Compositions eliminating onset of translational mobility in cured polymers

Abstract

The disclosure relates to cured polymer compositions exhibiting improved thermomechanical properties over large temperature ranges. More specifically, the disclosure relates to systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges.

Description

COMPOSITIONS ELIMINATING ONSET OF TRANSLATIONAL MOBILITY INCURED POLYMERSTECHNICAL FIELD

[0001] The disclosure is directed to cured polymer compositions exhibiting improved thermomechanical properties over large temperature ranges. More specifically, the disclosure is directed to systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges.BACKGROUND

[0002] Additive manufacturing, prioritizing materials with an onset temperature of translational mobility of critical chain length that is higher (e.g., PEI, Tg=~220 °C), expands its applicability across industries that demand high thermal stability and mechanical performance. In aerospace, where lightweight, high-strength materials are crucial, 3D printing with higher Tg polymers becomes essential for crafting components like advanced engine parts, structural elements, and thermally resistant housing for sensitive equipment. Likewise, the automotive industry benefits from these materials for producing components exposed to extreme temperatures, such as under-the-hood applications and exhaust systems, ensuring improved durability and performance. Furthermore, in electronics, particularly for sophisticated electronic devices and circuits prone to high temperatures during operation, materials with a higher Tg become integral for maintaining structural integrity and reliability. In addition, applications in the oil and gas sector, where downhole tools and equipment endure harsh thermal and chemical conditions, necessitate materials with an elevated onset temperature of translational mobility for increased durability and lifespan.

[0003] One significant 3D printing application requiring materials with a high onset temperature of translational critical chain length mobility (glass transition temperature (Tg) is the fabrication of Integrated Circuit (IC) packages and printed circuit boards (PCBs). IC packages serve as protective enclosures for semiconductor devices, ensuring their functionality and reliability. The high Tg of the final product can be crucial in this context due to the demandingoperating conditions and thermal stresses that IC packages and PCBs may experience during their lifecycle.

[0004] In the context of applications requiring materials with an elevated onset temperature of translational critical chain length mobility, Stereolithography (SLA), Digital Light Processing (DLP), and Inkjet Printing offer advantages over Fused Filament Fabrication (FFF) and Fused Deposition Modeling (FDM). SLA and DLP utilize liquid resin photopolymers cured layer by layer with precision, enabling the creation of intricate, high-resolution parts. This precision is particularly beneficial for applications in aerospace, automotive, electronics, and industrial tooling, where complex geometries and fine details are crucial. Inkjet Printing, depositing liquid materials onto a build platform, allows for the utilization of a wide range of materials, including high- temperature resistant polymers, offering versatility in material selection. While FFF and FDM excel in rapid prototyping and are well-suited for certain applications, SLA, DLP, and Inkjet Printing stand out in scenarios demanding intricate designs, high resolution, and diverse material capabilities.

[0005] Utilizing inherently high glass transition temperature (Tg) materials like polyetheretherketone (PEEK), polyetherimide (PEI), and polyphenylene sulfide (PPS) in additive manufacturing processes such as Stereolithography (SLA), Inkjet Printing, and Digital Light Processing (DLP) poses several challenges. These materials demand elevated processing temperatures or different curing procedures during 3D printing for fundamental reasons.

[0006] The heightened temperatures enable the transformation of these polymers from a solid to a molten state, ensuring optimal flowability, molecular alignment, and layer adhesion, promoting the creation of structurally sound and homogeneous printed objects. Additionally, high temperatures help alleviate internal stresses, prevent material decomposition, and facilitate fusion between layers, ensuring the final 3D-printed parts possess the desired mechanical properties and thermal stability. While necessitating advanced equipment and energy considerations, these elevated processing temperatures are vital for achieving the intended performance characteristics of these high-performance materials.

[0007] These often-necessitated elevated processing temperatures typically surpass the capabilities of certain 3D printing technologies. In SLA, the operating temperatures typically employed are not sufficient to handle the high Tg requirements and the presence of solvents of thermoplastic materials like PEEK or PEI. Similarly, in Inkjet Printing, the operating temperaturesare generally lower than what is needed for effective processing of these polymers. Likewise, DLP may face challenges in processing the solvents present in the ink composition (if operating at the typical processing temperatures), and / or achieving the elevated temperatures required for proper curing and post-curing of high Tg materials.

[0008] Thus, there is a need for compositions, systems and methods enabling efficient and precise fabrication of complex articles or components with increased thermomechanical stability.SUMMARY

[0009] Disclosed, in various implementations, are systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges.

[0010] In an implementation, provided herein is a method of substantially eliminating the onset of translational mobility of a polymer chain segment following phase change, over a predetermined temperature range, the method including forming a curable liquid composition including: admixing into a solution including a multifunctional acrylate polymer or its oligomer, a multifunctional crosslinking agent (MCA) and a photoinitiator (PI) at a predetermined volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer to the MCA; and curing the curable liquid composition, thereby forming a cured polymer network, wherein the fractional concentration of the MCA in cured polymer network is configured to be above the three dimensional (3D) bond percolation threshold of the cured polymer network.

[0011] In another implementation, provided herein is a curable dielectric resin composition configured, upon curing, to substantially eliminate the onset of translational mobility of a polymer’s chain, or its oligomer segment over a predetermined temperature range including: a multifunctional acrylate polymer or its oligomer; a multifunctional crosslinking agent (MCA); and (optionally) a photoinitiator (PI), wherein the volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer - to the MCA is between 1:10 and 11:20.

[0012] The curable dielectric resin compositions disclosed herein may find application as inks in printing processes or printing devices such as 3D printers and 3D printing processes. The curable dielectric resin compositions may be used as coatings, adhesives or may be used in carbon fiber molding processes or composite manufacturing.

[0013] These and other features of the methods and compositions for fabricating components and / or articles exhibiting no onset temperature indicative of translational mobility of critical polymer or oligomer chain length, shall become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.BRIEF DESCRIPTION OF THE FIGURES

[0014] For a better understanding of the systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges, with regard to the implementations thereof, reference is made to the accompanying examples and figures, in which:

[0015] FIG. 1A Dynamic Mechanical Analysis (DMA) & Thermogravimetric Analysis (TGA) Curve of an example polymer system, while FIG. IB is a schematic DMA-curves of polymer blends and their corresponding Homo-polymers;

[0016] FIG. 2A illustrates Thermomechanical Analysis (TMA) Tests of different resin compositions, and 2B is a schematic TMA diagram of a thermoset;

[0017] FIG. 3 illustrates the effect of composition on thermal decomposition and outgassing of the printed specimens; and

[0018] FIG.4 illustrates the effect of composition on Storage modulus;

[0019] FIGS. 5A-5C illustrate the effect of BMI / Methacrylate ratio on measured thermomechanical;

[0020] FIG. 6 illustrates the effect of the loading, size and surface-modification of the silica nanoparticles on the viscosity of the base resin;

[0021] FIG. 7 illustrates the effect of BMI concentration on thermogravimetric analysis;

[0022] FIG. 8 illustrates the effect of BMI type and concentration on the storage modulus;

[0023] FIG. 9 illustrates the effect of thermal initiator (TI) type and concentration on stiffness of the polymerized resin;

[0024] FIG. 10 illustrates the effect of BMI type and the presence of TI on the storage modulus;

[0025] FIG. 11 illustrates the effect of BMI at the same concentration on the storage modulus; and

[0026] FIG. 12 illustrates a differential scanning calorimetry analysis of the BMI containing resin.DETAILED DESCRIPTION

[0027] Provided herein are implementations of systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges.

[0028] The combination of (Meth-)Acrylate and bis-maleimide (BMI) resins leads to materials with extraordinary thermal properties. Polymers typically have a defined glass transition temperature (Tg), or softening point, at which the polymeric network gains translational chain mobility and thus the material shows significant decrease in mechanical properties, e.g., tensile strength and Young’s modulus, as well as an increase of the coefficient of thermal expansion (CTE), impact strength & elongation at break.

[0029] Typically, when mixing two or more types of polymers, the resulting resin, depending on the thermodynamic compatibility between (among) the polymers, will exhibit either multiple glass transition temperatures (see e.g., FIG. IB), corresponding to the individual components, or a defined glass transition temperature, somewhere between the Tg’s of the individual polymer and as a function of their fractional concentration. By combining (Methacrylates and BMI, the glass transition temperature of the resulting polymer shifts to a temperature that is higher than of those of the individual components (in other words, the Tgs of the pure acrylate and the pure BMI). This shift can be so significant that the glass transition temperature vanishes completely as the material decomposes before it reaches the shifted theoretical glass transition temperature.

[0030] Whereas typical polymers exhibit temperature stabilities of up to 250°C, the combination of (Meth-) Acrylate and BMI lead in certain implementations, to materials having a temperature stability to changes in thermomechanical properties of up to 350°C, thereby opening entirely new high-temperature fields of applications for polymers.

[0031] In products formed of polymers and polymer blends, the glass transition temperature(Tg) is a crucial parameter affecting thermomechanical properties that drive material behavior. Polymers undergo a transition from a rigid, glassy state to a more flexible, rubbery state as the temperature surpasses Tg. As temperature increases, the free volume (Vf, referring to the voids in the amorphous regions of polymers or free spaces between polymer chains, and the mobility of polymer chains is strongly influenced by these free volumes) of the system increases, to the pointwhere the free volume, is larger than that critical chain length (representing the minimum polymer length required for polymer chains to exhibit cooperative motion), thereby facilitating the (glass) transition.

[0032] This kinematic (in other words, time-related) transition significantly impacts key characteristics such as modulus, hardness, and thermal expansion. The storage modulus (E') and loss modulus (E") undergo notable changes in the vicinity of Tg, marking shifts in material stiffness and energy dissipation. Additionally, Tg influences the coefficient of thermal expansion, affecting dimensional stability and response to temperature variations. In polymer blends, the glass transition becomes a complex interplay of multiple Tg values, resulting in a broadened transition range and diverse mechanical responses. The damping behavior, often associated with viscoelasticity, experiences alterations due to Tg-related transitions, affecting material resilience and fatigue resistance. Furthermore, the glass transition influences creep and stress relaxation, crucial parameters in applications where long-term mechanical performance is critical.

[0033] Furthermore, dielectric properties, such as, for example, dielectric loss (e) are also affected by Tg. In the case of dielectric loss, as the temperature increases over Tg and the material transitions into a more flexible, rubbery state, the increased molecular mobility allows for greater polarization and alignment of dipoles in response to an electric field. For example, the disclosed formulation produce dielectric material exhibiting dielectric loss of less than 0.005, and a dielectric constant of between about 2.5 and about 3.0 at RT.

[0034] Here too, thermo-mechanical properties, such as, for example one of: coefficient of thermal expansion (a), tensile strength, Young's Modulus (E), Glass Transition Temperature (Tg), and the brittle-ductile transition temperature (Tp), and [Tp / Tg] ratio, each as measured on the cured layer, can be further improved composition by controlling a plurality of parameters, for example, at least one of: the type of monomer used, degree of polymerization, cross-link density, fractional concentration of the monomer, oligomer and / or polymer and their combination in the composition, and the like.

[0035] Accordingly, and in an implementation, provided herein is a method of substantially eliminating the onset of translational mobility of a polymer chain segment following phase change (in other words, as a result of heating by increasing temperature at a certain rate), over a predetermined temperature range, the method including forming a curable liquid composition including: admixing into a solution including a multifunctional acrylate polymer or its oligomer, amultifunctional crosslinking agent (MCA) and (optionally) a photoinitiator (PI) at a predetermined volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer - to the MCA; and curing the curable liquid composition, thereby forming a cured polymer network, wherein the fractional concentration of the MCA in cured polymer network is configured to be above the three dimensional (3D) bond percolation threshold of the cured polymer network.

[0036] In the context of the disclosure, the term “curing” refers to the process by which the cross-linking or curing agent such as photopolymerization initiators (PI) react with the crosslinkable functional groups to form the cross-linked network characteristic of a cured compositions. The cured compositions as employed herein, in certain implementations, refer to a non-deformable solid exhibiting limited or no solubility in conventional solvents. “When cured”, as used herein with reference to the compositions as a basis for weight fractions of, for example, fillers, may refer to a portion of the thermoset resin composition remaining in solid form after curing, which excludes solvents, volatiles, and volatile reaction components that may be generated during curing. Reaction products are only generated during curing, and not after, since any reaction will have been completed (termination reactions) when curing is done. Curing is carried out in certain implementations, by exposing the various composition to actinic radiation in a predetermined wavelength, such as between about 190 nm and about 470 nm for a predetermined time, for example between about 5 milliseconds (ms) and about 10 minutes, depending on the compositions and the thermo-mechanical parameters sought to be improved and / or modulated.

[0037] Further, the term “percolation” as used herein, is assigned to the theory of connectivity of MCAs (each having at least three (3) functional ends), in randomized lattice structures. Likewise, the term “percolation threshold” is used herein to refer, for example, to a state achieved when a crosslinked phase forms a continuous, at least three dimensional (3D) interconnecting network throughout the bulk resin. In other words, the continuous crosslinked phase is one where the crosslinked polymer phase is substantially uniformly distributed within the whole volume of the bulk phase (referring to uniform physical and / or chemical composition).

[0038] For example, the multifunctional acrylate composition can be a branched resin whereby thermo-mechanical properties can be controlled by the degree of branching, backbone length between branches, cross link density and the like. For example, the multifunctional acrylate composition can further include polyester (PES), polyethylene (PE), polyvinyl alcohol (PVOH),poly(vinylacetate) (PVA), Poly (vinylpyrrolidone), or a combination including a mixture, a monomer, an oligomer, and a copolymer of one or more of the foregoing.

[0039] As such, the multi-functional acrylate used for substantially eliminating the onset of translational mobility of a polymer chain segment following phase change, over a predetermined temperature range (e.g., between -25 °C (or 248 K) and 350 °C), used in the methods disclosed herein, can be at least one of a monomer, oligomer, polymer, and copolymer of: 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A-diglycidyl ether diacrylate, hydroxypivalic acid neopentanediol diacrylate, ethoxylated bisphenol-A- diglycidyl ether diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris(2-acryloyloxyethyl)isocyanurate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate or a multifunctional acrylate composition including one or more of the foregoing.

[0040] Other matrix (build materials) can be used and include, for example vinylbenzyl compound resin, a polyolefin compound, a maleimide resin, urethane resin, urethane-modified polyester resin, or a combination thereof. For example, the vinylbenzyl compound resin is vinylbenzyl etherified-bicyclopentadiene phenol resin; the polyolefin compound is at least one of styrenebutadiene-divinylbenzene copolymer, hydrogenated styrene-butadiene-divinylbenzene copolymer, styrene-butadiene-maleic anhydride copolymer, polybutadiene-urethane-methyl methacrylate copolymer, urethane-methyl methacrylate copolymer, styrene-butadiene copolymer, polybutadiene homopolymer, styrene-isoprene- styrene copolymer, maleinized styrene-butadiene copolymer, methylstyrene copolymer, petroleum resin and cyclic olefin copolymer.

[0041] In an implementation, the MCA includes a Bismaleimide (BMI) monomer, oligomer or polymer represented by the formula:where: X is an aliphatic spacer, an aromatic spacer, or their combination.

[0042] In some embodiments, an aliphatic spacer may be a saturated linear or branched alkyl group which includes between 5 and 5000 carbon atoms, for example between 5 and 1000 carbon atoms, between 5 and 250 carbon atoms, or between 5 and 50 carbon atoms. For example, an aliphatic spacer may be a 2,2,4-trimethyl hexane spacer or a spacer having a C36-alkylene backbone, e.g. as present in BMI-689. In some embodiments, an aliphatic spacer may be an unsaturated linear or branched alkene including between 5 and 5000 carbon atoms, for example between 5 and 1000 carbon atoms, between 5 and 250 carbon atoms, or between 5 and 50 caron atoms. For example, an aliphatic spacer may be 5,6-diheptenyl cyclohexene.

[0043] Further non-limiting examples of aliphatic spacers may include saturated or unsaturated carbocyclic ring systems (e.g. cyclopentane, cyclohexane or cycloheptane) which are substituted with linear or branched, saturated or unsaturated, alkyl and / or alkenyl substituents (e.g. linear or branched C3 to C20 alkanes or linear or branched C3 to C20 alkenes, for example Ce to Cs alkanes).

[0044] Further non-limiting examples of aliphatic spacers may include saturated or unsaturated heterocyclic ring systems (e.g. tetrahydrofuran, pyridine or piperidine) which are substituted with linear or branched, saturated or unsaturated, alkyl and / or alkenyl substituents (e.g. linear or branched C3 to C20 alkanes or linear or branched C3 to C20 alkenes, such as Ce to Cs alkanes).

[0045] An aromatic spacer may be a spacer that includes one or more aromatic ring systems, for example a benzene, naphthalene or anthracene spacer. In some embodiments, the aromatic spacer further includes one or more alkyl or alkenyl substituents. The one or more alkyl or alkenyl substituents may link the one or more aromatic ring systems or may include terminal substituents on the one or more aromatic ring systems. The one or more alkyl or alkenyl substituents may link the aromatic spacer to the maleimide substituents. Non-limiting examples of aromatic spacers may include: toluene, 4-methyl-l,3-phenylene, methylenedi-4,1 -phenylene, 5,6-(diheptylen-phenylene,or m-xylylene. In some embodiments, an aromatic spacer includes a C36-alkylenedi-5,5’-[(l- methylethylidene)bis(4,l-phenyleneoxy)]bis[l,3-isobenzofurandione] monomer, oligomer or polymer.

[0046] Oligomers, as disclosed herein, may be molecules that include a small number of repeating units linked together in a chain or structure. Oligomers may include between 2 and 20 repeating units. Non-limiting examples of oligomers may include polyethylene glycol oligomers (- (CH2-CH2O)n-), aliphatic urethane-based oligomers ((-R-CO)-NH-(CH2)n-NH-CO-R-), or dimethylsiloxane oligomers (-(Si(CH3)2)-O)n-).

[0047] Polymers, as disclosed herein, may be molecules that include a large number of repeating units linked together in a chain or structure. For example, polymers may include more than 20 repeating units (e.g. 100, 500 repeating units), such as polyethylene glycol polymers (- (CH2-CH2O)n-), aliphatic urethane-based polymers ((-R-CO)-NH-(CH2)n-NH-CO-R-), or dimethylsiloxane polymers (-(Si(CH3)2)-O)n-).

[0048] For example, X is an aliphatic chain having the general formula (CFDn, wherein n is an integer between 1 and 1500. For example, X is an aliphatic chain having the general formula (CH2)n, wherein n is an integer between 1 and 200. For example, X is an aliphatic chain having the general formula (CFDn, wherein n is an integer between 1 and 50.

[0049] For example, the BMI resin used can be at least one of 4,4'-bismaleimidodiphenyl methane (MDAB), phenylmethane maleimide oligomer, N,N'-m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'- (4-methyl-l,3-phenylene) bismaleimide, l,6-bismaleimido-(2,2,4- trimethyl)hexane (MATMD), 2,3-dimethylphenylmaleimide, 2,6-dimethylphenylmaleimide, N- phenylmaleimide, 2,4- bismaleimidotoluene (TDAB), (l,l-(methylenedi-4,l -phenylene) bismaleimide (MDPB), bis(3-methyl-5-ethyl-4-maleimidophenyl) methane, a 2,2-bis(4-maleimido phenoxyphenyl)propane, (5,6-(diheptylen-phenylene) bismaleimide, bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, mxylylenebismaleimide (MXBI), and the prepolymer of the abovementioned compound.

[0050] In another implementation, the volume ratio (V / V) between the BMI and the acrylate polymer, or oligomer is between 1:10 and 11:20.

[0051] Photoinitiators that can be used with the acrylates described herein can be, for example, radical photoinitiators. These radical photoinitiators can be, for example Irgacure® 500from CIBA SPECIALTY CHEMICAL and Darocur® 1173, Irgacure® 819, Irgacure® 184, TPO- L (ethyl(2,4,6, trimethyl benzoyl) phenyl phosphinate) benzophenone and acetophenone compounds and the like. For example, the radical photoinitiator can be cationic photo-initiator, such as mixed triarylsulfonium hexafluoroantimonate salts. Another non-limiting example of the free radical photoinitiator used, is at least one of: be 2-ispropylthioxanthone (ITX), 2,4- Diethylthioxanthone (DETX), benzophenone, 4-methylbenzophenone, ethyl-4- dimethylaminobenzoate (EDAB), and 2,2-Dimethoxy-2-phenylacetophenone. In an implementation, two or more Pi’s are used, for example, ITX and EDAB, or in another example, EDAB, ITX and TPO-L.

[0052] In an implementation, the fractional volume concentration of the MCA in the cured polymer network (in other words, in its solid state), is between about 16% and about 50% (v / v).

[0053] For example, in an implementation, the BMI is bis (1,2 maleimidoheptane) 5,6- diheptenyl cyclohexene, and the multifunctional acrylate is: Tris (2-hydroxy ethyl) isocyanuratetriacrylate, or Dipentaerythriolhexaacrylate, at a BMLto the multifunctional acrylate (in other words, the Tris (2-hydroxy ethyl) isocyanuratetriacrylate, orDipentaerythriolhexaacrylate) ratio of 1:3.

[0054] In another implementation, the methods disclosed are used to create a curable dielectric resin composition, that will form a dielectric resin to be used in various additive manufacturing printer, for example, inkjet printing, stereolithography (STL), and digital light printing (DLP). Accordingly, provided herein is a curable dielectric resin composition configured, upon curing, to substantially eliminate the onset of translational mobility of a polymer’s chain or its oligomer segment at a predetermined temperature range including: a multifunctional acrylate polymer or its oligomer; a multifunctional crosslinking agent (MCA); and (optionally) a photoinitiator (PI), wherein the volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer - to the MCA is between 1:10 and 11:20.

[0055] The term “forming” (and its variants "formed", etc.) refers in an implementation to pumping, injecting, pouring, releasing, displacing, spotting, circulating, or otherwise placing a fluid or material (e.g., the conductive ink) in contact with another material (e.g., the substrate, the resin or another layer) using any suitable manner known in the art.

[0056] The printed Dl / resinous ink can be fabricated from resin-rich ink compositions, for example, suspensions, emulsions, solutions and the like. The term “resin-rich” refers tocompositions in which larger proportions of polymer resin components are included than are needed to bind the Dl / resinous ink layer to the underlying substrate, conductive layer, or to a layer of another component having resinous / dielectric, and metallic / conductive constituents with voids therein, or support portion and their combination. For example, a resin-rich component layer may include polymer Dl / resins in amounts that are at least 95% by weight of the total Dl / resin ink weight.

[0057] The term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and / or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives.

[0058] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “a”, “an” and “the” herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the constituent(s) includes one or more constituent). Reference throughout the specification to “one implementation”, “another implementation”, “an implementation”, and so forth, when present, may refer to a particular element (e.g., feature, structure, and / or characteristic) described in connection with the implementation which is included in at least one implementation described herein, and may or may not be present in other implementations. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various implementations .

[0059] Likewise, the term "about" may refer to amounts, sizes, formulations, parameters, and other quantities and characteristics which are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such.

[0060] The curable dielectric resin composition may be used as a resin in printing processes, for example 3D printing processes. In some embodiments, the curable dielectric resin composition may include an MCA selected from a group consisting of: l,l’-C36-alkylenebis-lH- pyrrole-2, 5-dione, (BMI-689) and C36-alkylenedi-5,5’-[(l-methylethylidene)bis(4,l- phenyleneoxy)]bis[l,3-isobenzofurandione] bismaleimide oligomer (BMI-1400); and includes ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator (PI). The curable dielectric resin composition may include a multifunctional acrylate polymer such as a tricyclodecandedimethanol dimethacrylate polymer (SR834). The curable dielectric resin composition may be UV-curable and shows high temperature resistance and durability.

[0061] In printing processes, such as 3D printing processes, the recommended exposition times at room temperature (rt) at a wavelength of 405 nm may be: 2.7 mW / cm2: 5.7 secs, 3 mW / cm2: 5.2 secs, 5.5-16 mW / cm2: 2.0-2.3 secs, or 10 secs as the base layer. Room temperature may be a temperature between 15 to 25 °C. Elevated temperature may ease the fabrication of large cross-sections and / or complex geometries. In case of flashing, a delay before the exposition start may be added.

[0062] Post-printing processes may include a washing step with suitable solvents, e.g. a mixture of water and 3 -methoxy-3 -methyl- 1 -butanol (MMB) mixed at a ratio of 30:70 by weight and drying step, e.g. using pressurized air or in an oven at a temperature of 90°C. Recommended cleaning agents may be pure 3-methoxy-3-methyl-l-butanol. The maximum soaking time in the cleaning agent may be 2 minutes, then the parts can be rinsed with water.

[0063] In UV post-curing processes any type of UV treatment may be suitable, as there is no risk of over-curing. Non-limiting examples for drying conditions may include: 6x10s @50% (Hoenle UV Cube 100 IC) or 2x30 min (CureBox Wicked Engineering).

[0064] Thermal post- treatment can include the application of heat for 2 h (e.g. at 200°C) followed by a slow cooling process. For bulky parts, slow heating may be applied to allow the material to be heated evenly before curing is initiated. The temperature ramp in the heating process may be dependent on the thickness the parts.

[0065] Curable resin compositions may be used in carbon fiber molding. Carbon fiber molding processes may be manufacturing processes that are used to produce parts, e.g. spare parts for cars, by injecting molten material into a specially designed mold. For example, curable electric resin compositions may be used in carbon fiber molding processes using a wet lay-up. Dryenforcement materials, e.g. fiber cuts, may be placed in a mold and curable electric resin compositions may be applied to them, e.g. using a brush, roller or spray gun. Once the enforcement materials are impregnated with a liquid resin, e.g. in form of a curable electric resin composition, they can be cured at a defined temperature, e.g. room temperature, 100 °C, 200 °C, etc..

[0066] Alternative methods for carbon fiber molding processes in which curable electric resin compositions may be applied can include prepreg lamination and resin transfer molding. In prepreg lamination processes, composite materials may be produced by layering pre-impregnated fibers. Pre-impregnated layers may be prepared by impregnation of fibers with a curable electric resin composition. Optionally, in some cases, pre-impregnated fibers may be partially cured to create a coating on the surface of the fiber layers or may be cut into a desired shape. Preimpregnated layers may be layered in a desired orientation and to a desired thickness. Vacuum application may remove trapped air and may consolidate the prepreg layers. Subsequent curing, e.g. in an autoclave, may provide the desired composite material.

[0067] Curable dielectric resin compositions may be used in processing technologies for continuous fiber-reinforced composites: High performance resins may require either a hot-melt process (melting the resin before curing it) or a solvent-based process due to the high viscosity or the solid state at room temperature. A disadvantage of the hot-melt process is that the reaction may begin to increase the viscosity as the reaction time progresses.

[0068] A disadvantage of solvent-based processes is the presence of a solvent (evaporation, residuals, environmental issues etc.).

[0069] An advantage of the compositions and methods disclosed herein may be the low viscosity of the compositions at rt. This allows processing of the compositions, e.g. shaping and arrangement of the composition, at rt.

[0070] Non-limiting examples of processing technologies and conditions for curable dielectric resin compositions in continuous fiber-reinforced composites may include: a. Draping (e.g. by hand, vacuum bag): i. Processing Temperatures: 23-80°C ii. Processing Times: 30min - 24h iii. Typical Fiber Content(vol.): 30-50% iv. Processing Pressures: 0 to 1 bar b. Autoclave:i. Processing temperatures: 120-200°C ii. Processing times: 3-8 hours iii. Typical Fiber Content(vol.): 40-70% iv. Processing Pressures: 3 to 20 bar c. Filament Winding: i. Processing Temperatures: 23-30°C ii. Processing Times: 3-24h (Continuous process) iii. Typical Fiber Content(vol.): 40-60% iv. Processing Pressures: ambient d. Liquid Composite Molding(e.g. Resin-Transfer Molding): i. Processing Temperatures: 20- 120°C ii. Processing Times: 15min to 3h iii. Typical Fiber Content(vol.): 40-60% iv. Processing Pressures: 4-20 bar

[0071] Non-limiting examples of processing technologies and conditions for curable dielectric resin compositions in discontinuous (“chopped”) fiber-reinforced composites may include: a. Sheet molding compounds (SMCs): An SMC process may include the steps of: spreading a resin paste onto a carrier film, adding chopped fibers, e.g. glass fibers, to the paste, sandwiching it between another film, compressing the assembly to create a sheet of material. The sheet may be cut into "batches" and placed in a mold. By heating and applying pressure, the sheet can be cured into the desired shape. i. Processing Temperatures: 120-170°C°C (Mold) ii. Processing Times: 30s - lOmin. “Baking time” after shaping step required. iii. Typical Fiber Content (vol.): up to 50% iv. Processing Pressures: 60-100 bar b. Bulk molding compounds (BMCs): A BMC process may include the steps of: mixing ingredients including a curable dielectric resin composition, injecting the composition into a mold, applying pressure, and curing the material. i. Processing Temperatures: 120-180°C (Mold).ii. Processing Times: in injection molds: 30s - lOmin, in hot molds: 15-30 minutes. “Baking time” after shaping step required. iii. Typical Fiber Content (vol.): 20-40% iv. Processing Pressures: in injection machines: 80 to 180 bar, in hot molds: 20-100 bar.

[0072] Curable resin compositions may be used as a coating. Deposits of coatings may be applied to a surface by, for example, spray coating or electro spraying. Since the curable electric resin compositions disclosed herein show a low viscosity when applied at low temperatures (e.g. a temperature between 10 and 80°C), it may be possible to provide high-temperature stable coatings which exhibit ultra-low loss properties.

[0073] Curable resin compositions may be adapted to coating techniques, e.g. for use in thin film deposition. For example, the fluid physical properties (such as viscosity) of a curable resin composition may be adapted to the coating application by modifying the length of the spacer present in a multifunctional crosslinking agent.

[0074] As a result of the low viscosity of the curable resin compositions (e.g. viscosities in the range of 10-2000 mPas), they can be deposited using various deposition techniques, including, but not limited to: spin-, dip-, spray-, slot-die-coating, or dispensing systems.

[0075] Advantageously, in some embodiments, the curable resin compositions are singlecure systems and rely on an external (UV light) system in the curing process. Accordingly, the curable resin compositions are not limited to specific processing times, but can be amended in their shape for a prolonged period of time, e.g. for several minutes or hours. Further, due to the fast reaction times of the curable resin compositions in the curing process (reactions times between 0.5- 15 seconds), they can be cured with low UV-dosages (<200 mW / cm2) in the curing process.

[0076] Processing conditions for curable resin compositions in coatings may include: i. Viscosity: 10-2000 mPas ii. Hg-lamps / LED lamps: 250 - 405 nm iii. UV Intensity: <200 mW / cm2iv. Curing times: 0.5-15 seconds v. Processing temperatures 23-30°C vi. Controlled atmosphere: N2 / CO2 to mitigate oxygen inhibition

[0077] A curable resin composition may be used as an adhesive, for example in cartridges, dispensers, sprays, or inkjets. As a result of the low viscosity of the curable electric resin compositions at low temperatures (e.g. a temperature between 10 and 80°C), an application of the composition, e.g. in the form of a curable resin may be possible at low temperatures. Consequently, when photoinitiators are used, it may not be necessary to store the compositions at low temperatures (e.g. in a freezer below 0°C).

[0078] Adhesives may be deposited by a variety of deposition techniques, including, but not limited to: spray-, slot-die-coating, manual coating, casting or dispensing systems.

[0079] Advantageously, in some embodiments, the curable resin compositions are singlecure systems. Thus, adhesives including curable resin compositions have excellent storage stability and no mixing procedures are required prior to application of the adhesives. Further, since the curable resin compositions are single component systems, they can be cured photonically and / or thermally. This may allow the compositions to be used in a variety of applications, such as undercuts / shaded areas. a. Non-limiting examples of conditions for the thermal curing of adhesives, including the curable resin compositions, may include: i. Storage conditions: -40 - 25°C ii. Viscosity: 10 - 5000 mPas iii. Processing conditions: 25 - 40°C iv. Curing conditions: 80 - 150°C b. Non-limiting examples of conditions for the photonic curing of adhesives, including the curable resin compositions, may include: i. Storage conditions: -40 - 25°C ii. Viscosity: 10 - 5000 mPas iii. Hg-lamps / LED lamps: 250 - 405 nm iv. UV Intensity: <200 mW / cm2v. Curing times: 0.5-15 seconds vi. Processing temperatures 23-30°C vii. Controlled atmosphere: N2 / CO2 to mitigate oxygen inhibition viii. Processing time: <30 minutes

[0070] Curable resin / ink composition may be used as a composite matrix material Rasen transfer molding (RTM), prepreg, SMC, BMC Lay-up process, automatic fiber placement. Due to low viscosity excellent impregnation of fibers can occur, yielding in high temperature stable matrix materials.

[0080] As a result of the low viscosity of the curable resin compositions (e.g. viscosities in the range of 10-2000 mPas), it can be used as a sealant, e.g. to protect electronic assemblies and circuits boards from moisture, vibration and other environmental factors. The sealant may act as a potting compound and may be filled in an electronic assembly and may act as a protective layer that is resistant to shock or vibration. Curable, dielectric resin compounds may be applied, e.g. by casting or dispensing. As the resin compositions are photonically and / or thermally curable, the casting compound can also be cured in shaded or not visually accessible volumes. a. Non-limiting examples of conditions for the application of the curable resin compositions as casting resins or potting compounds may include: i. Storage conditions: -40 - 25°C ii. Viscosity: 10 - 1000 mPas iii. Processing conditions: 25 - 40°C iv. Crosslinking: 80 - 180°C v. Hg-lamps / LED lamps: 250 - 405 nm vi. UV Intensity: <200 mW / cm2

[0070] As disclosed herein, the terms “ink” and “resin” may be used interchangeably in some of the embodiments described in this application, e.g. with relation to printing applications or when referring to a curable dielectric resin composition or curable dielectric ink composition. Resins or inks may be viscous liquids thank can be used, for example, in printing applications. Inks or resins may include dyes, pigments and / or mixtures of organic compounds. They can be converted into polymers.EXAMPLESMaterials'.

[0081] BML689 (Designer Molecules Inc.) was mixed with the acrylates Miramer M410 (Di(Trimethylolpropane) tetraacrylate), Miramer M600 (Rahn Chemie, Dipentaery thriolhexaacry late), SR368 (Tris (2-hydroxy ethyl) isocyanuratetriacrylate) andSR833S (Arkema Satomer, Tricyclodecanedimethanol Diacrylate) as well as with the methacrylate SR834 (Arkema Satomer, Tricyclodecanedimethanol Dimethacrylate) at mass fractions (w / w) 25:75, 50:50 and 75:25. The raw materials were used as received. To fabricate UV-curable resins 1 wt.% TPO-L (Arkema Satomer) was added to base resin. Furthermore silica nanoparticles (Denka Chemicals) with and without an methacrylate surface modification and different size distribution were dispersed in the base resin with a 3-Stage-Mill (EXAKT) at weight concentrations of 35.5, 48 and 59 wt.%.Methods:Viscosity

[0082] The viscosity of the base resin was measured with a hybrid rheometer DHR20 (WATERS™ I TA Instruments) with a plate / plate-geometry at shear rates between 1 and 1000 1 / s between 30 and 80 °C with three measurement points per order of magnitude.TMA

[0083] The thermal expansion of the material was measured with thermomechanical analyzer TMA 450 (WATERS™ I TA Instruments) with two heat-up and one cool-down cycle with a heating resp. cooling rate of 3 K / min from -10 to 300 °C.TGA

[0084] The thermal decomposition of the material was measured with thermogravimetric analyzer TGA 550 (WATERS™ I TA Instruments) with a heating rate of 10 K / min until 800°C in a platinum crucible. Below 600°C the probe was flushed with dry nitrogen. Above 600°C the probe was flushed with dry oxygen.DMA

[0085] The thermo-mechanical properties were tested with a hybrid rheometer DHR20 (WATERS™ I TA Instruments) in a temperature range from 25°C to 400°C with a heating rate of 3 K / min with a dynamic load of 0.1 % with a frequency of 1 Hz and a preload of 0.5%.DSC

[0086] DSC and Cp measurements were performed with a DSC 204 Fl Phoenix (Netzsch) from 0 resp. 20 to 300 °C with a heating rate of 10 K / min. Indium (Tm=156.6 °C), Tin (Tm=231.9 °C), Bismuth (Tm=271.4 °C), were used as standards to calibrate the instrument.Specimen Fabrication

[0087] Specimens were printed with a commercially available SLA printer (Prusa SL1S). The exposure times were adjusted according to the inorganic filler content and varied between 28 and 55 s. The specimens were washed with isopropyl alcohol and dried with pressurized air. UV post-curing was performed in a UV-LED cube (LED Cube 100 IC Hbnle) for 60 s at 50 %. Thermal annealing was performed in a convection oven (Binder) at 200°C for 2h and let cool down to room temperature.Mechanical Testing

[0088] Tensile modulus, strain and stress at break were tested according to ISO 527-1 / -2 and 1BA geometries with speeds of 1 mm / min and 5 mm / min respectively on a tensile tester (Zwick ZwickiLine 2.5kN). The flexural modulus, flexural strength and stress at break were tested according to IPC-TM-650 with 1 % / min on a three point bending geometry on the above-mentioned Zwick ZwickiLine 2.5kN. The impact strength was measured according to ASTM D4812:2006 at room temperature and 1 J (Zwick Impact Tester).EXAMPLE I: EFFECT OF LOADING, SIZE AND SURFACE-MODIFICATION OF THE SILICA NANOPARTICLES ON THE VISCOSITY OF THE BASE RESIN

[0089] The viscosity of the base resin as a function of the loading, size and surfacemodification of the silica nanoparticles was measured with rotational rheometer. As can be seen in FIG. 6, and in the following table, the viscosity increases with increasing particle load. Furthermore, the presence of the silica nanoparticles increase the shear thinning behavior of the inks.

[0090] The non-modified nanoparticles led to viscosities >26000 mPas, which is far outside of the printable regime for SLA-printers.Table 1.

[0091] To be able to print test specimens 2 wt.% TPO-L was added as a photoinitiator. Based on the viscosity measurements the (acrylate) surface-modified nano-particles were added and specimens were printed for tensile test, bending and impact tests, as well as DMA and TMA measurements. Specimens for the thermogravimetric measurements were taken from the tensile test specimens.EXAMPLE II: TGA MEASUREMENT

[0092] To measure the thermal decomposition and out-gasing of the printed specimens, a TGA was performed. As can be seen in FIG. 3, only marginal mass losses were measured below 250°C. The “Base Resin” curve shows the temperature-dependent Residual Mass [%] for unfilled BML689 and lwt% TPO-L. The “Base Resign higher PI content” curve shows the temperaturedependent Residual Mass [%] for unfilled BML689 and 2wt% TPO-L. The “Base Resin with Silica” curve shows the temperature-dependent Residual Mass [%] for unfilled BML689 in combination with 48wt% SFP130mod and 2wt% TPO-L. The “Base Resin with higher Silica content” curve shows the temperature-dependent Residual Mass [%] for unfilled BML689 in combination with 59wt% SFP130mod and 2wt% TPO-L.

[0093] A significant mass loss started to occur for temperatures >325 °C. The mass loss at 250 °C as well as TD2, TDS and Toecomp. Are displayed in table 2:Table 2: Effect of BMI Concentration on (w / w) decomposition:

[0094] When switching to oxygen at temperatures >600°C the last of the remaining organic content decomposes, and only the inorganic silica particles remained at the respective weight percentages.

[0095] When comparing the decomposition temperatures of different bmi-methacrylate- concentrations, the improved thermal stability of the resin can be observed as illustrated in FIG. 7. While the shift is only minor in the lower concentrations, a larger increase is observed for concentrations between 30 and 50% (w / w) of BMI.EXAMPLE III: THERMAL EXPANSION COEFFICIENT

[0096] To determine the thermal expansion coefficient (a), TMA measurements were performed. To release initial internal stresses, samples were heated to 300 °C. The thermal expansion coefficient was then determined in the first cool down ramp from 300 to -10 °C and in the second heat-up ramp to 300 °C. As it can be seen in FIG. 2A, a steady slope of the dimension change over the whole temperature range was observed.

[0097] With increasing filler content (namely silica beads, with acrylate surface modification (SFP130mod), the thermal expansion decreases from 97.5 ppm / K to 50.6 ppm / K for a temperature range of 35-230 °C.

[0098] As shown in Table 3:Table 3: Effect of particle loading on CTECTE [pp / K]0-110 °C 110-200 °C 200-300 °C 35-230 °CBMI-SR834 25 / 75 2wt.% TPO-L 72.9 103.6 123.4 97.5BMI-SR834 25 / 75 + 48wt% 45.0 72.6 116.3 66.0SFP1 0mod 2wt.%> TPO-LBMI-SR834 25 / 75 + 59wt% 36.1 54.7 62.3 50.6SFP1 0mod 2wt.% TPO-LEXAMPLE IV: MECHANICAL PROPERTIES:Thermo-mechanical Properties

[0099] To determine the mechanical properties of the material at elevated temperatures DMA measurements were performed at a temperature range from room temperature to 420 °C. As expected, the mechanical stability decreases steadily with increasing temperature reaching a sudden drop above 350 °C indicating the complete failure. Interestingly, a drop in the Storage- Modulus [VPa] indicating a glass transition temperature cannot be observed (see e.g., FIG. 4). The “Base Resin” curve shows the temperature-dependent Storage Modul for unfilled BML689 and lwt% TPO-L. The “Base Resign higher PI content” curve shows the temperature-dependent Storage Modul for unfilled BML689 and 2wt% TPO-L. The “Base Resin with Silica” curve shows the temperature-dependent Storage Modul for unfilled BML689 in combination with 48wt% SFP130mod and 2wt% TPO-L. The “Base Resin with higher Silica content” curve shows the temperature-dependent Storage Modul for unfilled BML689 in combination with 59wt% SFP130mod and 2wt% TPO-L.

[0100] The effect of BMLacrylate-concentrations on the storage modulus (E) as a function of temperature was performed, and is illustrated in FIG. 8. As illustrated, pure acrylate (0% BMI) has an accelerated loss of stiffness from ~240°C on, while 10% and 20% BMI concentrations show improved thermal stability, and are ultimately crossed by the 0% curve. Although 30% to 50% BMI concentrations exhibit a steeper slope, still, and unlike the SR833S combination is observed (which is an acrylate that does not work in combination with the BMI), no glass-transition (Tg) can be observed.

[0101] Furthermore, as illustrated in FIG. 9, the excellent thermo-mechanical properties are also obtained not only with a photo-initiator content of 2% TPO-L but also with combinations of TPOL (4%) and ethyl 4-(dimethylamino)benzoate (EDB, 2%) as well as TPO-L (1%) and phenylbis( 2,4,6-trimethyl benzoyl) phosphine oxide (BAPO) (1%). The sudden loss in stiffness of the TPOL& EDB sample can be attributed to a breaking of the sample.

[0102] Additionally, the influence of a thermal initiator 2,2'-Azobisisobutyronitrile (AIBN) with a concentration of 2% was investigated. As clearly illustrated in FIG. 10 the sample does not exhibit the onset of translation mobility expressed as glass transition temperature (Tg).

[0103] As further illustrated in FIG. 11, as an alternative to the BML689, the thermomechanical stability as expressed by the storage modulus E, was analyzed using a combination of BML1400 and SR834 (25wt% and 75wt% respectively) was investigated, again showing the arrest of the onset of translation mobility expressed as glass transition temperature (Tg).Differential Scanning Calorimetry (DSC)

[0104] As illustrated in FIG 12, neither the DSC signal (lower curve), nor the heat capacity Cp (top curve), show a discontinuity in the heat flow - typical of a glass transition temperature. The dip of the curves above 250 °C is related to a thermal degradation and thus mass loss of roughly 0.3 % at 300 °C as determined in the TGA measurements illustrated herein.Discussion

[0105] The aliphatic, UV curable and thermally stable bismaleimide resin 1,6- bismaleimido- (2,2,4-trimethyl)hexane (MATMD, BML689) served as the basic component of the studied formulations in various contents. In addition to acrylate resins with high intrinsic glass transition temperatures or multi-functionalities, other resins and aromatic and high molecular weight BMI resins were also used as a further component. The BML689 formulations with acrylate resins showed very homogeneous mixtures, while a formulation with the aromatic BMI could only be added at very small contents. The reactivity of all prepared formulations was investigated with the help of UV rheology. All systems showed a curing of the material under UV exposure. The test specimens were manufactured using the mSLA process and were successful for the formulations with acrylate content. Both UV and thermal curing of the specimens were carried out. The thermal and mechanical tests of the materials with BML689 and acrylate resins in different mixing ratios illustrated in FIGs 5A-5C clearly showed the influence of the aliphatic BMI system. The higherthe BMI content in the systems, the lower the values for the glass transition, the CTE and also flexural characteristics such as modulus, strength and strain. The acrylates with aromatic units in the structure showed high 7g values and the CTE below the 7'g was low.

[0106] Not wishing to be bound by theory, it appears that due to the heterogeneous (BMIAcrylate) network formed, no 7'g could be measured for the systems with multifunctional acrylates; and the CTE values were also reduced. The flexural properties were also influenced by the flexible BMI-689.BMI-689 is represented by the formula:

[0107] The lower the BMI content, the higher the flexural modulus, strength, and strain. The decomposition temperature was positively influenced by the addition of the BMI. Higher contents showed higher thermal stability over a long temperature range.1. Accordingly and in an implementation, provided herein is a method of substantially eliminating the onset of translational mobility of a polymer chain segment following phase change, over a predetermined temperature range, the method including forming a curable liquid composition including: admixing into a solution including a multifunctional acrylate polymer or its oligomer, a multifunctional crosslinking agent (MCA) and a photoinitiator (PI) at a predetermined volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer - to the MCA; and curing the curable liquid composition, thereby forming a cured polymer network, wherein the fractional concentration of the MCA in cured polymer network is configured to be above the three dimensional (3D) bond percolation threshold of the cured polymer network, wherein (i) the MCA has at least 3 functional ends, (ii) includes a Bismaleimide (BMI) monomer represented by the formula:where: X is an aliphatic spacer, an aromatic spacer, or their combination, or (iii) wherein X is an aliphatic chain having the general formula (CH2)n, wherein n is an integer between 1 and 70, wherein (iv) the BMI is: a 4,4'-bismaleimidodiphenylmethane MDAB), and / or a 2,4- bismaleimidotoluene (TDAB), and / or (l,l-(methylenedi-4,l -phenylene) bismaleimide (MDPB), and / or bis(3-methyl-5- ethyl-4-maleimidophenyl) methane, and / or a 2,2-bis(4-maleimido phenoxyphenyl)propane, and / or (5,6-(diheptylen-phenylene) bismaleimide, and / or bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, and / or m-xylylenebismaleimide (MXBI), and / or a 1,6- bismaleimido(trimethyl)hexane (MATMD), wherein (v) the volume ratio between the BMI and the acrylate polymer, or oligomer is between 1:10 and 11 :20, wherein (vi) the acrylate polymer or oligomer is a multifunctional acrylate selected from the group including: 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4- butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A-diglycidyl ether diacrylate, hydroxypivalic acid neopentanediol diacrylate, ethoxylated bisphenol-A- diglycidyl ether diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris(2-cryloyloxyethyl)isocyanurate, pentaerythritol triacrylate, Tris (2-hydroxy ethyl) isocyanuratetriacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate or a multifunctional acrylate composition including one or more of the foregoing and their oligomers, wherein (vii) the photoinitiator is present in the liquid composition at a concentration of between 0.01% and 10%, and is selected from: ethyl(2,4,6, trimethyl benzoyl) phenyl phosphinate), benzophenone and acetophenone compounds, mixed triarylsulfonium hexafluoroantimonate salts, 2-ispropylthioxanthone or a photoinitiator composition including one or more of the foregoing, wherein (viii) the fractional volume concentration of the MCA in the cured polymer network is between about 8% and about 75% (v / v), (ix) the BMI is bis (1,2 maleimidoheptane) 5,6-diheptenylcyclohexene, and the multifunctional acrylate is: Tris (2-hydroxy ethyl) isocyanuratetriacrylate, or Dipentaerythriolhexaacrylate, at a BMI-to the multifunctional acrylate ratio of 1:3, and wherein (x) the predetermined temperature range is between -25 °C (248K) and 400 °C.2. In another implementation, provided herein is a curable dielectric resin composition configured, upon curing, to substantially eliminate the onset of translational mobility of a polymer’s chain, or its oligomer segment at a predetermined temperature range including: a multifunctional acrylate polymer or its oligomer; a multifunctional crosslinking agent (MCA); and a photoinitiator (PI), wherein the volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer - to the MCA is between 1:10 and 11 :20, wherein (xi) the fractional volume concentration of the MCA upon curing the curable dielectric resin composition, is between about 8% and about 75% (v / v), (xii) the MCA includes a Bismaleimide (BMI) monomer represented by the formula:where: X is an aliphatic spacer, an aromatic spacer, or their combination, and / or (xiii) X is an aliphatic chain having the general formula (CH2)n, wherein n is an integer between 1 and 70, wherein (xiv) the BMI is: a 4,4'-bismaleimidodiphenylmethane (MDAB), and / or a 2,4- bismaleimidotoluene (TDAB), and / or (l,l-(methylenedi-4,l -phenylene) bismaleimide (MDPB), and / or bis(3-methyl-5-ethyl-4- maleimidophenyl) methane, and / or a 2,2-bis(4-maleimido phenoxyphenyl)propane, and / or (5,6- (diheptylen-phenylene) bismaleimide, and / or bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, and / or m-xylylenebismaleimide (MXBI), and / or a 1,6- bismaleimido(trimethyl)hexane (MATMD), wherein (xv) the acrylate polymer or oligomer is a multifunctional acrylate selected from the group including: 1,2-ethanediol diacrylate, 1,3- propanediol diacrylate, 1,4-butanediol diacrylate, 1,6- hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A-diglycidyl ether diacrylate, hydroxypivalic acid neopentanediol diacrylate, ethoxylated bisphenol-A-diglycidyl ether diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris(2-acryloyloxyethyl)isocyanurate, pentaerythritol triacrylate, Tris (2-hydroxy ethyl)isocyanuratetriacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate or a multifunctional acrylate composition including one or more of the foregoing and their oligomers, (xvi) the photoinitiator is present in the liquid composition at a concentration of between 0.01% and 10%, and is selected from: ethyl(2,4,6, trimethyl benzoyl) phenyl phosphinate), benzophenone and acetophenone compounds, mixed triarylsulfonium hexafluoroantimonate salts, 2-ispropylthioxanthone or a photoinitiator composition including one or more of the foregoing, wherein (xvii) the BMI is bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, and the multifunctional acrylate is: Tris (2- hydroxy ethyl) isocyanuratetriacrylate, or Dipentaerythriolhexaacrylate, at a BMI-to the multifunctional acrylate ratio of 1:3, and (xviii) the predetermined temperature range is between - 25 °C and 400 °C.

[0108] Although the foregoing disclosure for systems, methods and compositions for substantially eliminating the onset of translational critical chain length mobility of cured polymer, resulting in articles of manufacture exhibiting improved thermomechanical properties over large temperature ranges has been described in terms of some implementations, other implementations will be apparent to those of ordinary skill in the art from the disclosure herein. Moreover, the described implementations have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods, programs, libraries and systems described herein may be embodied in a variety of other forms without departing from the spirit thereof. Accordingly, other combinations, omissions, substitutions and modifications will be apparent to the skilled artisan in view of the disclosure herein.

Claims

CLAIMSWhat is claimed:

1. A curable dielectric resin composition configured, upon curing, to substantially eliminate the onset of translational mobility of a polymer’s chain or its oligomer segment at a predetermined temperature range, the curable dielectric resin composition comprising: a) a multifunctional acrylate polymer or its oligomer; b) a multifunctional crosslinking agent (MCA); and c) a photoinitiator (PI), wherein the volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer to the MCA is between 1:10 and 11:20.

2. The curable dielectric resin composition of claim 1, wherein a fractional volume concentration of the MCA upon curing the curable dielectric resin composition, is between about 8% and about 75% (v / v) in the cured polymer.

3. The curable dielectric resin composition according to any of claims 1-2, wherein the MCA comprises a Bismaleimide (BMI) monomer represented by the formula:where: X is an aliphatic spacer, an aromatic spacer, or a combination thereof.

4. The curable dielectric resin composition of claim 3, wherein the MCA comprises at least one of: a 4,4'-bismaleimidodiphenylmethane (MDAB), a 2,4-bismaleimidotoluene (TDAB), (1,1- (methylenedi-4,1 -phenylene) bismaleimide (MDPB), bis(3-methyl-5-ethyl-4-maleimidophenyl) methane, a 2,2-bis(4-maleimido phenoxyphenyl)propane, (5,6-(diheptylen-phenylene) bismaleimide, bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, m-xylylenebismaleimide (MXBI), and a 1,6- bismaleimido(trimethyl)hexane (MATMD).

5. The curable dielectric resin composition of claim 3, wherein X is an aliphatic chain having the general formula (CH2)n, wherein n is an integer between 1 and 70.

6. The curable dielectric resin composition according to any of claims 1-5, wherein the multifunctional acrylate polymer or oligomer is a multifunctional acrylate selected from the group comprising: 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6- hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol- A-diglycidyl ether diacrylate, hydroxypivalic acid neopentanediol diacrylate, ethoxylated bisphenol-A-diglycidyl ether diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris(2- acryloyloxyethyl)isocyanurate, pentaerythritol triacrylate, Tris (2-hydroxy ethyl) isocyanuratetriacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate or a multifunctional acrylate composition comprising one or more of the foregoing and their oligomers.

7. The curable dielectric resin composition according to any of claims 1-6, wherein the photoinitiator is present in the liquid composition at a concentration of between 0.01% and 10%, and is selected from: ethyl(2,4,6, trimethyl benzoyl) phenyl phosphinate), benzophenone and acetophenone compounds, mixed triarylsulfonium hexafluoroantimonate salts, 2- ispropylthioxanthone or a photoinitiator composition comprising one or more of the foregoing.

8. The curable dielectric resin composition of claim 7, wherein the BMI is bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, and the multifunctional acrylate is: Tris (2- hydroxy ethyl) isocyanuratetriacrylate, or Dipentaerythriolhexaacrylate, at a BMI-to the multifunctional acrylate ratio of 1:3.

9. The curable dielectric resin composition according to any of claims 1-8, wherein the predetermined temperature range is between -25 °C and 400 °C.

10. The curable dielectric resin composition of claim 1, wherein: a) the MCA is selected from the group consisting of: l,l’-C36-alkylenebis-lH- Pyrrole-2,5-dione (BMI-689) and C36-alkylenedi-5,5’-[(l-methylethylidene)bis(4,l- phenyleneoxy)]bis[l,3- isobenzofurandione] bismaleimide oligomer (BMI-1400); andb) the photoinitiator (PI) comprises ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.

11. The curable dielectric resin composition of claim 10, wherein the multifunctional acrylate polymer is a tricyclodecandedimethanol dimethacrylate polymer (SR834).

12. An article of manufacture comprising the composition of any of claims 1-11.

13. A method of 3D printing, comprising applying a curable dielectric resin composition according to any of claims 1-11 with a 3D printer.

14. A method of adhering, comprising applying a curable dielectric resin composition according to any of claims 1-11 to a substrate to be adhered.

15. A method of coating, comprising applying a curable dielectric resin composition according to any of claims 1-11 to a substrate.

16. A method of carbon fiber molding comprising supplying a curable dielectric resin composition according to any of claims 1-11 in a carbon fiber molding process.

17. A method of composite manufacturing, comprising manufacturing a composite with a curable dielectric resin according to any of claims 1-11.

18. An ink for 3D printing comprising the curable dielectric resin composition according to any of claims 1-11.

19. An adhesive comprising the curable dielectric resin composition according to any of claims 1- 11.

20. A coating comprising the curable dielectric resin composition according to any of claims 1-11.

21. Use of the curable dielectric resin composition according to any of claims 1-11 as a resin in 3D printing.

22. Use of the curable dielectric resin composition according to any of claims 1-11 as an adhesive.

23. Use of the curable dielectric resin composition according to any of claims 1-11 as a coating.

24. Use of the curable dielectric resin composition according to any of claims 1-11 in carbon fiber molding.

25. Use of the curable dielectric resin composition according to any of claims 1-11 in composite manufacturing.

26. A method of substantially eliminating the onset of translational mobility of a polymer chain segment following phase change, over a predetermined temperature range, the method comprising forming a curable liquid composition, the method comprising: a) admixing into a solution comprising a multifunctional acrylate polymer or its oligomer, a multifunctional crosslinking agent (MCA) and a photoinitiator (PI) at a predetermined volume ratio (v / v) of the multifunctional acrylate polymer or its oligomer to the MCA; and b) curing the curable liquid composition, thereby forming a cured polymer network, wherein the fractional concentration of the MCA in cured polymer network is configured to be above the three dimensional (3D) bond percolation threshold of the cured polymer network.

27. The method of claim 26, wherein the MCA has at least 3 functional ends.

28. The method of claim 27, wherein the MCA comprises a Bismaleimide (BMI) monomer represented by the formula:where: X is an aliphatic spacer, an aromatic spacer, or a combination thereof.

29. The method of claim 28, wherein the MCA comprises at least one of: a 4,4'- bismaleimidodiphenylmethane MDAB), a 2,4-bismaleimidotoluene (TDAB), (l,l-(methylenedi- 4,1- phenylene) bismaleimide (MDPB), bis(3-methyl-5-ethyl-4-maleimidophenyl) methane, a 2,2- bis(4- maleimido phenoxyphenyl)propane, (5,6-(diheptylen-phenylene) bismaleimide, bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, m-xylylenebismaleimide (MXBI), and a 1,6- bismaleimido(trimethyl)hexane (MATMD) .

30. The method of claim 28, wherein X is an aliphatic chain having the general formula (CH2)n, wherein n is an integer between 1 and 70.

31. The method according to any of claims 26-29, wherein the volume ratio between the BMI and the acrylate polymer, or oligomer is between 1:10 and 11:20.

32. The method according to any of claims 26-31, wherein the multifunctional acrylate polymer or oligomer is a multifunctional acrylate selected from the group comprising: 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A-diglycidyl ether diacrylate, hydroxypivalic acid neopentanediol diacrylate, ethoxylated bisphenol-A- diglycidyl ether diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris(2- acryloyloxyethyl)isocyanurate, pentaerythritol triacrylate, Tris (2-hydroxy ethyl) isocyanuratetriacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate or a multifunctional acrylate composition comprising one or more of the foregoing and their oligomers.

33. The method according to any of claims 26-32, wherein the photoinitiator is present in the liquid composition at a concentration of between 0.01% and 10%, and is selected from: ethyl(2,4,6, trimethyl benzoyl) phenyl phosphinate), benzophenone and acetophenone compounds, mixed triarylsulfonium hexafluoroantimonate salts, 2-ispropylthioxanthone or a photoinitiator composition comprising one or more of the foregoing.

34. The method according to any of claims 26-33, wherein a fractional volume concentration of the MCA in the cured polymer network is between about 8% and about 75% (v / v) in the cured polymer.

35. The method of claim 34, wherein the BMI is bis (1,2 maleimidoheptane) 5,6-diheptenyl cyclohexene, and the multifunctional acrylate is: Tris (2-hydroxy ethyl) isocyanuratetriacrylate, or Dipentaerythriolhexaacrylate, at a BMI-to the multifunctional acrylate ratio of 1:3.

36. The method according to any of claims 26-35, wherein the predetermined temperature range is between -25 °C (248K) and 400 °C.

37. The method according to claim 26, wherein: a) the MCA is selected from the group consisting of: l,l’-C36-alkylenebis-lH- Pyrrole-2, 5-dione, (BMI-689) and C36-alkylenedi-5,5’-[(l-methylethylidene)bis(4,l- phenyleneoxy)]bis[l,3- isobenzofurandione] bismaleimide oligomer (BMI-1400); and b) the PI comprises ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate(TPO-L).

38. The method according to claim 37, wherein the multifunctional acrylate polymer is tricyclodecandedimethanol dimethacrylate polymer (SR834).

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