating of an aminoplast resin, such as melamine resin. Particles coated with aminoplast resin are described in U.S. Patent No. 8,993,691. Such microcapsules can be formed by heating microcapsules containing a foaming agent surrounded by a thermoplastic shell. Uncoated low-density microcapsules can be reacted with an aminoplast resin, such as urea / formaldehyde resin, to provide a thermosetting resin coating on the outer surface of the particles.
[0247] By coating with aminoplast resin, the aminoplast-coated microcapsules may be characterized by having a specific gravity in the range of 0.02-0.08, 0.02-0.07, 0.02-0.06, 0.03-0.07, 0.03-0.065, 0.04-0.065, 0.045-0.06, or 0.05-0.06, and the specific gravity is determined according to ASTM D1475.
[0248] The co-reactive 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 trademark name ACumist®, from INEOS under the trademark name Eltrex®, and from Mitsui Chemicals America, Inc. under the trademark name Mipelon®.
[0249] The co-reactive composition may contain 1% to 90% by weight of low-density filler, 1% to 60% by weight, 1% to 40% by weight, 1% to 20% by weight, 1% to 10% by weight, or 1% to 5% by weight of low-density filler, where the weight percentage is based on the total weight of the composition.
[0250] The co-reactive composition may contain more than 1% by weight of low-density filler, more than 1% by weight, more than 2% by weight, more than 3% by weight, more than 4% by weight, more than 1% by weight, or more than 10% by weight of low-density filler, where the weight percentage is based on the total weight of the composition.
[0251] The co-reactive composition may contain 1% to 90% by volume of 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 low-density filler, where the volume percentage is based on the total volume of the co-reactive composition.
[0252] The co-reactive composition may contain more than 0.5 volume% of low-density filler, more than 1 volume%, more than 5 volume%, more than 10 volume%, more than 20 volume%, more than 30 volume%, more than 40 volume%, more than 50 volume%, more than 60 volume%, more than 70 volume%, or more than 80 volume%, where the volume percentage is based on the total volume of the co-reactive composition.
[0253] Conductive filler Co-reactive compositions may include conductive fillers or combinations of conductive fillers. Conductive fillers may include conductive fillers, semiconducting fillers, thermally conductive fillers, magnetic fillers, EMI / RFI shielding fillers, electrostatic dissipative fillers, electroactive fillers, or any combination of the above.
[0254] Suitable conductive fillers include metals, metal alloys, conductive oxides, semiconductors, carbon, carbon fibers, and any combination of the aforementioned.
[0255] Other conductive fillers may include electrically conductive precious metal fillers such as pure silver; precious metals plated with 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 nanoparticles, precious metal-plated aluminum, or precious metal-plated plastic nanoparticles; precious metal-plated mica; and other such precious metal conductive fillers. Non-precious metal materials may also be used, such as 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. The combination and shape of conductive fillers may be used to achieve the desired conductivity, EMI / RFI shielding effect, hardness, and other properties suitable for specific applications.
[0256] The amount and type of conductive filler should result in a conductivity of 0.50 Ω / cm² when cured. 2 Sheet resistance less than 0.15Ω / cm (4-point resistance) 2 Co-reactive compositions may be selected to produce a sheet resistance of less than 1 MHz. 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 co-reactive composition.
[0257] Conductive fillers can be provided by coating organic fillers, inorganic fillers, and low-density fillers with metal.
[0258] The conductive filler may contain graphene. Graphene is composed of sp(s) arranged in a two-dimensional lattice, with a thickness equal to the atomic size of a single carbon atom. 2 It includes a densely packed honeycomb crystal lattice made of carbon atoms, having a monolayer of hybridized carbon atoms.
[0259] Conductive fillers may include magnetic fillers or combinations of magnetic fillers.
[0260] Magnetic fillers may include soft magnetic metals. This can enhance the permeability of the magnetic molding resin. As the main component of the soft magnetic metal, at least one magnetic material selected from Fe, Fe-Co, Fe-Ni, Fe-Al, and Fe-Si may be used. The magnetic filler may be a soft magnetic metal with high bulk permeability. The at least one magnetic material selected as the soft magnetic metal may be Fe, FeCo, FeNi, FeAl, and FeSi, and may be used as permalloy (FeNi alloy), superpermalloy (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, Sm2Co 17Possible examples include powders, Nd-B-Fe powder, barium ferrite BaFe2O4, bismuth ferrite BiFeO3, chromium dioxide CrO2, SmFeN, NdFeB, and SmCo.
[0261] Reactive diluent Co-reactive compositions may include hydroxyl-functional vinyl ethers or combinations of hydroxyl-functional vinyl ethers. Reactive diluents can be used to reduce the viscosity of the composition. Reactive diluents are low molecular weight compounds, such as those with a molecular weight of less than 400 Da, having at least one functional group capable of reacting with at least one of the main reactants of the composition, and can be part of a crosslinking network. Reactive diluents may have one or two functional groups. Reactive diluents may be used to control the viscosity of the composition or to improve the wetting of fillers in the co-reactive composition.
[0262] A hydroxyl-functional vinyl ether may have formula (12), CH2=CH-O-(CH2) t -OH (12) In the formula, t is an integer between 2 and 10. In the hydroxyl-functional vinyl ether of formula (12), t may be 1, 2, 3, 4, 5, or t may be 6. Suitable hydroxyl-functional vinyl ethers include 1-methyl-3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and combinations thereof. The hydroxyl-functional vinyl ether may be 4-hydroxybutyl vinyl ether.
[0263] The co-reactive composition may contain 0.1% to 10% by weight, 0.2% to 9% by weight, 0.3% to 0.7% by weight, and 0.4% to 0.7% by weight of hydroxyl-functionalized vinyl ether, where the weight percentage is based on the total weight of the curable composition.
[0264] The co-reactive 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 may have the structure of formula (13), CH2=CH-O-(CH2) w -NH2(13) In the formula, w is an integer between 2 and 10. In the amino-functional vinyl ether of formula (13), w may be 1, 2, 3, 4, or 5, or t may be 6. Suitable amino-functional vinyl ethers include 1-methyl-3-aminopropyl vinyl ether, 4-aminobutyl vinyl ether, and any combination of the aforementioned. The amino-functional vinyl ether may be 4-aminobutyl vinyl ether as a reactive diluent. The co-reactive composition may contain 0.1% to 10% by weight, 0.2% to 9% by weight, 0.3% to 0.7% by weight, and 0.4% to 0.7% by weight of amino-functional vinyl ether, where the weight percentage is based on the total weight of the co-reactive composition.
[0266] The co-reactive composition may include, as a reactive diluent, styrene, α-methylstyrene, and vinyl-based diluents such as para-vinyltoluene; vinyl acetate; and / or n-vinylpyrrolidone.
[0267] plasticizer Co-reactive compositions may contain plasticizers or combinations of plasticizers. Plasticizers may be included to adjust the viscosity of the composition and to facilitate application.
[0268] Suitable plasticizers include phthalates, terephthalic acid, isophthalic acid, hydrogenated terphenyl, quaterphenyl and higher polyphenyls, phthalate esters, chlorinated paraffin, modified polyphenyls, tung oil, benzoates, dibenzoates, thermoplastic polyurethane plasticizers, phthalate esters, naphthalene sulfonates, trimellitates, adipates, sebacates, maleates, sulfonamides, organic phosphates, polybutenes, butyl acetates, butyl cellosolve, butyl carbitol acetates, dipentenes, tributyl phosphates, hexadecanol, diallyl phthalate, sucrose acetate isobutyrate, epoxy esters of isooctyl phthalate, benzophenone, and any combination of the above.
[0269] The co-reactive composition may contain 0.5% to 7% by weight of a plasticizer or combination of plasticizers, 1% to 6% by weight, 2% to 5% by weight, or 2% to 4% by weight of a plasticizer or combination of plasticizers, where the weight percentage is based on the total weight of the co-reactive composition.
[0270] The co-reactive composition may contain less than 8% by weight of a plasticizer, less than 6% by weight, less than 4% by weight, or less than 2% by weight of a plasticizer or combination of plasticizers, where the weight percentage is based on the total weight of the co-reactive composition.
[0271] Photochromic agents Co-reactive compositions may contain photochromic agents sensitive to the degree of curing or exposure to chemical radiation. Curing indicators may change color upon exposure to chemical radiation, and this change may be permanent or reversible. Curing indicators may be initially transparent and become colored upon exposure to chemical radiation, or they may be initially colored and become transparent upon exposure to chemical radiation.
[0272] Corrosion inhibitor The coreactive compositions provided by this disclosure may include a corrosion inhibitor or a combination of corrosion inhibitors.
[0273] Suitable corrosion inhibitors include zinc phosphate-based corrosion inhibitors, lithium silicate corrosion inhibitors such as lithium orthosilicate (Li4SiO4) and lithium metasilicate (Li2SiO3), MgO, azoles, monomeric amino acids, dimeric amino acids, oligomeric amino acids, nitrogen-containing heterocyclic compounds (such as azoles, oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, indidines and triazines, tetrazoles, and / or tolyltriazoles), corrosion-resistant particles such as inorganic oxide particles (including zinc oxide (ZnO), magnesium oxide (MgO), cerium oxide (CeO2), molybdenum oxide (MoO3), and / or silicon dioxide (SiO2)), and any combination of the above.
[0274] The co-reactive composition may contain less than 5% by weight of a corrosion inhibitor or combination of corrosion inhibitors, less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight of a corrosion inhibitor or combination of corrosion inhibitors, where the weight percentage is based on the total weight of the co-reactive composition.
[0275] Fire retardant Coreactive compositions may include fire retardants or combinations of fire retardants.
[0276] Examples of fire retardants include inorganic fire retardants, organic fire retardants, or combinations thereof.
[0277] Suitable inorganic fire retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, antimony oxide, hydromagnesite, aluminum trihydrate (ATH), calcium phosphate, titanium dioxide, zinc oxide, magnesium carbonate, barium sulfate, barium borate, kaolinite, silica, antimony oxide, and any combination of the aforementioned.
[0278] Suitable organic fire retardants include halocarbons, halogenated esters, halogenated ethers, chlorinated and / or brominated flame retardants, halogen-free compounds such as organophosphorus compounds and organic nitrogen compounds, and any combination of the aforementioned. The fire retardants may be in solid (e.g., powder) or liquid form.
[0279] The co-reactive composition may contain 1% to 30% by weight of a flame retardant or a combination of flame retardants, for example, 1% to 20% by weight or 1% to 10% by weight, based on the total weight of the co-reactive composition. The co-reactive composition may contain less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, or less than 2% by weight of a flame retardant or a combination of flame retardants, based on the total weight of the co-reactive composition.
[0280] Moisture control additive The co-reactive composition may include a moisture-controlling additive or a combination of moisture-controlling additives.
[0281] Suitable moisture control additives include synthetic zeolites, activated alumina, silica gel, calcium oxide, magnesium oxide, molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, alkoxysilanes, and any combination of the aforementioned.
[0282] The co-reactive composition may contain less than 5% by weight of a moisture control additive or combination of moisture control additives, less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight of a moisture control additive or combination of moisture control additives, where the weight percentage is based on the total weight of the co-reactive composition.
[0283] UV stabilizer Co-reactive compositions may include UV stabilizers or combinations of UV stabilizers. UV stabilizers may include UV absorbers and hindered amine light stabilizers. Suitable UV stabilizers include products with the trademark names Cyasorb® (Solvay), Uvinul® (BASF), and Tinuvin® (BASF).
[0284] Additive manufacturing of linear sealing components Figure 4 is a simplified diagram illustrating a method 400 for additive manufacturing of linear sealing components. Method 400 includes a process 402 for transporting a first co-reactive component and a second co-reactive component into a mixing chamber; a process 404 for mixing the first co-reactive component and the second co-reactive component to form a reactive mixture; a process 406 for depositing the reactive mixture layer by layer to form an elongated body; and a process 408 for curing the deposited reactive mixture via a chemical source. The foregoing is presented using a selected group of processes for the method, but many alternatives, modifications, and variations are possible. Some of the processes can be extended and / or combined. Other processes can be inserted into those listed above. Some processes can be deleted or replaced. Depending on the embodiment, the order of the processes can be replaced.
[0285] Process 402 for transporting the first co-reactive component and the second co-reactive component to a mixing chamber may include transporting the first co-reactive component from a first reservoir (e.g., by pumping) and transporting the second co-reactive component from a second reservoir to a mixing chamber (e.g., by pumping). 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 any combination thereof. The first co-reactive component may include a thiol-terminated polythioether. The second co-reactive component may include a polyemen prepolymer, which may be a polyvinyl ether. The first co-reactive component and / or the second co-reactive component may further include flame-retardant filler particles, rheology-modified filler particles (e.g., organic and / or inorganic), lightweight filler particles, and / or sound-dampening filler particles.
[0286] Process 404, which mixes a first co-reactive component and a second co-reactive component to form a reactive mixture, may include actively (e.g., via a propeller) and / or passively (e.g., via the static structure of the chamber) mixing the co-reactive components to form a homogeneous reactive mixture. The reactive mixture may be partially cured in the mixing chamber before deposition to obtain desired rheological characteristics and / or self-supporting strength (e.g., to enable overhang printing and / or to prevent gravity-induced deformation such as sagging). In some situations, bubbles may be removed from the reactive mixture before deposition so that printing defects that may result in acoustically weak points (e.g., acoustically leaky points) can be minimized.
[0287] Process 406 for depositing a reactive mixture layer by layer to form an elongated body may include using a controller (e.g., a computer) to guide an extrusion nozzle and applying pressure (or more) to a mixing chamber (e.g., by pressurizing a reservoir connected thereto) to extrude the reactive mixture to form an elongated body of a linear sealing component.
[0288] Process 408 for curing a deposited reactive mixture via a chemical source may include exposing the reactive mixture extruded from an elongated body and / or extrusion nozzle to a chemical beam (e.g., ultraviolet light) during and / or after deposition. The mixing chamber may be chemically permeable so that the chemical beam can be applied while the reactive mixture is inside the mixing chamber to partially cure the reactive mixture before deposition. The chemical source may be spaced 20 to 30 inches, for example, 23 inches, from the extrusion nozzle and / or mixing chamber. The chemical source may be covered with a layer of polarizing film facing the direction of the extrusion nozzle. The chemical source may be 230 mW / cm². 2 This could be a 395nm ultraviolet lamp with a baseline intensity. Once the linear sealing component is printed, deposition is stopped and a secondary curing step can be implemented for at least 30 minutes using the same 395nm ultraviolet lamp in a chamber lined with aluminum foil. Upon curing, the elongated body may have a porous structure, such as a closed porous structure within its walls.
[0289] Linear sealing components can be fabricated using co-reactive three-dimensional printing.
[0290] Co-reactive 3D 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 3D printing, a portion of the co-reactive composition can be pumped into a 3D printing apparatus, 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. Once mixed, the co-reactive compounds can react and begin to cure at temperatures below 30°C, for example, 20°C to 25°C, forming a thermosetting polymer matrix. Alternatively, after mixing, the co-reactive compounds may not react initially 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 system for manufacturing parts may include one or more pumps, one or more mixers, and one or more nozzles. One or more co-reactive compositions can be pumped into one or more mixers and, under pressure, passed through one or more nozzles directed to a surface or a pre-coated layer.
[0292] The three-dimensional printing equipment may 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] A three-dimensional printing apparatus may be equipped with a construction device for moving a nozzle in three dimensions relative to a surface. The movement of the three-dimensional printing apparatus may be controlled by a processor.
[0294] Linear sealing components can be manufactured by depositing a co-reactive composition containing at least two co-reactive components, and then depositing additional portions or layers of the co-reactive composition on the deposited portion or layer below and / or adjacent already deposited portion or layer to form a continuous portion or layer of the article. Layers may be deposited continuously on and / or adjacent to pre-deposited layers to construct a sound-insulating portion. The co-reactive composition may be mixed and then deposited, or the co-reactive components may be deposited separately. If deposited separately, the co-reactive components may be deposited simultaneously, continuously, or both simultaneously and continuously.
[0295] Co-reactive compositions can be deposited using any suitable co-reactive 3D printing apparatus. The selection of a suitable co-reactive 3D printing apparatus may depend on several factors, including the deposition volume, viscosity of the co-reactive composition, deposition rate, reaction rate of the co-reactive compounds, and the complexity and size of the chemical-resistant parts to be manufactured. Each of two or more co-reactive components can be introduced into an independent pump and injected into a mixer to combine and mix the two co-reactive components to form a co-reactive composition. A nozzle can be coupled to the mixer, and the mixed co-reactive composition can be passed through the nozzle under pressure or extruded through the nozzle.
[0296] The pump may be a positive displacement pump, syringe pump, piston pump, or progressive cavity pump. Two pumps delivering 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 a mixer using two pumps in series.
[0297] Two or more co-reactive components may be deposited by distributing the material through disposable nozzles attached to a progressive cavity two-component system in which the co-reactive components are mixed in-line. The two-component system may include two progressive cavity pumps that separately administer the co-reactive components to disposable static mixer-distributors or dynamic mixers. Other suitable pumps include positive displacement pumps, syringe pumps, piston pumps, and progressive cavity pumps. After mixing to form a co-reactive composition, the co-reactive composition may be deposited on a base to provide an initial layer of chemical-resistant parts by passing the co-reactive composition under pressure through one or more dies and / or one or a nozzle, thereby forming an extruded and a continuous layer deposited on and / or adjacent to the pre-deposited layer. The deposition system may be positioned perpendicular to the base, but may also be set to any suitable angle for forming the extruded so that the extruded and the deposition system form an obtuse angle with the extruded, which is parallel to the base. An extruded product refers to a co-reactive composition obtained after mixing co-reactive components in a static or dynamic mixer. The extruded product can be formed 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 connected to construct a three-dimensional chemical-resistant part. The movement can be performed in a predetermined manner, which can be carried out using any suitable CAD / CAM method and apparatus, such as robotics and / or computerized machine tool interfaces.
[0299] Extruded materials formed by extruding a co-reactive composition through the nozzles of a three-dimensional printing apparatus can be deposited in any orientation. The nozzles can be directed downward, upward, laterally, or at any angle in between. In this way, the co-reactive composition can be deposited as a vertical wall or as an overhang. The extruded material can be deposited on a vertical wall, on the underside of an inclined wall, or on the bottom surface of a horizontal surface. By using extruded materials with a rapid-curing chemical reaction, the ability to deposit upper layers adjacent to lower layers can be enhanced so that angled surfaces can be produced. Angled surfaces can be inclined upward with respect to the horizontal, or inclined downward with respect to the horizontal.
[0300] The extruded material can be distributed continuously or intermittently to form an initial layer and a subsequent layer. For intermittent deposition, the deposition system may interface with a switch to shut off a pump, such as a progressive cavity pump, thereby interrupting the flow of the co-reactive composition.
[0301] The three-dimensional printing system may include an in-line static mixer and / or dynamic mixer, as well as a separate pressurized pump transport section for holding and supplying at least two co-reactive components to the static and / or dynamic mixer. Mixers, such as the active mixer, may feature a variable-speed central impeller with high-shear blades within the nozzle. Nozzles may be used with minimum dimensions in the following ranges: 0.2mm to 100mm, 0.5mm to 75mm, 1mm to 50mm, or 5mm to 25mm. Nozzles may have minimum dimensions such as greater than 1mm, greater than 2mm, greater than 5mm, greater than 10mm, greater than 20mm, greater than 30mm, greater than 40mm, greater than 50mm, greater than 60mm, greater than 70mm, greater than 80mm, or greater than 90mm. The nozzle may have minimum dimensions 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 dimensions such as circular, spherical, elliptical, rectangular, square, trapezoidal, triangular, planar, or other suitable shapes. The aspect ratio or ratio of the orthogonal dimensions may be any suitable dimension suitable for manufacturing chemical-resistant parts, such as 1:1, 1:2, 1:3, 1:5, or 1:10.
[0302] A series of static and / or dynamic mixing nozzles may be used, having outlet orifice dimensions of 0.6 mm to 2.5 mm and lengths of 30 mm to 150 mm. The outlet orifice diameter may be 0.2 mm to 4.0 mm, 0.4 mm to 3.0 mm, 0.6 mm to 2.5 mm, 0.8 mm to 2 mm, or 1.0 mm to 1.6 mm. The static and / or dynamic mixers may have lengths of 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 dispensing section coupled to the static and / or dynamic mixing section. The static and / or dynamic mixing section may be configured to combine and mix co-reactive materials. The dispensing section may be a straight tube having any of the aforementioned orifice diameters. The length of the dispensing section may be configured to provide a region in which the co-reactive components can initiate a reaction and build viscosity before being deposited in the article. The length of the distribution section can be selected based on the deposition rate, the reaction rate of the co-reactants, and the viscosity of the co-reactive composition.
[0303] Co-reactive compositions may have residence times in static and / or dynamic mixing nozzles of 0.25 to 5 seconds, 0.3 to 4 seconds, 0.5 to 3 seconds, or 1 to 3 seconds. Other residence times may be used as needed, based on the curing chemical reaction and curing rate.
[0304] Generally, a suitable residence time is less than the gelation time of the co-reactive composition.
[0305] The co-reactive composition may have a volumetric flow rate of 0.1 mL / min to 20,000 mL / min, for example, 1 mL / min to 12,000 mL / min, 5 mL / min to 8,000 mL / min, or 10 mL / min to 6,000 mL / min. The volumetric flow rate may depend on the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive compound.
[0306] Co-reactive compositions can be used at deposition rates of 1 mm / sec to 400 mm / sec, for example, 5 mm / sec to 300 mm / sec, 10 mm / sec to 200 mm / sec, or 15 mm / sec to 150 mm / sec. The deposition rate may depend on the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive compound. The deposition rate refers to the speed at which the nozzle used to extrude the co-reactive composition moves relative to the surface on which the co-reactive composition is deposited.
[0307] Static and / or dynamic mixing nozzles can be heated or cooled to control the reaction rate between co-reactive compounds and / or the viscosity of the co-reactive components. The orifice of the deposition nozzle can have any preferred shape and dimensions. The system may include multiple deposition nozzles. The nozzles may have fixed orifice dimensions and shapes, or the nozzle orifice can be controlled. The mixer and / or nozzles can be cooled to control the heat generated by the reaction of the co-reactive compounds.
[0308] The rate at which a co-reactive composition reacts to form a thermosetting polymer matrix can be determined and / or controlled by the selection of reactive functional groups in the co-reactive compound. The reaction rate can also be determined by factors that reduce the activation energy of the reaction, such as heat and / or catalysts.
[0309] The reaction rate can be reflected in the gelation time of the co-reactive composition. Rapid curing chemical reactions refer to chemical reactions in which the co-reactive compound has a gelation 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. Co-reactive compositions may have gelation times 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. The gelation time is the time after mixing the co-reactive components until the co-reactive composition can no longer be stirred by hand. The gelation time of a latent co-reactive composition refers to the time from when the curing reaction is first initiated until the co-reactive composition can no longer be stirred by hand.
[0310] Because the co-reactive components can be uniformly combined and mixed, the co-reactive composition can begin to harden immediately upon mixing of the dimensions of the co-reactive composition, and the extruded material passed through the nozzle is not particularly limited. Therefore, the production of co-reactive additives facilitates the use of large-dimensional extruded material, thereby promoting the ability to quickly produce both small and large seal caps.
[0311] Using a coreactive three-dimensional printing method, coreactive compositions can be deposited at speeds of 1 mm / sec to 400 mm / sec and / or at flow rates of 0.1 mL / min to 20,000 mL / min.
[0312] Embodiments of the present invention This disclosure may be further defined by one or more of the following embodiments:
[0313] Embodiment 1. Additive-manufactured sealing component comprising an elongated 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 defining a centerline, a first volume on the first side of the centerline, a second volume on the second side of the centerline, and a third volume between the first crescent-shaped recess and the second crescent-shaped recess, the third volume through which the centerline passes, wherein the first crescent-shaped recess comprises a first crescent-shaped recess opening, a first tip of the first volume, and a second Additively manufactured sealing component comprising a thermosetting polymer formed by: forming a coreactive mixture by mixing at least a first coreactive component and a second coreactive component; depositing the reactive mixture layer by layer to form an elongated body; and curing the deposited reactive mixture via a chemical source.
[0314] Embodiment 2. The additively manufactured sealing component according to Embodiment 1, wherein the first crescent-shaped recess and the second crescent-shaped recess are configured to receive panels having a thickness of 1 to 10 times the size of the recess opening of the crescent-shaped recess, respectively.
[0315] Embodiment 3. An additively manufactured sealing component according to Embodiment 1 or 2, wherein the first crescent-shaped recess and the second crescent-shaped recess extend along the entire length of the elongated body.
[0316] Embodiment 4. An additively manufactured sealing component according to any one of Embodiments 1 to 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 to 4, wherein the elongated body has a porous structure.
[0318] Embodiment 6. An additively manufactured sealing component according to any one of Embodiments 1 to 5, wherein the first crescent-shaped recess and the second crescent-shaped recess are triangular.
[0319] Embodiment 7. An additively manufactured sealing component according to any one of Embodiments 1 to 6, wherein the first crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the first crescent-shaped recess is received, 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 when a panel having a thickness greater than the opening of the second crescent-shaped recess is received, the third tip, the fourth tip, and the second wall secure the panel via three-point contact.
[0320] Embodiment 8. An additively manufactured sealing component according to any one of Embodiments 1 to 7, wherein the first crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the first crescent-shaped recess is received, the first tip and the second tip are elastically deformed to widen the opening of the first crescent-shaped recess, and the second crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the second crescent-shaped recess is received, the third tip and the fourth tip are elastically deformed to widen the opening of the second crescent-shaped recess.
[0321] Embodiment 9. An additively manufactured sealing component according to any one of Embodiments 1 to 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 to 9, wherein an elongated body is configured to receive a first panel in a first crescent-shaped recess and a second panel in a second crescent-shaped recess, and the distance between the first crescent-shaped recess and the second crescent-shaped recess is variable by at least twice the wall thickness of the sealing component.
[0323] Embodiment 11. An additively manufactured sealing component according to any one of Embodiments 1 to 10, wherein the first co-reactive component comprises a sulfur-containing prepolymer.
[0324] Embodiment 12. An additively manufactured sealing component according to Embodiment 11, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or any combination thereof.
[0325] Embodiment 13. The addition-manufactured sealing component according to Embodiment 12, wherein the polythioether is a thiol-terminated polythioether.
[0326] Embodiment 14. An additively manufactured sealing component according to any one of Embodiments 1 to 13, wherein the second co-reactive component comprises a polyemprepolymer.
[0327] Embodiment 15. The additively manufactured sealing component according to Embodiment 14, wherein the polyembrone polymer is a polyvinyl ether.
[0328] Embodiment 16. An additively manufactured sealing component according to any one of Embodiments 1 to 15, wherein at least one of the first co-reactive component and the second co-reactive component further comprises flame-retardant filler particles.
[0329] Embodiment 17. An additively manufactured sealing component according to any one of Embodiments 1 to 16, wherein at least one of the first co-reactive component and the second co-reactive component further comprises rheologically modified filler particles.
[0330] Embodiment 18. The additively manufactured sealing component according to Embodiment 17, wherein the rheologically modified filler particles include organic filler particles or inorganic filler particles.
[0331] Embodiment 19. An additively manufactured sealing component according to any one of Embodiments 1 to 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. An additively manufactured sealing component according to any one of Embodiments 1 to 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 recess and a second crescent recess opposite to the first crescent recess, wherein the first crescent recess and the second crescent recess define a centerline, the first crescent recess is firmly fixed to the first panel, and the second crescent recess is firmly fixed to the second panel, a first volume on the first side of the centerline, a second volume on the second side of the centerline, and a third volume between the first crescent recess and the second crescent recess, such that the centerline passes through the third volume, wherein the first crescent recess has an opening for the first crescent recess and a first tip of the first volume An aircraft component comprising a thermosetting polymer formed by: forming a reactive mixture by 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 an elongated seal component; and curing the deposited reactive mixture via a chemical source.
[0334] Embodiment 22. The aircraft component according to Embodiment 21, wherein the first crescent-shaped recess and the second crescent-shaped recess are configured to receive panels having a thickness of 1 to 10 times the size of the recess opening of the crescent-shaped recess, respectively.
[0335] Embodiment 23. The aircraft component according to Embodiment 21 or 22, wherein the first crescent-shaped recess and the second crescent-shaped recess extend along the entire length of the elongated body.
[0336] Embodiment 24. An aircraft component according to any one of Embodiments 21 to 23, wherein a substantial portion of the elongated body has a uniform cross-sectional shape.
[0337] Embodiment 25. An aircraft component according to any one of Embodiments 21 to 24, wherein the elongated body has a porous structure.
[0338] Embodiment 26. An aircraft according to any one of Embodiments 21 to 25, wherein the first crescent-shaped recess and the second crescent-shaped recess are triangular.
[0339] Embodiment 27. An aircraft according to any one of Embodiments 21 to 26, wherein the first recess is configured such that when a panel having a thickness greater than the opening of the first crescent-shaped recess is received, the first tip, the second tip, and the first wall fix the panel via three-point contact, and the second crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the second crescent-shaped recess is received, the third tip, the fourth tip, and the second wall fix the panel via three-point contact.
[0340] Embodiment 28. An aircraft according to any one of Embodiments 21 to 27, wherein the first recess is configured such that when a panel having a thickness greater than the first crescent-shaped recess opening is received, the first tip and the second tip are elastically deformed to widen the first crescent-shaped recess opening, and the second crescent-shaped recess is configured such that when a panel having a thickness greater than the second crescent-shaped recess opening is received, the third tip and the fourth tip are elastically deformed to widen the second crescent-shaped recess opening.
[0341] Embodiment 29. An aircraft component according to 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, the distance between the first crescent-shaped recess and the second crescent-shaped recess decreases.
[0342] Embodiment 30. An aircraft component according to any one of Embodiments 21 to 29, wherein the distance between the first crescent-shaped recess and the second crescent-shaped recess is at least twice the wall thickness of the sealing component.
[0343] Embodiment 31. An aircraft component according to any one of Embodiments 21 to 30, wherein the first co-reactive component comprises a sulfur-containing prepolymer.
[0344] Embodiment 32. The aircraft component according to Embodiment 31, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or any combination thereof.
[0345] Embodiment 33. The aircraft component according to Embodiment 32, wherein the polythioether is a thiol-terminated polythioether.
[0346] Embodiment 34. An aircraft component according to any one of Embodiments 21 to 33, wherein the second co-reactive component comprises a polyembrone polymer.
[0347] Embodiment 35. The aircraft component according to Embodiment 34, wherein the polyembrone polymer is a polyvinyl ether.
[0348] Embodiment 36. An aircraft component according to any one of Embodiments 21 to 35, wherein at least one of the first co-reactive component and the second co-reactive component further comprises flame-retardant filler particles.
[0349] Embodiment 37. An aircraft component according to any one of Embodiments 21 to 36, wherein at least one of the first co-reactive component and the second co-reactive component further comprises rheologically modified filler particles.
[0350] Embodiment 38. The aircraft component according to Embodiment 37, wherein the rheologically modified filler particles include organic filler particles or inorganic filler particles.
[0351] Embodiment 39. An aircraft component according to any one of Embodiments 21 to 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. An aircraft component according to 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 for additively manufacturing a sealing component, comprising: transporting a first co-reactive component and a second co-reactive component into 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 a chemical source, wherein the elongated body comprises a first crescent-shaped recess and a second crescent-shaped recess opposite the first crescent-shaped recess. A method comprising a first crescent-shaped recess and a second crescent-shaped recess opposite the first crescent-shaped recess, the crescent-shaped recess defining a centerline; a first volume on the first side of the centerline; a second volume on the second side of the centerline; and a third volume between the first crescent-shaped recess and the second crescent-shaped recess, the third volume through which the centerline passes, wherein the first crescent-shaped recess is contoured by an opening of the first crescent-shaped recess, 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 contoured by an opening of the second crescent-shaped recess, a third tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume.
[0354] Embodiment 42. The method according to Embodiment 41, wherein the first crescent-shaped recess and the second crescent-shaped recess are configured to receive panels having a thickness of 1 to 10 times the size of the recess opening of the crescent-shaped recess, respectively.
[0355] Embodiment 43. The method according to Embodiment 41 or 42, wherein the first crescent-shaped recess and the second crescent-shaped recess extend along the entire length of the elongated body.
[0356] Embodiment 44. The method according to any one of Embodiments 41 to 43, wherein a substantial portion of the elongated body has a uniform cross-sectional shape.
[0357] Embodiment 45. The method according to any one of Embodiments 41 to 44, wherein the elongated body has a porous structure.
[0358] Embodiment 46. The method according to 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 according to any one of Embodiments 41 to 46, wherein the first recess is configured such that when a panel having a thickness greater than the opening of the first crescent-shaped recess is received, the first tip, the second tip, and the first wall fix the panel via three-point contact, and the second crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the second crescent-shaped recess is received, the third tip, the fourth tip, and the second wall fix the panel via three-point contact.
[0360] Embodiment 48. The method according to any one of Embodiments 41 to 47, wherein the first recess is configured such that when a panel having a thickness greater than the opening of the first crescent-shaped recess is received, the first tip and the second tip are elastically deformed to widen the opening of the first crescent-shaped recess, and the second crescent-shaped recess is configured such that when a panel having a thickness greater than the opening of the second crescent-shaped recess is received, the third tip and the fourth tip are elastically deformed to widen the opening of the second crescent-shaped recess.
[0361] Embodiment 49. The method according to any one of Embodiments 41 to 48, wherein the third volume is compressible at least along the center line 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 according to any one of Embodiments 41 to 49, wherein an elongated body is configured to receive a first panel in a first crescent-shaped recess and a second panel in a second crescent-shaped recess, and the distance between the first crescent-shaped recess and the second crescent-shaped recess is variable from at least twice the wall thickness of the sealing component.
[0363] Embodiment 51. The method according to any one of Embodiments 41 to 50, wherein the first co-reactive component comprises a sulfur-containing prepolymer.
[0364] Embodiment 52. The method according to Embodiment 51, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or any combination thereof.
[0365] Embodiment 53. The method according to Embodiment 52, wherein the polythioether is a thiol-terminated polythioether.
[0366] Embodiment 54. The method according to any one of Embodiments 41 to 53, wherein the second co-reactive component comprises a polyemprepolymer.
[0367] Embodiment 55. The method according to Embodiment 54, wherein the polyembrone polymer is a polyvinyl ether.
[0368] Embodiment 56. The method according to 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 according to 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 rheologically modified filler particles.
[0370] Embodiment 58. The method according to Embodiment 57, wherein the rheologically modified filler particles include organic filler particles or inorganic filler particles.
[0371] Embodiment 59. The method according to any one of Embodiments 41 to 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 according to 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-damping filler particles.
[0373] Embodiment 61. A composition of a substance comprising: a first co-reactive component comprising a sulfur-containing prepolymer; a second co-reactive component comprising a polyembrone prepolymer, wherein the second co-reactive component is reactive with the first co-reactive component when mixed and exposed to a chemical source; and flame-retardant filler particles dispersed in the composition of the substance.
[0374] Embodiment 62.0. The composition according to Embodiment 61, having a tensile strength of 310 to 360 psi when cast to a thickness of 125 inches and cured. [Examples]
[0375] Embodiments provided by this disclosure are further illustrated by reference to the following examples describing additively manufactured linear sealing components, methods for 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 to both materials and methods can be made without departing from the scope of this disclosure.
[0376] Example 1 UV-cured polythioether linear sealing components Linear sealing components were 3D printed using a chemically wire-curable thiol-ene 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 Figure 2A.
[0377] The thiol-ene formulation contained a mixture of thiol-terminated and alkenyl-terminated resins, rheology modifiers and fillers, and a photoinitiator. The formulation was stored in a UV opaque tube at -40°C and thawed to 23°C before use. The thiol-ene formulation was 3D printed using a custom-built 3D printer consisting of a LulzBot Taz 3D printing gantry and a print bed integrated with a ViscoTec preeflow® Eco-DUO dual extruder. A UV source (UltraFire® WF-501B UV LED flashlight with a nominal peak wavelength of 395 nm) was mounted on the ViscoTec extruder and directed from the extruder to the application point at a distance of 23 inches from the extruder.
[0378] The thiol and alkenyl components were filled into opaque Nordson cartridges and connected to a ViscoTec extruder using polytetrafluoroethylene tubing wrapped in aluminum foil to prevent ambient light transmission. The filled cartridges were then subjected to 80 psi (0.551 N / mm²) under nitrogen. 2 Printing was performed using custom-written G-codes that simultaneously directed the printhead and printbed, while switching the flow of a co-reactive composition formed by pressurizing and mixing thiol and alkenyl components through a ViscoTec extruder.
[0379] After initiating the extrusion, the UV LED light was switched on. The liquid thiol-ene compound was extruded onto the print bed through a static mixing nozzle with an inner diameter of 0.6 mm. Linear sealing components were printed using a printhead speed of 120 mm / sec and a flow rate of 1.2 mL / min. Under these conditions, the extruded co-reactive composition cured within 5 seconds after exiting the extruder.
[0380] Example 2 Acoustic testing Figure 5 shows an acoustic test apparatus 500 used to perform sound attenuation performance tests on a linear sealing component. As shown, the acoustic test apparatus 500 includes an acoustic chamber 502 having a first panel 504 and a second panel 506 on the first side of the acoustic chamber. The first panel 504 and the second panel are configured to be adjusted to form a panel gap of various gap sizes between them. 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 acoustic 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 within 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 positioned outside the sound chamber near the panel gap.
[0381] The chamber, which includes adjustable panels, is assembled from aluminum panels, and the panel gaps simulate noise leakage areas such as those in an aircraft cabin environment. By inserting linear sealing components into the panel gaps, acoustic insertion loss performance can be measured. To conduct an acoustic attenuation test, linear sealing components are placed between the panels, a sound source is activated to deliver sound pressure into the acoustic chamber, and then a first microphone performs a first measurement(s) corresponding to the noise level inside the chamber, while a sound intensity probe performs a second measurement(s) corresponding to the noise level outside the chamber. The test conditions for Example 2 include an 18-inch × 12-inch × 12-inch acoustic chamber with an adjustable gap of 1 / 8 inch between two 1 / 8-inch 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 inside the acoustic chamber. The sound intensity probe was centrally positioned next to the linear sealing component outside the acoustic chamber, approximately 2 inches away from the panel gap. The sound intensity probe may include two microphones configured to detect the measured pressure level at frequencies from 50 Hz to 12.5 kHz (1 / 3 octave bandwidth). The sound intensity probe can measure an average of 16 seconds per point. The sound test environment was room temperature and in an anechoic chamber.
[0382] Example 3 Sound pressure level frequency spectrum Figure 6 shows the sound pressure level frequency spectrum from 50 Hz to 12.5 kHz, a 1 / 3 octave band, for the open gap configuration and the gap sealed with the linear sealing component according to Example 1. As shown, high insertion loss, which can be determined by calculating the difference between the sound pressure level measured in the open gap configuration and the sealed gap configuration, was observed for the linear sealing component of Example 1 across the entire frequency spectrum.
[0383] Example 4 Overall sound pressure level with and without sealant Figure 7 shows comparative histograms illustrating the reduction in overall sound pressure levels with and without a sealer. The sound pressure level from the source reference was measured inside the sound chamber using a microphone. As shown, the overall sound pressure level outside the sound chamber with an open gap of 1 / 8 inch width was 90.6 dB(A). After installing a typical foam sealer, the overall sound pressure level outside the sound chamber decreases to 79.7 dB(A). With the linear sealing component described in Example 1 installed, the overall sound pressure level outside the sound chamber decreases to 75.1 dB(A).
[0384] UV-curable polythioether chemistry A chemically ray curable thiol-ene coreactive composition was prepared by combining a first component (i.e., part A) and a second component (i.e., part B).
[0385] Thiol-ene coreactive compositions can cure at least partially under ambient conditions without chemical radiation, which can help the extruded composition withstand its weight during layer-by-layer extrusion and / or subsequent chemical radiation. Such multi-curing properties of thiol-ene coreactive compositions can help achieve covalent bonding throughout a 3D printed part.
[0386] The thiol-ene compound contained a mixture of thiol-terminated and alkenyl-terminated resins, rheological modifiers and fillers, and a photoinitiator. [Table 1]
[0387] The thiol-ene compound of Example 5 was prepared with a mixing ratio of part B to part A of 100 to 8.37. [Table 2]
[0388] The thiol-ene compound of Example 6 was prepared with a mixing ratio of part B to part A of 100 to 8.05. [Table 3]
[0389] The thiol-ene compound of Example 7 was prepared with a mixing ratio of part B to part A of 100 to 8.05. [Table 4]
[0390] The thiol-ene compound of Example 8 was prepared with a mixing ratio of part B to part A of 100 to 7.57. [Table 5]
[0391] The thiol-ene compound of Example 9 was prepared with a mixing 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 Uncured sealant formulations were measured at room temperature without light exposure, using a 25 mm parallel plate configuration. 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] Figure 8A shows the viscosity of uncured coreactive compositions from Examples 5-9 within a given shear rate range.
[0394] Figure 8B shows the 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 to a thickness of 0.125 inches (3.175 mm). The sealant was exposed to UVA radiation at 1 J / cm²–2 J / cm². 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. The curing depth was measured by applying the sealant formulation to a groove 0.4 inches deep. The curing depth was obtained by determining the depth to which the sample was completely cured after exposure. [Table 6] [Table 7]
[0396] Datasets marked with an asterisk contain samples with zero values, indicating a self-extinguishing state. Results obtained in accordance with the specifications of CFR14 §25.853(a) Appendix F Part I(a)1(iv). Average burn rate not exceeding 2.5 inches / min.
[0397] Example 13 Dimensions of linear sealing components Figure 9 shows the dimensions of linear sealing components according to various embodiments of the present disclosure. It should be understood that the linear sealing components of the present disclosure can be scaled up or down to fit between panels of different thicknesses and panel gaps of different sizes. In certain examples, the relationship between panel thickness (t), gap size (w), component wall thickness (z), recess opening size (x), recess depth (y), and recess inner wall width (v) can be described by one or more of equations (14), (15), (16), and (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 recesses are coupled to a panel. The dimensions of the wing recesses may be described by one or more of equations (18), (19), and (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 alternative methods exist for carrying out the embodiments disclosed herein. Therefore, these embodiments should be considered illustrative and not restrictive. Furthermore, the claims should not be limited to the details given herein, but rather encompass the entire scope and its equivalents.
Claims
1. Additively manufactured sealing component, A first recess and a second recess opposite to the first recess, wherein the first recess and the second recess define a center line, The first volume on the first side of the center line, The second volume on the second side of the center line, and The body comprises a third volume between the first recess and the second recess, such that the center line passes through the third volume. The first recess is contoured by a first recess opening, a first tip of the first volume, a third tip of the second volume, and a first wall of the third volume. The second recess is contoured by the second recess opening, the second tip of the first volume, the fourth tip of the second volume, and the second wall of the third volume. The aforementioned main body, A coreactive mixture is formed by mixing at least a first coreactive component and a second coreactive component, The co-reactive mixture is deposited in layers to form the main body, An additively manufactured sealing component comprising a thermosetting polymer formed by curing the deposited co-reactive mixture via a chemical radiation source.
2. The additively manufactured sealing component according to claim 1, wherein the first recess and the second recess are configured to receive panels having a thickness of 1 to 10 times the size of the recess opening of the recess, respectively.
3. The additively manufactured sealing component according to claim 1, wherein the first recess and the second recess extend along the entire length of the main body.
4. The additively manufactured sealing component according to claim 1, wherein the main body has a uniform cross-sectional shape.
5. The additively manufactured sealing component according to claim 1, wherein the main body has a porous structure.
6. The additively manufactured sealing component according to claim 1, wherein the first recess and the second recess are triangular.
7. The first recess is configured such that, when a panel having a thickness greater than the first recess opening is received, the first tip, the third tip, and the first wall fix the panel through three-point contact. The additively manufactured sealing component according to claim 1, wherein the second recess is configured such that, when receiving a panel having a thickness greater than the second recess opening, the second tip, the fourth tip, and the second wall secure the panel via three-point contact.
8. The first recess is configured such that, when a panel having a thickness greater than the first recess opening is received, the first tip and the third tip elastically deform to widen the first recess opening. The additively manufactured sealing component according to claim 1, wherein the second recess is configured such that, when a panel having a thickness greater than the second recess opening is received, the second tip and the fourth tip elastically deform to widen the second recess opening.
9. The additively manufactured sealing component according to claim 1, wherein the third volume is compressible at least along the center line such that when the third volume is compressed, the distance between the first recess and the second recess decreases.
10. The aforementioned main body, The first recess is configured to receive a first panel, and the second recess is configured to receive a second panel. The additively manufactured sealing component according to claim 1, wherein the distance between the first recess and the second recess is variable by at least twice the wall thickness of the sealing component.
11. The addition-produced sealing component according to claim 1, wherein the first co-reactive component comprises a sulfur-containing prepolymer.
12. The additively manufactured sealing component according to claim 11, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or any combination thereof.
13. The addition-manufactured sealing component according to claim 12, wherein the polythioether is a thiol-terminated polythioether.
14. The addition-produced sealing component according to claim 1, wherein the second co-reactive component comprises a polyembrone polymer.
15. The addition-manufactured sealing component according to claim 14, wherein the polyemprepolymer is a divinyl ether.
16. The additively manufactured sealing component according to claim 1, wherein at least one of the first co-reactive component and the second co-reactive component further comprises flame-retardant filler particles.
17. The additively manufactured sealing component according to claim 1, wherein at least one of the first co-reactive component and the second co-reactive component further comprises sound-damping filler particles.
18. The additively manufactured sealing component according to claim 1, wherein at least one of the first co-reactive component and the second co-reactive component further comprises rheologically modified filler particles and / or lightweight filler particles, the rheologically modified filler particles comprising organic filler particles or inorganic filler particles.
19. The first panel and The second panel, A first recess and a second recess opposite to the first recess, wherein the first recess and the second recess define a center line, the first recess is firmly bonded to the first panel, and the second recess is firmly bonded to the second panel, The first volume on the first side of the center line, The second volume on the second side of the center line, and A seal component comprising: a third volume between the first recess and the second recess, such that the center line passes through the third volume; The first recess is contoured by a first recess opening, a first tip of the first volume, a third tip of the second volume, and a first wall of the third volume. The second recess is contoured by the second recess opening, the second tip of the first volume, the fourth tip of the second volume, and the second wall of the third volume. The aforementioned seal component A reactive mixture is formed by 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 divinyl ether. The reactive mixture is deposited in layers to form the seal component, An aircraft component comprising a thermosetting polymer formed by curing the deposited reactive mixture via a chemical radiation source.
20. A method for additively manufacturing sealing components, The method involves transporting a first co-reactive component and a second co-reactive component to a mixing chamber, wherein the first co-reactive component contains a thiol-terminated polythioether and the second co-reactive component contains a divinyl ether. The first co-reactive component and the second co-reactive component are mixed to form a reactive mixture, The reactive mixture is deposited in layers to form the main body, This includes curing the deposited reactive mixture via a chemical radiation source, The aforementioned main body, A first recess and a second recess opposite to the first recess, wherein the first recess and the second recess define a center line, The first volume on the first side of the center line, The second volume on the second side of the center line, and A third volume between the first recess and the second recess, the third volume such that the center line passes through the third volume, The first recess is contoured by a first recess opening, a first tip of the first volume, a third tip of the second volume, and a first wall of the third volume. A method wherein the second recess is contoured by a second recess opening, a second tip of the first volume, a fourth tip of the second volume, and a second wall of the third volume.
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