WO2020191579A1 - Curable compositions, articles therefrom, and methods of making and using same - Google Patents

Curable compositions, articles therefrom, and methods of making and using same Download PDF

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Publication number
WO2020191579A1
WO2020191579A1 PCT/CN2019/079523 CN2019079523W WO2020191579A1 WO 2020191579 A1 WO2020191579 A1 WO 2020191579A1 CN 2019079523 W CN2019079523 W CN 2019079523W WO 2020191579 A1 WO2020191579 A1 WO 2020191579A1
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Prior art keywords
curable composition
composition according
previous
curable
substrate
Prior art date
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PCT/CN2019/079523
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English (en)
French (fr)
Inventor
Li Yao
Michael A. Kropp
Matthew J. Kryger
Wayne S. Mahoney
Mario A. Perez
Shuang Wu
Lingjie TONG
Ahmad Shaaban
Adrian T. Jung
Jeremy M. Higgins
Ying Lin
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to PCT/CN2019/079523 priority Critical patent/WO2020191579A1/en
Priority to CN201980094568.5A priority patent/CN113646383A/zh
Priority to EP19920805.9A priority patent/EP3947560A1/en
Priority to US17/440,976 priority patent/US20220162376A1/en
Priority to JP2021556940A priority patent/JP7689496B2/ja
Priority to PCT/CN2019/125303 priority patent/WO2020192185A1/en
Priority to EP19922124.3A priority patent/EP3947510B1/en
Priority to US17/593,250 priority patent/US20220153987A1/en
Priority to CN201980094301.6A priority patent/CN113646353B/zh
Publication of WO2020191579A1 publication Critical patent/WO2020191579A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/262—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders with fastening means, e.g. locks
    • H01M50/264—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders with fastening means, e.g. locks for cells or batteries, e.g. straps, tie rods or peripheral frames
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure generally relates to curable compositions that include an epoxy composition and a thiol composition.
  • the curable compositions may be used, for example, as thermally conductive gap fillers, which may be suitable for use in electronic applications such as battery assemblies.
  • curable compositions based on epoxy or polyamide resins have been disclosed in the art. Such curable compositions are described in, for example, U.S. Pat. 9,926,405, U.S. Pat. App. Pub. 2013/0165600, and EP Patent 1291390.
  • a curable composition in some embodiments, includes a first part comprising an epoxy resin; and a second part comprising a multifunctional, functional thiol containing compound.
  • the curable composition further includes an inorganic filler present in an amount of at least 20 weight %, based on the total weight of the curable composition.
  • the multifunctional, functional thiol containing compound comprises an ether in the backbone thereof.
  • FIG. 1 illustrates the assembly of an exemplary battery module according to some embodiments of the present disclosure.
  • FIG. 2 illustrates the assembled battery module corresponding to FIG. 1.
  • FIG. 3 illustrates the assembly of an exemplary battery subunit according to some embodiments of the present disclosure.
  • Thermal management plays an important role in many electronics applications such as, for example, electric vehicle (EV) battery assembly, power electronics, electronic packaging, LED, solar cells, electric grid, and the like.
  • EV electric vehicle
  • Certain thermally conductive materials e.g., adhesives
  • the gap filler application As a thermally conductive material, currently, one such application that utilizes a thermally conductive material is the gap filler application.
  • requirements for the gap filler application include high thermally conductivity, good overlap shear adhesion strength, good tensile strength, good elongation at break for toughness, and damping performance, and good hydrolytic stability, in addition to having low viscosity before curing.
  • thermal conductivity typically, a large amount of inorganic thermally conductive filler is added to the composition.
  • the high loading of thermally conductive fillers however, has a deleterious impact on adhesion performance, toughness, damping performance, and viscosity.
  • compositions useful for the gap filler application should have relatively fast curing profiles to accommodate the automated processing requirements of the industry.
  • thermally conductive materials that attain adequate green strength after room temperature cure of about 10 minutes or less may be particularly advantageous.
  • a filled curable composition that includes an epoxy resin, a polyamide composition, an amino functional compound, and a multi-functional (meth) acrylate provides many of the above discussed attributes but does not provide, in some applications, sufficient hydrolytic stability.
  • Another filled curable composition that includes an epoxy composition and a polyamide composition, the polyamide composition including a polyamide having one or more tertiary amides in the backbone thereof, also provides many of the above discussed attributes but does not provide, in some applications, sufficient green strength.
  • a curable composition providing a good balance of the above discussed desired properties
  • the curable compositions of the present disclosure also exhibit good hydrolytic stability and green strength.
  • room temperature refers to a temperature of 22°C to 25°C.
  • curable refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
  • a cured or crosslinked polymer is generally characterized by insolubility, but may be swellable in the presence of an appropriate solvent.
  • unfilled when used in connection with a component or a composition refers to all the materials that make up that component or composition except for inorganic fillers (e.g., thermally conductive fillers) .
  • backbone refers to the main continuous chain of a polymer.
  • aliphatic refers to C1-C40, suitably C1-C30, straight or branched chain alkenyl, alkyl, or alkynyl which may or may not be interrupted or substituted by one or more heteroatoms such as O, N, or S.
  • cycloaliphatic refers to cyclized aliphatic C3-C30, suitably C3-C20, groups and includes those interrupted by one or more heteroatoms such as O, N, or S.
  • alkyl refers to a monovalent group that is a radical of an alkane and includes straight-chain, branched, cyclic, and bicyclic alkyl groups, and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the alkyl groups typically contain from 1 to 30 carbon atoms. In some embodiments, the alkyl groups contain 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 include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.
  • alkylene refers to a divalent group that is a radical of an alkane and includes groups that are linear, branched, cyclic, bicyclic, or a combination thereof. Unless otherwise indicated, the alkylene group typically has 1 to 30 carbon atoms. In some embodiments, the alkylene group has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Examples of “alkylene” groups include methylene, ethylene, 1, 3-propylene, 1, 2-propylene, 1, 4-butylene, 1, 4-cyclohexylene, and 1, 4-cyclohexyldimethylene.
  • aromatic refers to C3-C40, suitably C3-C30, aromatic groups including both carbocyclic aromatic groups as well as heterocyclic aromatic groups containing one or more of the heteroatoms, O, N, or S, and fused ring systems containing one or more of these aromatic groups fused together.
  • aryl refers to a monovalent group that is aromatic and, optionally, carbocyclic.
  • the aryl has at least one aromatic ring. Any additional rings can be unsaturated, partially saturated, saturated, or aromatic.
  • the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring.
  • the aryl groups typically contain from 6 to 30 carbon atoms. In some embodiments, the aryl groups contain 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of an aryl group include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.
  • arylene refers to a divalent group that is aromatic and, optionally, carbocyclic.
  • the arylene has at least one aromatic ring.
  • the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring. Any additional rings can be unsaturated, partially saturated, or saturated.
  • arylene groups often have 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • alkyl refers to a monovalent group that is an alkyl group substituted with an aryl group (e.g., as in a benzyl group) .
  • alkaryl refers to a monovalent group that is an aryl substituted with an alkyl group (e.g., as in a tolyl group) .
  • the alkyl portion often has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms and an aryl portion often has 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • the present disclosure provides a highly filler loaded thermally conductive curable composition formulated by blending an epoxy composition and a thiol composition.
  • the epoxy compositions may include one or more epoxy resins.
  • Suitable epoxy resins may include aromatic polyepoxide resins (e.g., a chain-extended diepoxide or novolac epoxy resin having at least two epoxide groups) , aromatic monomeric diepoxides, aliphatic polyepoxide, ormonomeric diepoxides.
  • a crosslinkable epoxy resin typically will have at least two epoxy end groups.
  • the aromatic polyepoxide or aromatic monomeric diepoxide typically contains at least one (in some embodiments, at least 2, in some embodiments, in a range from 1 to 4) aromatic ring that is optionally substituted by a halogen (e.g., fluoro, chloro, bromo, iodo) , alkyl having 1 to 4 carbon atoms (e.g., methyl or ethyl) , or hydroxyalkyl having 1 to 4 carbon atoms (e.g., hydroxymethyl) .
  • a halogen e.g., fluoro, chloro, bromo, iodo
  • alkyl having 1 to 4 carbon atoms e.g., methyl or ethyl
  • hydroxyalkyl having 1 to 4 carbon atoms e.g., hydroxymethyl
  • the rings may be connected, for example, by a branched or straight-chain alkylene group having 1 to 4 carbon atoms that may optionally be substituted by halogen (e.g., fluoro, chloro, bromo, iodo) .
  • halogen e.g., fluoro, chloro, bromo, iodo
  • examples of aromatic epoxy resins useful in the epoxy compositions disclosed herein may include novolac epoxy resins (e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof) , bisphenol epoxy resins (e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof) , resorcinol epoxy resins, tetrakis phenylolethane epoxy resins and combinations of any of these.
  • novolac epoxy resins e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof
  • bisphenol epoxy resins e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof
  • resorcinol epoxy resins etrakis phenylolethane epoxy resins and combinations of any of these.
  • useful epoxy compounds include diglycidyl ethers of difunctional phenolic compounds (e.g., p, p′-dihydroxydibenzyl, p, p′-dihydroxydiphenyl, p, p′-dihydroxyphenyl sulfone, p, p′-dihydroxybenzophenone, 2, 2′-dihydroxy-1, 1-dinaphthylmethane, and the 2, 2′, 2, 3′, 2, 4′, 3, 3′, 3, 4′, and 4, 4′isomers of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylphenylmethane, dihydroxydiphenylbutylphenylmethane, dihydroxydiphenyltolylethan
  • the adhesive includes a bisphenol diglycidyl ether, wherein the bisphenol (i.e., -O-C 6 H 5 -CH 2 -C 6 H 5 -O-) may be unsubstituted (e.g., bisphenol F) , or either of the phenyl rings or the methylene group may be substituted by one or more halogens (e.g., fluoro, chloro, bromo, iodo) , methyl groups, trifluoromethyl groups, or hydroxymethyl groups.
  • the bisphenol i.e., -O-C 6 H 5 -CH 2 -C 6 H 5 -O-
  • the phenyl rings or the methylene group may be substituted by one or more halogens (e.g., fluoro, chloro, bromo, iodo) , methyl groups, trifluoromethyl groups, or hydroxymethyl groups.
  • examples of aromatic monomeric diepoxides useful in the epoxy compositions according to the present disclosure include the diglycidyl ethers of bisphenol A and bisphenol F and mixtures thereof.
  • Bisphenol epoxy resins may be chain extended to have any desirable epoxy equivalent weight. Chain extending epoxy resins can be carried out by reacting a monomeric diepoxide, for example, with a bisphenol in the presence of a catalyst to make a linear polymer.
  • Other aromatic epoxy resins may include difunctional epoxy resins that have a polysulfide polymer backbone such as block coplymer of Thiokol LP and bisphenol F epoxy resin (e.g. FLEP-60 available from Toray Fine Chemicals Co., Ltd., Tokyo, Japan.
  • the aromatic epoxy resin (e.g., either a bisphenol epoxy resin or a novolac epoxy resin) may have an epoxy equivalent weight of at least 150, 170, 200, or 225 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight of up to 2000, 1500, or 1000 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight in a range from 150 to 2000, 150 to 1000, or 170 to 900 grams per equivalent. In some embodiments, the first epoxy resin has an epoxy equivalent weight in a range from 150 to 450, 150 to 350, or 150 to 300 grams per equivalent. Epoxy equivalent weights may be selected, for example, so that the epoxy resin may be used as a liquid or solid, as desired.
  • the epoxy resins of the present disclosure may include one or more non-aromatic epoxy resins.
  • non-aromatic epoxy resins can be useful as reactive diluents that may help control the flow characteristics of the compositions.
  • Non-aromatic epoxy resins useful in the curable compositions according to the present disclosure can include a branched or straight-chain alkylene group having 1 to 20 carbon atoms optionally interrupted with at least one -O-and optionally substituted by hydroxyl.
  • the non-aromatic epoxy can include a poly (oxyalkylene) group having a plurality (x) of oxyalkylene groups, OR 1 , wherein each IV is independently C 2 to C 5 alkylene, in some embodiments, C 2 to C 3 alkylene, x is 2 to about 6, 2 to 5, 2 to 4, or 2 to 3.
  • useful non-aromatic epoxy resins will typically have at least two epoxy end groups. Examples of useful non-aromatic epoxy resins include glycidyl epoxy resins such as those based on diglycidyl ether compounds comprising one or more oxyalkylene units.
  • Examples of these include resins made from ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, propanediol diglycidyl ether, butanediol diglycidyl ether, and hexanediol diglycidyl ether.
  • Non-aromatic epoxy resins include a diglycidyl ether of cyclohexane dimethanol, a diglycidyl ether of neopentyl glycol, a triglycidyl ether of trimethylolpropane, and a diglycidyl ether of 1, 4-butanediol.
  • Crosslinked aromatic epoxies that is, epoxy polymers as described herein can be understood to be preparable by crosslinking aromatic epoxy resins.
  • the crosslinked aromatic epoxy typically contains a repeating unit with at least one (in some embodiments, at least 2, in some embodiments, in a range from 1 to 4) aromatic ring (e.g., phenyl group) that is optionally substituted by one or more halogens (e.g., fluoro, chloro, bromo, iodo) , alkyl groups having 1 to 4 carbon atoms (e.g., methyl or ethyl) , or hydroxyalkyl groups having 1 to 4 carbon atoms (e.g., hydroxymethyl) .
  • aromatic ring e.g., phenyl group
  • halogens e.g., fluoro, chloro, bromo, iodo
  • alkyl groups having 1 to 4 carbon atoms e.g., methyl or ethyl
  • hydroxyalkyl groups having 1 to 4 carbon atoms
  • the rings may be connected, for example, by a branched or straight-chain alkylene group having 1 to 4 carbon atoms that may optionally be substituted by halogen (e.g., fluoro, chloro, bromo, iodo) .
  • halogen e.g., fluoro, chloro, bromo, iodo
  • the epoxy resins of the present disclosure may be liquid at room temperature.
  • curable epoxy resins useful in the epoxy compositions according to the present disclosure may be commercially available.
  • epoxy resins of various classes and epoxy equivalent weights are available from Olin Corporation, Clayton MO; Hexion Inc., Columbus, Ohio; Huntsman Advanced Materials, The Woodlands, Tex. ; CVC Specialty Chemicals Inc. Akron, Ohio (acquired by Emerald Performance Materials) ; and Nan Ya Plastics Corporation, Taipei City, Taiwan.
  • Examples of commercially available glycidyl ethers include diglycidylethers of bisphenol A (e.g.
  • EPICLON those available under the trade designation “EPICLON” from Dainippon Ink and Chemicals, Inc. (e.g., “EPICLON 830” ) ) ; polyglycidyl ethers of novolac resins (e.g., novolac epoxy resins, such as those available under the trade designation “D.E.N. ” from Olin Corporation. (e.g., D.E.N. 425, 431, and 438) ) ; and flame retardant epoxy resins (e.g., “D.E.R. 560” , a brominated bisphenol type epoxy resin available from Olin Corporation) .
  • non-aromatic epoxy resins include the glycidyl ether of cyclohexane dimethanol, available from Hexion Inc., under the trade designation “HELOXY MODIFIER 107” .
  • aromatic epoxy resins useful in the epoxy compositions disclosed herein may include a flexible bisphenol A, bisphenol F, or bisphenol Z epoxy resin represented by the following structural formula:
  • Ar is an aromatic group (which can include bisphenol A, bisphenol F, or bisphenol Z) having from10 to 20 carbon atoms and from 0 to 5 substiuents selected from aliphatic hydrocarbon groups, ether groups, or combinations thereof.
  • Suitable aromatic epoxy resins include those available under the trade designation ARALDITE PY-4122 available from Huntsman (Woodlands, TX) , SE-4125P available from SHIN-A T&C and Epon 872 available from Hexion (Columbus, OH) .
  • the epoxy compositions of the present disclosure may include epoxy resin in an amount of between 5 wt. %and 40 wt. %, 10 wt. %and 30 wt. %, 15 wt. %and 30 wt. %, or 20 wt. %and 30 wt. % (or may be even higher (up to 95%, 99%, or 100%) for curable compositions that do not include fillers) , based on the total weight of the epoxy composition.
  • the epoxy compositions of the present disclosure may include epoxy resin in an amount of at least 10 wt. %, at least 20 wt.%, at least 30 wt. %, at least 40 wt. %, or at least 50 wt. %, based on the total weight of the epoxy composition.
  • the thiol composition may include one or more multifunctional, functional thiol containing compounds.
  • a thiol refers to an organosulfur compound that contains a carbon-bonded sulfhydryl or mercapto (–C–SH) group.
  • the multifunctional, functional thiol containing compounds may include at least two functional thiols.
  • one or more of the functional thiols in the multifunctional, functional thiol containing compounds may be a terminal thiol.
  • the multifunctional, functional thiol containing compounds may include an ether in the backbone thereof.
  • the multifunctional, functional thiol containing compounds may include, for example, one or more alcohol or amine functional functional groups.
  • the multifunctional, functional thiol can be a di-functional thiol, tri-functional thiol, tetra-functional thiol, or a polyfunctional thiol.
  • the multifunctional, functional thiol containing compounds may include a compound represented by the following structural formula:
  • R is a aliphatic hydrocarbon having from 3 to 11 or 5 to 9 carbon atoms
  • n is 0 to 20 or 1 to 10
  • m is 2 to 4, or 2 to 3.
  • the multifunctional, functional thiol containing compounds may include a compound represented by the following structural formula:
  • each R1, R2 and R3 is, independently, an alkyl groups having 1 to 4 or 1 to 3 carbon atoms or hydrogen, and n is 0 to 20 or 1 to 10.
  • Suitable commercially available multifunctional, functional thiol containing compounds include those available under the trade designation GPM-800LO, GPM-800 and Capcure 3-800 available from Gabriel Chemical (Akron, OH) , and tetra (ethylene glycol) dithiol, DMDO (1, 8-Dimercapto-3, 6-dioxaoctane) from Sigma Aldrich (Saint Louis, MO) .
  • the multifunctional, functional thiol containing compounds may be used alone or as a mixture of two or multiple different thiol-functionalized compounds.
  • the multifunctional, functional thiol containing compounds of the thiol composition may be liquid (e.g., a viscous liquid having a viscosity of about 500-50,000 cP) at room temperature.
  • the epoxy and thiol compositions may be present in the curable compositions based on stoichiometric ratios of the functional groups of the respective components. Employing such relative amounts may be advantageous in that it can reduce the amount of residual unreacted thiol or epoxy in the cured composition, which residual components can migrate or provide environmental or health challenges.
  • the curable compositions of the present disclosure may be provided (e.g., packaged) as a two-part composition, in which a first part includes the epoxy composition (hereinafter “the first part” ) and a second part includes the thiol composition (hereinafter “the second part” ) .
  • the first part may include epoxy resin in an amount of at least 50 wt. %, at least 60 wt. %, or at least 68 wt. %; or between 50 and 90 wt. %, between 60 and 80 wt. %, or between 65 and 70 wt. %, based on the total weight of the unfilled first part.
  • the second part may include multifunctional, functional thiol containing compounds in an amount of at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, or at least 76 wt%; or between 50 and 90 wt. %, between 65 and 88 wt. %, or between 73 and 78 wt. %, based on the total weight of the unfilled second part.
  • the curable composition may include epoxy resin in an amount of at least 20 wt. %, at least 30 wt. %, or at least 35 wt. %; or between 20 and 60 wt. %, between 35 and 45 wt.
  • the curable composition may include multifunctional, functional thiol containing compounds in an amount of at least 10 wt. %, at least 20 wt. %, or at least 30 wt. %; or between 20 and 60 wt. %, between 35 and 45 wt. %, or between 33 and 35 wt. %, based on the total weight of the unfilled curable composition.
  • the first part and the second part may, independently, include one or more additives such as inorganic fillers, coupling agents, tougheners, dispersants, catalysts, antioxidants, and the like, which are described in further detail below.
  • the present disclosure further provides a dispenser comprising a first chamber and a second chamber.
  • the first chamber comprises the first part and the second chamber comprises the second part.
  • the curable compositions may include one or more inorganic fillers (e.g. thermally conductive inorganic fillers) .
  • Inorganic fillers may be provided to the curable compositions via the first part, the second part, both parts, or following mixing of the first and second parts.
  • the selection and loading levels of the inorganic fillers may be used to control the thermal conductivity of the curable composition.
  • inorganic filler loadings may be at least 20 vol. %, at least 30 vol. %, at least 40 vol. %, at least 50 vol. %, at least 60 vol. %, at least 70 vol. %, at least 80 vol.
  • inorganic filler loadings may be between 20 and 90 vol. %, between 30 and 80 vol. %, between 50 and 70 vol. %, or between 60 and 65 vol. %, based on the total volume of any or all of the epoxy composition, the thiol composition, or the curable composition.
  • thermally conductive fillers may be used, although electrically insulating fillers may be preferred where breakthrough voltage is a concern.
  • Suitable electrically insulating, thermally conductive fillers include ceramics such as oxides, hydroxides, oxyhydroxides, silicates, borides, carbides, and nitrides.
  • Suitable ceramic fillers include, e.g., silicon oxide, aluminum oxide, aluminum trihydroxide (ATH) , boron nitride, silicon carbide, and beryllium oxide.
  • the thermally conductive filler includes ATH.
  • thermally conducting fillers include carbon-based materials such as graphite and metals such as aluminum and copper.
  • Thermally conductive filler particles are available in numerous shapes, e.g. spheres, irregular, platelike, & acicular. Through-plane thermal conductivity may be important in certain applications. Therefore, in some embodiments, generally symmetrical (e.g., spherical or semi-spherical) fillers may be employed. To facilitate dispersion and increase filler loading, in some embodiments, the thermally conductive fillers may be surface-treated or coated. Generally, any known surface treatments and coatings may be suitable, including those based on silane, titanate, zirconate, aluminate, and organic acid chemistries. For powder handling purposes, many fillers are available as polycrystalline agglomerates or aggregates with or without binder. To facilitate high thermal conductivity formulations, some embodiments may include mixtures of particles and agglomerates in various size and mixtures.
  • the curable compositions of the present disclosure may include one or more silane coupling agents.
  • Silane coupling agents were discovered to meaningfully improve overlap shear strength, after aging, of the cured curable compositions.
  • silane coupling agents may be provided to the curable compositions via the first part, the second part, both parts, or following mixing of the first and second parts.
  • Sutiable silane coupling agents may include silane thiols, silane amines (e.g., silane secondary amines) , or silane epoxies.
  • suitable silane coupling agents may include those described in E.P. Plueddemann, Silane Coupling Agents, 2nd ed., Springer US, New York, 1991, which is herein incorporated by reference in its entirety.
  • suitable silane coupling agents may be described as organosilicone compounds having two functional groups with different reactivity -one of the two functional groups reacts with inorganic materials and the other generally reacts with organic materials.
  • the silane coupling agents may have the following general structural formula:
  • Y is a functional group that is compatable with, or links with, organic materials, e.g. a vinyl, epoxy, amino, thiol, isocyanate group, or the like;
  • R is an aliphatic group (typically, an aliphatic group having from 2-6 carbon atoms) ; and
  • X is a functional group that undergoes hydrolysis by water or moisture to form silanol (e.g., a chlorine, alkoxy, or acetoxy group)
  • n is 1-3 or 1-2.
  • silane coupling agents including 3-glycidoxypropyltriethoxysilane, 5, 6-epoxyhexyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, mercaptoproyltriethoxysilane, s- (octanoyl) mercaptopropyltriethoxysilane, hydroxy (polyethyleneoxy) propyltriethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, or comboinations therof.
  • the first part may include a silane epoxy and the second part may include either or both of a silane thiol and a silane amine.
  • silane coupling agents may be present in the curable composition in an amount of at least 0.1 wt. %, at least 10 wt. %, or at least 15 wt. %; or between 0.1 and 60 wt. %, between 9 and 20 wt. %, or between 14 and 17 wt. %, based on the total weight of the unfilled curable composition.
  • silane coupling agents may be present in the first part in an amount of at least 0.1 wt. %, at least 15 wt. %, or at least 20 wt. %; or between 50 and 90 wt. %, between 60 and 80 wt. %, or between 65 and 70 wt.
  • silane coupling agents may be present in the second part in an amount of at least 0.1 wt. %, at least 5 wt. %, or at least 10 wt. %; or between 0.1 and 40 wt. %, between 5 and 16 wt. %, or between 9 and 11 wt. %, based on the total weight of the unfilled second part.
  • the curable compositions according to the present disclosure may include one or more catalysts.
  • the catalysts may act to accelerate the cure of the curable composition.
  • Suitable catalysts according to the present disclosure may include basic catalysts, Lewis acid catalysts, or a combination thereof.
  • the suitbale basic catalyst may include nitrogen-containing catalysts.
  • the nitrogen-containing catalysts may include amine-containing catalysts.
  • the amine-containing catalysts may include at least two groups of formula-NR 1 R 2 , where R 1 and R 2 are, independently, selected from hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • R 1 and R 2 are, independently, selected from hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • Suitibale alkyl groups often have 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the alkyl group can be cyclic, branched, linear, or a comination thereof.
  • Suitable aryl group usually have 6 to 12 carbon atoms such as a phenyl or biphenyl group.
  • Suitable alkylaryl group can include the same aryl and alkyl groups discussed above.
  • the amine-containing catalysts may be an imidazole, an imidazole-salt, and imidazoline, or a comination thereof.
  • Aromatic tertiary amines may also used as a catlyst, including those having the structure formula:
  • R 4 is hydgoen or an alkyl group
  • R 5 , R 6 and R 7 are, independently, hydrogen or CHNR 8 R 9 , wherein at least one of R5, R6 and R7is CHNR 8 R 9 , and R 8 and R 9 are, independently, alkyl groups.
  • the akyl groups of R 4 , R 8 , and/or R 9 are methyl or ethyl groups.
  • the amine-containing catalysts may include tris-2, 4, 6- (dimethylaminomethyl) phenol, commercially available under the tradename ANCAMINE K54 from Evonik Corporation (Parsippany, NJ) , as the structural formula:
  • the nitrogen-containing catalysts may include cyclic or bridged nitrogen containing compounds, including amidine compounds such as 1, 5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1, 8-diaza-bicyclo [5.4.0] undec-7-ene (DBU) , and also diazabicyclo [2.2.2] octane (DABCO) from Sigma Aldrich (Saint Louis, MO, US) with the structual formula:
  • the catalysts may be present in the curable composition (or either or both of the first part and the second part) in an amount between 100 and 10,000 ppm or 200 and 5,000 ppm, based on the total weight or volume of any or all of the unfilled curable composition, the unfilled first part, or the unfilled second part.
  • cyclic-type nitrogen containing catalysts such as DABCO
  • non-cyclic nitrogen containing catalysts such as K54
  • basic catalysts may be present in the curable composition in an amount of at least 1 wt. %, at least 2 wt. %, or at least 3 wt. %; or between 1 and 20 wt. %, between 2 and 10 wt. %, or between 3 and 5 wt. %, based on the total weight of the unfilled curable composition.
  • the second part may include a basic catalyst.
  • basic catalysts may be present in the second part in an amount of at least 0.5 wt. %, at least 5 wt. %, or at least 7 wt. %; or between 0.5 and 30 wt. %, between 5 and 15 wt.
  • the second part may include a Lewis acid catalyst.
  • Lewis acid catalyst may be present in the curable composition in an amount of at least 1 wt. %, at least 2 wt. %, or at least 3 wt. %; or between 1 and 20 wt. %, between 2 and 10 wt. %, or between 3 and 5 wt. %, based on the total weight of the unfilled curable composition.
  • Lewis acid catalysts may be present in the second part in an amount of at least 0.5 wt. %, at least 5 wt. %, or at least 7 wt. %; or between 0.5 and 30 wt. %, between 5 and 15 wt. %, or between 7 and 10 wt. %, based on the total weight of the unfilled second part.
  • the curable compositions according to the present disclosure may include one or more dispersants.
  • the dispersants may act to stabilize the inorganic filler particles in the composition -without dispersant, the particles may aggregate, thus adversely affecting the benefit of the particles in the composition.
  • Suitable dispersants may depend on the specific identity and surface chemistry of filler.
  • suitable dispersants according to the present disclosure may include at least a binding group and a compatibilizing segment.
  • the binding group may be ionically bonded to the particle surface. Examples of binding groups for alumina particles include phosphoric acid, phosphonic acid, sulfonic acid, carboxylic acid, and amine.
  • the compatibilizing segment may be selected to be miscible with the curable matrix.
  • useful compatibilizing agents may include polyalkylene oxides, e.g., polypropylene oxide, polyethylene oxide, as well as polycaprolactones, and combinations thereof.
  • Commercially available examples include BYK W-9010 (BYK Additives and Instruments) , BYK W-9012 (BYK Additives and Instruments) , Disberbyk 180 (BYK Additives and Instruments) , and Solplus D510 (Lubrizol Corporation) .
  • the dispersants may be present in the curable composition in an amount between 0.1 and 10 wt. %, 0.1 and 5 wt. %, 0.5 and 3 wt. %, or 0.5 and 2 wt.
  • the dispersants may be present in the unfilled curable composition (or the first part or the second part) in an amount between 0.1 and 30 wt. %, 1 and 20 wt. %, 5 and 15 wt. %, or 7 and 10 wt. %, based on the total weight of the total weight of the unfilled first part, the unfilled second part, or the unfilled curable compostion.
  • the dispersant may be pre-mixed with the inorganic filler prior to incorporating into any or all of the first part, the second part, or the curable composition.
  • Such pre-mixing may facilitate the filled systems behaving like Newtonian fluids or enable shear-thinning effects behavior.
  • additives can be included in one or both of the first and second parts.
  • additives if present, are added in an amount effective for their intended purpose.
  • the curable compositions of the present disclosure may exhibit thermal, mechanical, and rheological properties that render the compositions particularly useful as thermally conductive gap fillers.
  • curable compositions of the present disclosure provide an optimal blend of tensile strength, elongation at break, and overlap shear strength (even after aging) for certain EV battery assembly applications.
  • the cured compositions may have an elongation at break that ranges from 0.1 to 100 %, 0.5 to 80 %, 1 to 50%, or 8 to 15 %, with the pulling rate between 0.8 and 1.5 mm/min for fully cured systems (for purposes of the present application, elongation at break values are as measured in accordance with ASTM D638-14, “Standard Test Method for Tensile Properties of Plastics. ” ) ; or at least 1%, at least 3%, at least 7%, at least 10%, at least 15%with the pulling rate between 0.8 and 1.5 mm/min for fully cured systems.
  • the cured compositions may have an overlap shear strength on a bare aluminum substrate ranging from 1-30 N/mm 2 , 1-25 N/mm 2 , 4-20 N/mm 2 , 6-20 N/mm 2 , 2 -16 N/mm 2 , or 3 -8 N/mm 2 , for fully cured systems (for purposes of the present application, overlap sheer strength values are as measured on untreated aluminum substrates (i.e., aluminum substrates having no surface treatments or coatings other than native oxide layers) according to the procedures of ASTM D1002-01, “Standard Test Method for Apparent Shear Strength of Single-Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading (Metal-to-Metal) ) . ”
  • the cured compositions may have a tensile strength ranging from 0.5-16 N/mm 2 , 1 -10 N/mm 2 , or 2 -8 N/mm 2 , with the pulling rate between 0.8 and 1.5 mm/min for fully cured systems (for purposes of the present application, tensile strength values are as measured in accordance with ASTM D638-14, “Standard Test Method for Tensile Properties of Plastics. ” ) .
  • the cured compositions may be hydrolytically stable.
  • the cured composistions may exhibit over 70%retention of overlap shear strength (measured as described above) after humidity testing according to PR 308.2 Test Method. Additionally, or alternatively, the cured composistions may exhibit less than 30%reduction in tensile strength (measured as described above) after humidity testing according to PR 308.2 Test Method.
  • the compositions may have desirable cure rates.
  • the curable compositions of the present disclosure may, at room temperature, exhibit gelation times (time at which G’ (storage modulus) is equal to G” (loss modulus) ) of no more than 10 minutes, 30 minutes, 60 minutes, or 80 minutes, as determined in using an oscillating shear rheometer measurement at 100 rad/sangular frequency at 1%strain on a Discovery HR-3 Rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven accessory.
  • G’ storage modulus
  • G loss modulus
  • the curable compositions of the present disclosure may have a thermal conductivity ranging from 1.0 to 5 W/ (m*K) , 1.0 to 2 W/ (m*K) , or 1.5 to 1.8 W/ (m*k) (for purposes of the present application, thermal conductivity values are as determined by, first, measuring diffusivity according to ASTM E1461-13, “Standard Test Method for Thermal Diffusivity by the Flash Method” and, then, calculating thermal conductivity from the measured thermal diffusivity, heat capacity, and density measurements according the formula:
  • k ⁇ ⁇ cp ⁇ , where k is the thermal conductivity in W/ (m K) , ⁇ is the thermal diffusivity in mm 2 /s, cp is the specific heat capacity in J/K-g, and ⁇ is the density in g/cm 3 .
  • the sample thermal diffusivity can be measured using a Netzsch LFA 467 “HYPERFLASH” directly and relative to standard, respectively, according to ASTM E1461-13. Sample density can be measured using geometric methods, while the specific heat capacity can measured using Differential Scanning Calorimetry. )
  • the viscosity of curable/partially cured composition measured at room temperature may range from 100 to 50000 poise, and at 60°C may range from 100 to 50000 poise.
  • the present disclosure is further directed to methods of making the above-described curable compositions.
  • the curable compositions of the present disclosure may be prepared by, first, mixing the components of the first part (including any additives) and, separately, mixing the components of the second part (including any additives) .
  • the components of both the first and second parts may be mixed using any conventional mixing technique, including by use of a speed mixer.
  • the dispersant may be pre-mixed with the inorganic filler prior to incorporating into the composition.
  • the first and second parts may be mixed together using any conventional mixing technique to form the curable composition.
  • the curable compositions of the present disclosure may be capable of curing without the use of catalyst or other cure agents.
  • the curable compositions may cure at typical application conditions, e.g., at room temperature without the need for elevated temperatures or actinic radiation (e.g., ultraviolet light) .
  • the first curable compositions cure at no greater than room temperature.
  • the curable compositions of the present disclosure may be provided as a two-part composition.
  • the two components of a two-part composition may be mixed prior to being applied to the substrates to be bonded. After mixing, the two-part composition may reach a desired handling strength, and ultimately achieve a desired final strength.
  • Applying the curable composition can be carried out, for example, by dispensing the curable composition from a dispenser comprising a first chamber, a second chamber, and a mixing tip, wherein the first chamber comprises the first part, wherein the second chamber comprises the second part, and wherein the first and second chambers are coupled to the mixing tip to allow the first part and the second part to flow through the mixing tip.
  • the curable compositions of the present disclosure may be useful for coatings, shaped articles, adhesives (including structural and semi-structural adhesives) , magnetic media, filled or reinforced composites, caulking and sealing compounds, casting and molding compounds, potting and encapsulating compounds, impregnating and coating compounds, conductive adhesives for electronics, protective coatings for electronics, as primers or adhesion-promoting layers, and other applications that are known to those skilled in the art.
  • the present disclosure provides an article comprising a substrate, having a cured coating of the curable composition thereon.
  • the curable composition may function as a structural adhesive, i.e. the curable composition is capable of bonding a first substrate to a second substrate, after curing.
  • the bond strength e.g. peel strength, overlap shear strength, or impact strength
  • the present disclosure provides an article comprising a first substrate, a second substrate and a cured composition disposed between and adhering the first substrate to the second substrate, wherein the cured composition is the reaction product of the curable composition according to any one of the curable compositions of the present disclosure.
  • the first and/or second substrate may be at least one of a metal, a ceramic and a polymer, e.g. a thermoplastic.
  • the curable compositions may be coated onto substrates at useful thicknesses ranging from 5 microns to 10000 microns, 25 micrometers to 10000 micrometers, 100 micrometers to 5000 micrometers, or 250 micrometers to 1000 micrometers.
  • Useful substrates can be of any nature and composition, and can be inorganic or organic.
  • useful substrates include ceramics, siliceous substrates including glass, metal (e.g., aluminum or steel) , natural and man-made stone, woven and nonwoven articles, polymeric materials, including thermoplastic and thermosets, (such as polymethyl (meth) acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate) , silicones, paints (such as those based on acrylic resins) , powder coatings (such as polyurethane or hybrid powder coatings) , and wood; and composites of the foregoing materials.
  • thermoplastic and thermosets such as polymethyl (meth) acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate
  • silicones such as those based on acrylic resins
  • the present disclosure provides a coated article comprising a metal substrate comprising a coating of the uncured, partially cured or fully cured curable composition on at least one surface thereof. If the substrate has two major surfaces, the coating can be coated on one or both major surfaces of the metal substrate and can comprise additional layers, such as bonding, tying, protective, and topcoat layers.
  • the metal substrate can be, for example, at least one of the inner and outer surfaces of a pipe, vessel, conduit, rod, profile shaped article, sheet or tube.
  • the present disclosure is further directed to a battery module that includes the uncured, partially cured or fully cured curable compositions of the present disclosure.
  • Battery module 50 may be formed by positioning a plurality of battery cells 10 on first base plate 20.
  • any known battery cell may be used including, e.g., hard case prismatic cells or pouch cells.
  • the number, dimensions, and positions of the cells associated with a particular battery module may be adjusted to meet specific design and performance requirements.
  • the constructions and designs of the base plate are well-known, and any base plate (typically metal base plates made of aluminum or steel) suitable for the intended application may be used.
  • Battery cells 10 may be connected to first base plate 20 through first layer 30 of a first curable composition according to any of the embodiments of the present disclosure.
  • First layer 30 of the curable composition may provide first level thermal management where the battery cells are assembled in a battery module.
  • a voltage difference e.g., a voltage difference of up to 2.3 Volts
  • breakthrough voltage may be an important safety feature for this layer. Therefore, in some embodiments, electrically insulating fillers like ceramics (typically alumina and boron nitride) may be preferred for use in the curable compositions.
  • layer 30 may comprise a discrete pattern of the first curable composition applied to first surface 22 of first base plate 20, as shown in FIG. 1.
  • a pattern of the material to the desired lay-out of the battery cells may be applied, e.g., robotically applied, to the surface of the base plate.
  • the first layer may be formed as a coating of the first curable composition covering all or substantially all of the first surface of the first base plate.
  • the first layer may be formed by applying the curable composition directly to the battery cells and then mounting them to the first surface of the first base plate.
  • the curable composition may need to accommodate dimensional variations of up to 2 mm, up to 4 mm, or even more. Therefore, in some embodiments, the first layer of the first curable composition may be at least 0.05 mm thick, e.g., at least 0.1 mm, or even at least 0.5 mm thick. Higher breakthrough voltages may require thicker layers depending on the electrical properties of the material, e.g., in some embodiments, at least 1, at least 2, or even at least 3 mm thick. Generally, to maximize heat conduction through the curable composition and to minimize cost, the curable composition layer should be as thin as possible, while still ensure good contact with the heat sink. Therefore, in some embodiments, the first layer is no greater than 5 mm thick, e.g., no greater than 4 mm thick, or even no greater than 2 mm thick.
  • the battery cells are held more firmly in-place.
  • the battery cells are finally fixed in their desired position, as illustrated in FIG. 2. Additional elements, such as bands 40 may be used to secure the cells for transport and further handling.
  • the curable composition cures at typical application conditions, e.g., without the need for elevated temperatures or actinic radiation (e.g., ultraviolet light) .
  • the first curable composition cures at room temperature, or no greater than 30 °C, e.g., no greater than 25 °C, or even no greater than 20 °C.
  • the time to cure is no greater than 60 minutes, e.g., no greater than 40 minutes, or even no greater than 20 minutes.
  • very rapid cure e.g., less than 5 minutes or even less than 1 minute
  • an open time of at least 5 minutes, e.g., at least 10 minutes, or even at least 15 minutes may be desirable to allow time for positioning and repositioning of the battery cells.
  • a plurality of battery modules 50 are assembled to form battery subunit 100.
  • the number, dimensions, and positions of the modules associated with a particular battery subunit may be adjusted to meet specific design and performance requirements.
  • the constructions and designs of the second base plate are well-known, and any base plate (typically metal base plates) suitable for the intended application may be used.
  • Individual battery modules 50 may be positioned on and connected to second base plate 120 through second layer 130 of a curable composition according to any of the embodiments of the present disclosure.
  • Second layer 130 of a second curable composition may be positioned between second surface 24 of first base plate 20 (see FIGS. 1 and 2) and first surface 122 of second base plate 120.
  • the second curable composition may provide second level thermal management where the battery modules are assembled into battery subunits. At this level, breakthrough voltage may not be a requirement. Therefore, in some embodiments, electrically conductive fillers such as graphite and metallic fillers may be used or alone or in combinations with electrically insulating fillers like ceramics.
  • the second layer 130 may be formed as coating of the second curable composition covering all or substantially all of first surface 122 of second base plate 120, as shown in FIG. 3.
  • the second layer may comprise a discrete pattern of the second curable composition applied to the surface of the second base plate.
  • a pattern of the material corresponding to the desired lay-out of the battery modules may be applied, e.g., robotically applied, to the surface of the second base plate.
  • the second layer may be formed by applying the second curable composition directly to second surface 24 of first base plate 20 (see FIGS. 1 and 2) and then mounting the modules to first surface 122 of second base plate 120.
  • the assembled battery subunits may be combined to form further structures.
  • battery modules may be combined with other elements such as battery control units to form a battery system, e.g., battery systems used in electric vehicles.
  • additional layers of curable compositions according to the present disclosure may be used in the assembly of such battery systems.
  • thermally conductive gap filler according to the present disclosure may be used to mount and help cool the battery control unit.
  • a curable composition comprising:
  • an inorganic filler present in an amount of at least 20 weight %, based on the total weight of the curable composition
  • the multifunctional, functional thiol containing compound comprises an ether in the backbone thereof.
  • R is an aliphatic hydrocarbon
  • n is 0 to 20
  • m is 2 to 4 .
  • R1, R2 and R3 is, independently, an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is 0 to 20.
  • Ar is bisphenol A, bisphenol F, bisphenol Z, or a mixture thereof.
  • silane coupling agent comprises an amine terminated silane coupling agent.
  • silane coupling agent comprises a mercaptan terminated silane coupling agent.
  • silane coupling agent comprises an epoxy terminated silane coupling agent.
  • curable composition according to any one of the previous embodiments, wherein epoxy resin is present in the curable composition in an amount of at least 20 wt. %, based on the total weight of the unfilled curable composition.
  • curable composition according to any one of the previous embodiments, wherein multifunctional, functional thiol containing compounds are present in the curable composition in an amount of at least 10 wt. %, based on the total weight of the unfilled curable composition.
  • curable composition according to any one of the previous embodiments, wherein the curable composition has, upon curing, (i) an elongation at break of greater than 5.5 %, and (ii) an overlap shear strength, on untreated aluminum, of 5-20 N/mm 2 .
  • curable composition according to any one of the previous embodiments, wherein the curable composition has, upon curing, a tensile strength of 1 to 16 N/mm2.
  • curable composition according to any one of the previous embodiments, wherein the curable composition exhibits a gelation time, at room temperature, of no more than 60 minutes, as determined with an oscillating shear rheometer measurement at 100 rad/sangular frequency at 1%strain on a Discovery HR-3 Rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven accessory.
  • a gelation time at room temperature, of no more than 60 minutes, as determined with an oscillating shear rheometer measurement at 100 rad/sangular frequency at 1%strain on a Discovery HR-3 Rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven accessory.
  • An article comprising a first substrate, a second substrate and a cured composition disposed between and adhering the first substrate to the second substrate, wherein the cured composition is the reaction product of the curable composition according to any one of embodiments 1-30.
  • a battery module comprising a plurality of battery cells connected to a first base plate by a first layer of the reaction product of the curable composition according to any one of embodiments 1-30.
  • a method of making a battery module comprising: applying a first layer of a curable composition according to any one of embodiments 1-30 to a first surface of a first base plate, attaching a plurality of battery cells to the first layer to connect the battery cells to the first base plate, and curing the curable composition.
  • Table 1 summarizes materials used in the examples.
  • Parts A and B were mixed individually as follows. First, the organic components were combined and mixed by hand. The thixotropic additive was then added, followed by hand mixing. A speed mixer (SPEEDMIXER DAC 400, FlackTek, Inc., Landrum, SC, US) was then used at 1500 rpm for 2 min to thoroughly mix the materials. The remaining filler materials were combined and added to the formulation in 2 portions. The addition of each portion was followed by mixing in the DAC 400 mixer at 2000 RPM for 2 min. In a final step the materials were mixed in the in DAC 400 mixer for 15 seconds at atmospheric pressure at 1500 RPM, then for two minutes at 30 Torr and 2000 RPM, and then a final 15 seconds at 1500 RPM as the pressure returned to atmospheric pressure.
  • Part A and Part B were mixed based on the stoichiometric ratios of the functional groups: moles of thiol groups in Part A and combined moles of epoxide groups in Part B.
  • a pneumatic dispensing system with a static mixing nozzle was used to mix Part A and Part B in the ratios listed in Tables 2 and 3.
  • OLS tests were conducted on an INSTRON Universal Testing Machine model 1122 (INSTRON Corporation, Norwood, MA, USA) according to the procedures of ASTM D1002-01, “Standard Test Method for Apparent Shear Strength of Single-Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading (Metal-to-Metal) . ”
  • the crosshead speed was 0.05 inch/minute (1.27 mm/minute) .
  • dog bone-shaped samples were made in accordance with ASTM D1708-13, “Standard Test Method for Tensile Properties of Plastics by Use of Microtensile Specimens” by pressing the mixed paste into a dog bone-shaped silicone rubber mold, which was then laminated with release liner on both sides.
  • the dog bone shape gives a sample with a length of about 0.6 inch (1.5 cm) in the center straight area, a width of about 0.2 inch (0.5 cm) in the narrowest area, and a thickness of about 0.06 to about 0.1 inch (about 1.5 mm to about 2.5 cm) .
  • Samples were then cured at room temperature for 24 hours, 100 °C for 1 hour, or 120 °C for 1 hour to be fully cured prior to tensile testing. The sample was then conditioned at room temperature for 30 minutes prior to tensile testing.
  • disk-shaped samples were made by pressing the mixed paste into a disk-shaped silicone rubber mold which was then laminated with release liner on both sides.
  • the disk shape gives samples with a diameter of 12.6 mm and a thickness of 2.2 mm.
  • the sample was then cured at room temperature for 24 hours, room temperature for 15 hours, or 100°C for 1 hour to give complete curing.
  • C p Specific heat capacity
  • Sample density was determined using a geometric method.
  • the weight (m) of a disk-shaped sample was measured using a standard laboratory balance, the diameter (d) of the disk was measured using calipers, and the thickness (h) of the disk was measured using a Mitatoyo micrometer.
  • Dielectric breakdown strength measurements were performed according to ASTM D149-09 (2013) , “Standard Test Method for Dielectric Breakdown Voltage and Dielectric Strength of Solid Electrical Insulating Materials at Commercial Power Frequencies” using a Model 6TC4100-10/50-2/D149 Automated Dielectric Breakdown Test Set (Phenix Technologies, Accident, MD, US) that is specifically designed for testing DC breakdown from 3-100 kV and AC breakdown in the 1-50 kV, 60 Hz range. Each measurement was performed while the sample was immersed in FLUORINERT FC-40 fluid (3M Corporation, Saint Paul, MN, US) . The average breakdown strength was based on an average of measurements up to 10 or more samples. As is typical, a frequency of 60 Hz and a ramp rate of 500 volts per second was utilized for these tests.
  • Step 1 start at 23°C at 20%relative humidity (RH) ;
  • Step 2 ramp up to 90°C and 80%RH in 1 hour;
  • Step 3 Stay at 90 °C and 80%RH for 4 hours;
  • Step 4 cool and dehumidify the system to 23°C and 20%RH;
  • Step 5 Cool the system to -30°C in 1 hour;
  • Step 6 Stay at -30°C for 4 hours;
  • Step 7 Heat the system to 23°C and 20%RH in 1 hour. 20 cycles were required to complete the aging test. Physical properties of the cured compositions were measured before and after PR308.2 cycling.
  • Storage modulus (G’) and loss modulus (G”) were measured using a 25 mm parallel-plate geometry at 1%strain on a Discovery HR-3 Rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven accessory, using oscillating mode at angular frequencies of 100 rad/sat 25°C for time study.
  • Viscosity was measured using a 25 mm parallel-plate geometry on an Discovery HR-3 Rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven accessory, using steady flow mode with shear rate sweep from 0.001 1/sto 100 1/sat 25°C.
  • Table 4 summarizes the viscosity of Parts A and B of Example 5 (with 81.6 wt%filler) at 25 °C and 35 °C, at shear rates of 1 sec -1 and 4 sec -1 . Thixotropic/shear thinning behavior was observed for both Part A and Part B.
  • Table 5 summarizes the physical properties of compositions fully cured at room temperature (RT) , typically more than two days, and then aged under high temperature and humidity for 20 cycles using the PR308.2 standard conditions described above.
  • CE1 showed an increase in elongation at break and a decrease in tensile strength after aging under PR308.2 test conditions; this is attributed to bond dissociation after exposure to temperature and humidity cycling. After temperature and humidity cycling, samples that retain a high degree of their initial tensile strength and OLS, and that exhibit little to no change in elongation at break after aging are interpreted herein as having good hydrolytic stability.
  • Tables 6 and 7 summarize the physical properties of compositions fully cured at room temperature (RT) , typically more than two days, and then aged either under high temperature and humidity for 20 cycles using the PR308.2 standard conditions described above, or at 40 °C and 95%relative humidity (RH) for 10 days.
  • Table 6 lists the measured data.
  • Table 7 lists the percentage of each property that was retained after aging, relative to the value of the property directly after curing.
  • Table 8 summarizes the open time and gelation time for several illustrative compositions.
  • Table 9 summarizes the thermal properties of several illustrative compositions after full cure at room temperature for 2 days.
  • Table 10 summarizes the electrical properties of several illustrative compositions after full cure at room temperature for 2 days.

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US17/440,976 US20220162376A1 (en) 2019-03-25 2019-03-25 Curable compositions, articles therefrom, and methods of making and using same
JP2021556940A JP7689496B2 (ja) 2019-03-25 2019-12-13 硬化性組成物、それからなる物品、並びにその製造及び使用方法
PCT/CN2019/125303 WO2020192185A1 (en) 2019-03-25 2019-12-13 Curable compositions, articles therefrom, and methods of making and using same
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