Curable compositions, articles made therefrom, and methods of making and using the same
阅读说明：本技术 可固化组合物、由其制得的制品，及其制造和使用方法 (Curable compositions, articles made therefrom, and methods of making and using the same ) 是由 姚犁 拉杰迪普·S·卡尔古特卡尔 马里奥·A·佩雷斯 韦恩·S·莫尼 杰里米·M·希金斯 于 2019-01-31 设计创作，主要内容包括：本发明提供了一种可固化组合物,该可固化组合物包含含有第一聚酰胺的聚酰胺组合物。该第一聚酰胺在其主链中包含叔酰胺并且是胺封端的。该可固化组合物还包含含有2至20个碳原子的氨基官能化合物、多官能(甲基)丙烯酸酯、环氧树脂和无机填料。该无机填料以基于可固化组合物的总重量计至少25重量％的量存在。(The present invention provides a curable composition comprising a polyamide composition comprising a first polyamide. The first polyamide comprises a tertiary amide in its main chain and is amine terminated. The curable composition further comprises an amino-functional compound containing 2 to 20 carbon atoms, a multifunctional (meth) acrylate, an epoxy resin, and an inorganic filler. The inorganic filler is present in an amount of at least 25 wt-%, based on the total weight of the curable composition.)
1. A curable composition comprising:
a polyamide composition comprising a first polyamide comprising a tertiary amide in its backbone and being amine terminated;
an amino-functional compound comprising 2 to 20 carbon atoms;
a polyfunctional (meth) acrylate;
an epoxy resin; and
an inorganic filler present in an amount of at least 25 weight percent based on the total weight of the curable composition.
2. The curable composition of claim 1, wherein the polyamide composition is present in the curable composition in an amount between 1 weight percent and 50 weight percent based on the total weight of the curable composition.
3. The curable composition of claim 1, wherein the amino-functional compound is present in the curable composition in an amount between 0.2 and 30 weight percent based on the total weight of the curable composition.
4. The curable composition of claim 1, wherein the multifunctional (meth) acrylate is present in the curable composition in an amount between 2 and 50 weight percent based on the total weight of the curable composition.
5. The curable composition of claim 1, wherein the epoxy resin is present in the curable composition in an amount between 0.2 and 50 weight percent based on the total weight of the curable composition.
6. The curable composition of claim 1 wherein tertiary amide is present in the first polyamide in an amount of at least 50 mole percent based on the total amide content present in the backbone of the first polyamide.
7. The curable composition of claim 1 wherein the first polyamide component comprises the reaction product of: (i) a diacid; and (ii) a diamine, wherein the diamine comprises a secondary diamine or a secondary/primary mixed diamine.
8. The curable composition of claim 1, the polyamide composition further comprising a second polyamide, wherein the second polyamide comprises a polyfunctional polyamidoamine.
9. The curable composition of claim 1, wherein the first polyamide component is present in the polyamide composition in an amount of at least 50 weight percent based on the total weight of polyamides in the polyamide composition.
10. The curable composition of claim 1 further comprising a catalyst comprising a lewis acid.
11. The curable composition of claim 1, wherein the curable composition, when cured, provides (i) an elongation at break of greater than 5.5%, and (ii) 2N/mm on untreated aluminum2To 20N/mm2Lap shear strength of (a).
12. The curable composition of claim 1, wherein the curable composition when cured at room temperature for no more than 10 minutes provides the composition exhibiting a lap shear strength of at least 0.2 MPa.
13. The curable composition of claim 1, wherein the curable composition, when cured, provides a tensile strength of from 0.5N/mm2 to 16N/mm 2.
14. The curable composition of claim 1, wherein the curable composition, when cured, provides an elongation at break of greater than 6%.
15. The curable composition of claim 1, wherein the curable composition, when cured, provides an elongation at break of greater than 7%.
16. The curable composition of claim 1, wherein the inorganic filler comprises ATH.
17. The curable composition of claim 1, wherein the inorganic filler comprises alumina.
18. The curable composition of claim 1, wherein the inorganic filler comprises spherical alumina particles and hemispherical alumina particles.
19. The curable composition of claim 1, wherein the inorganic filler comprises silane surface treated particles.
20. The curable composition of claim 1, wherein the curable composition, when cured, provides a thermal conductivity of from 0.5W/(mK) to 2W/(mK).
21. The curable composition of claim 1, wherein the curable composition, when cured, provides flame retardancy of at least UL 94-HB.
22. The curable composition of claim 1, wherein the curable composition, when cured, provides a dielectric breakdown strength of greater than 5kV/mm and at least 1 × 109Volume insulation resistance of Ω cm.
23. The curable composition of claim 1, further comprising a dispersant comprising a binding group and a compatible segment.
24. The curable composition of claim 1, wherein the amino-functional compound comprises a diamine.
25. An article comprising a cured composition, wherein the cured composition is a reaction product of the curable composition of claim 1.
26. The article of claim 25, wherein the cured composition has a thickness of between 5 micrometers and 10000 micrometers.
27. The article of claim 25, further comprising a substrate having a surface, wherein the cured composition is disposed on the surface of the substrate.
28. The article of claim 27, wherein the substrate is a metal substrate.
29. 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 a reaction product of the curable composition of claim 1.
30. A battery module comprising a plurality of battery cells connected to a first substrate by a first layer of the curable composition of claim 1.
31. A method of manufacturing a battery module, the method comprising: applying a first layer of the curable composition of claim 1 to a first surface of a first substrate, attaching a plurality of battery cells to the first layer to connect the battery cells to the first substrate, and curing the curable composition.
Technical Field
The present disclosure relates generally to curable compositions. These curable compositions can be used, for example, as thermally conductive gap fillers, which can be suitable for use in electronic applications, such as battery components.
Background
Curable compositions based on epoxy resins or polyamide resins have been disclosed in the art. Such curable compositions are described, for example, in U.S. patent 2,705,223 and U.S. patent 6,008,313.
Disclosure of Invention
In some embodiments, a curable composition is provided. The curable composition includes a polyamide composition including a first polyamide. The first polyamide comprises a tertiary amide in its main chain and is amine terminated. The curable composition further comprises an amino-functional compound containing 2 to 20 carbon atoms, a multifunctional (meth) acrylate, an epoxy resin, and an inorganic filler. The inorganic filler is present in an amount of at least 25 wt-%, based on the total weight of the curable composition.
It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure. Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood in the art. The definitions provided herein will facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure. As used in this specification and the appended claims, the singular forms "a", "an", and "the" encompass embodiments having plural referents, unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.
Drawings
Fig. 1 illustrates components of an exemplary battery module according to some embodiments of the present disclosure.
Fig. 2 shows an assembled battery module corresponding to fig. 1.
Fig. 3 illustrates components of an exemplary battery subunit, according to some embodiments of the present disclosure.
Detailed Description
Thermal management plays an important role in many electronic applications, such as Electric Vehicle (EV) battery packs, power electronics, electronic packaging, LEDs, solar cells, power grids, and the like. Certain thermally conductive materials (e.g., adhesives) may be an attractive option for these applications due to good electrical insulation properties, the feasibility of machining integrated components or complex geometries, and good conformability/wettability to different surfaces, particularly to effectively dissipate heat while having good adhesion to different substrates for assembly.
With respect to applications in EV battery components, currently, one such application that utilizes thermally conductive materials is gap filler applications. Generally, in addition to having a low viscosity prior to curing, the requirements for gap filler applications include high thermal conductivity, good lap shear adhesion strength, good tensile strength, good ductile elongation at break, and good damping properties. However, in order to achieve high thermal conductivity, a large amount of inorganic thermally conductive filler is generally added to the composition. However, high loadings of thermally conductive fillers have a detrimental effect on adhesion properties, toughness, damping properties and viscosity. In addition, compositions useful for gap filler applications should have relatively fast cure profiles to accommodate the automated processing requirements of the industry. For example, thermally conductive materials that achieve sufficient green strength after curing at room temperature for about 10 minutes or less can be particularly advantageous.
Many existing compositions employed in EV hot adhesive gap filler applications are based on polyurethane cure chemistry. While these polyurethane-based materials may exhibit properties that make them suitable for use as gap fill materials, the isocyanates used in such products pose safety hazards and have poor stability at elevated temperatures.
In order to solve the above-mentioned problems associated with high loadings of inorganic thermally conductive fillers, as well as the safety problems associated with polyurethane-based compositions, a curable composition has been found that provides a good balance of desirable properties, including a filled composition having an epoxy resin, a polyamide composition, an amino-functional compound, and a multifunctional (meth) acrylate. The polyamide of the curable composition may be branched, amorphous, and promotes hydrogen bonding, which may enhance adhesion in the presence of high filler loadings. The unique combination of polyamides of the present disclosure has advantages over polyurethanes for these applications at least because: (i) they are isocyanate-free compositions that do not interfere with environmental regulations, (ii) they provide better compatibility with various thermally conductive fillers, and (iii) they provide excellent adhesion to aluminum and steel substrates. The curable compositions of the present disclosure also achieve sufficient green strength after curing at room temperature for about 10 minutes or less.
As used herein:
the term "room temperature" refers to a temperature of 22 ℃ to 25 ℃.
The terms "cure" and "curable" refer to the joining together of polymer chains by covalent chemical bonds, typically through cross-linking molecules or groups, to form a network polymer. Thus, in the present disclosure, the terms "cured" and "crosslinked" may be used interchangeably. Generally, the cured or crosslinked polymer is characterized as insoluble, but can be swellable in the presence of a suitable solvent.
The term "backbone" refers to the predominantly continuous chain of the polymer.
The term "aliphatic" refers to C1-C40, suitably C1-C30 straight or branched chain alkenyl, alkyl, or alkynyl groups that may or may not be interrupted or substituted with one or more heteroatoms, such as O, N or S.
The term "cycloaliphatic" refers to a cyclized aliphatic C3-C30, suitably C3-C20 group, and includes those interrupted by one or more heteroatoms (such as O, N or S).
The term "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, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, the alkyl group contains 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. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, tert-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.
The term "alkylene" refers to a divalent group that is a radical of an alkane and includes straight chain groups, branched chain groups, cyclic groups, bicyclic groups, or combinations 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.
The term "aromatic" refers to C3-C40, suitably C3-C30, aromatic groups, including carbocyclic aromatic groups, as well as heterocyclic aromatic groups containing one or more of heteroatoms O, N or S and fused ring systems containing one or more of these aromatic groups fused together.
The term "aryl" refers to a monovalent group that is aromatic and optionally carbocyclic. The aryl group has at least one aromatic ring. Any additional rings may be unsaturated, partially saturated, or aromatic. Optionally, the aromatic ring can have one or more additional carbocyclic rings fused to the aromatic ring. Unless otherwise indicated, aryl groups typically contain 6 to 30 carbon atoms. In some embodiments, the aryl group contains 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. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.
The term "arylene" refers to a divalent group that is aromatic and optionally carbocyclic. The arylene group has at least one aromatic ring. Optionally, the aromatic ring can have one or more additional carbocyclic rings fused to the aromatic ring. Any additional rings may be unsaturated, partially saturated, or saturated. Unless otherwise specified, 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.
The term "aralkyl" refers to a monovalent group that is an alkyl group substituted with an aryl group (e.g., as in a benzyl group). The term "alkaryl" refers to a monovalent group that is an aryl group substituted with an alkyl group (e.g., as in a tolyl group). Unless otherwise specified, for both groups, the alkyl moiety often has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and the aryl moiety 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 term (meth) acrylate refers to an acrylate or methacrylate.
Repeat use of reference characters in the present specification is intended to represent same or analogous features or elements of the present disclosure. As used herein, the word "between … …" applied to a numerical range includes the endpoints of that range unless otherwise specified. The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range.
In some embodiments, the present disclosure provides a filler-filled thermally conductive curable composition formulated by blending a polyamide composition, an epoxy resin, an amino-functional compound, and a multifunctional (meth) acrylate. The composition provides excellent tensile strength, elongation at break and lap shear strength, as well as excellent adhesion to bare aluminum and steel substrates. In some embodiments, the polyamides of the present disclosure may contain tertiary amides in the backbone, which may enhance elongation at break at room temperature by reducing the bulk density of hydrogen bonding and crosslinking and providing chain flexibility, while maintaining good adhesion to metal substrates. In some embodiments, the structure and molecular weight of the polyamide may also be adjusted in order to reduce viscosity when high filler loading is used. Polyamide compatible dispersants may also be added to further reduce the compound viscosity.
In some embodiments, the curable composition of the present disclosure may comprise an epoxy composition and a polyamide composition comprising one or more polyamides having one or more tertiary amides in their backbone. The curable composition may further comprise an amino-functional compound and a multifunctional acrylate.
In some embodiments, the epoxy composition may comprise one or more epoxy resins. Suitable epoxy resin epoxides may include aromatic polyepoxide resins (e.g., chain extended diepoxides or novolac epoxy resins having at least two epoxide groups), aromatic monomeric diepoxides, aromatic monomeric monoepoxides, aliphatic polyepoxides, or monomeric diepoxides. The crosslinkable epoxy resin will generally have at least two epoxy end groups. The aromatic polyepoxides or aromatic monomeric diepoxides typically contain at least one (in some embodiments, at least 2, and in some embodiments, in a range from 1 to 4) aromatic ring, alkyl group having 1 to 4 carbon atoms (e.g., methyl or ethyl), or hydroxyalkyl group having 1 to 4 carbon atoms (e.g., hydroxymethyl) optionally substituted with a halogen (e.g., fluorine, chlorine, bromine, iodine). For epoxy resins containing two or more aromatic rings, the rings may be attached, for example, by a branched or straight chain alkylene group having 1 to 4 carbon atoms, which may optionally be substituted with halogen (e.g., fluoro, chloro, bromo, iodo).
In some embodiments, examples of aromatic epoxy resins useful in the epoxy compositions disclosed herein can include novolac epoxy resins (e.g., phenol novolac, o-cresol novolac, m-cresol novolac, or p-cresol novolac, or a combination thereof), bisphenol epoxy resins (e.g., bisphenol a, bisphenol F, halogenated bisphenol epoxies, and combinations thereof), resorcinol epoxy resins, tetraphenylphenol alkyl epoxy resins, and combinations of any of these. Useful epoxy compounds include bifunctional phenolic compounds (e.g., p, p ' -dihydroxydibenzyl, p, p ' -dihydroxydiphenyl, p, p ' -dihydroxyphenylsulfone, p, p ' -dihydroxybenzophenone, 2' -dihydroxy-1, 1-dinaphthylmethane, and 2,2', 2,3', 2,4', 3' of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylphenylmethane, dihydroxydiphenylbutylphenylmethane, dihydroxydiphenyltolylethane, dihydroxydiphenyltolylmethylmethane, dihydroxydiphenyldicyclohexylmethane, and dihydroxydiphenylcyclohexane, 3', 3,4', and 4,4' isomers). In some embodiments, the adhesive comprises a bisphenol diglycidyl ether in which the bisphenol (i.e., -O-C)6H5—CH2—C6H5-O-) may be unsubstituted (e.g., bisphenol F), or any of the phenyl rings or methylene groups may be substituted by one or moreA plurality of halogens (e.g., fluorine, chlorine, bromine, iodine), methyl groups, trifluoromethyl groups, or hydroxymethyl groups.
In some embodiments, examples of aromatic monomer diepoxides useful in epoxy compositions according to the present disclosure include diglycidyl ethers of bisphenol a and bisphenol F, and mixtures thereof. For example, the bisphenol epoxy resin may be chain extended to have any desired epoxy equivalent weight. Chain extension of epoxy resins can be carried out by reacting monomeric diepoxides, for example, with bisphenols, in the presence of a catalyst to produce linear polymers.
In some embodiments, the aromatic epoxy resin (e.g., 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. For example, the epoxy equivalent weight may be selected so that the epoxy resin may be used as a liquid or solid as desired.
In some embodiments, the epoxy resins of the present disclosure may include one or more non-aromatic epoxy resins in addition to or as an alternative to aromatic epoxy resins. In some cases, the non-aromatic epoxy resin may serve as a reactive diluent that may help control the flow characteristics of the composition. The non-aromatic epoxy resins useful in the curable compositions according to the present disclosure may comprise a branched or straight chain alkylene group having 1 to 20 carbon atoms optionally interrupted by at least one-O-and optionally substituted with a hydroxyl group. In some embodiments, the non-aromatic epoxy group may include a compound having a plurality (x) of oxyalkylene groups OR1Wherein each R is a poly (oxyalkylene) group of1Independently is C2To C5Alkylene, in some embodiments, is C2To C3Alkylene, x is 2 to about 6,2 to 5,2 to 4, or 2 to 3. For crosslinking into a network, useful non-aromatic epoxy resins will generally 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 containing one or more oxyalkylene units. Examples of these substances include resins made of 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 triglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and hexylene glycol diglycidyl ether. Other useful non-aromatic epoxy resins include the diglycidyl ether of cyclohexanedimethanol, the diglycidyl ether of neopentyl glycol, the triglycidyl ether of trimethylolpropane, and the diglycidyl ether of 1, 4-butanediol.
A crosslinked aromatic epoxide (i.e., an epoxy polymer) as described herein may be understood as capable of being prepared by crosslinking an aromatic epoxy resin. The crosslinked aromatic epoxy group typically contains a repeating unit having at least one (in some embodiments, at least 2, and in some embodiments, in the range of from 1 to 4) aromatic ring (e.g., phenyl group) optionally substituted with one or more halogen (e.g., fluorine, chlorine, bromine, iodine), alkyl group having from 1 to 4 carbon atoms (e.g., methyl or ethyl), or hydroxyalkyl group having from 1 to 4 carbon atoms (e.g., hydroxymethyl). For repeat units containing two or more aromatic rings, the rings can be attached, for example, by a branched or straight chain alkylene group having 1 to 4 carbon atoms, which can optionally be substituted with halogen (e.g., fluoro, chloro, bromo, iodo).
In some embodiments, the epoxy resins of the present disclosure may be liquid at room temperature. Several curable epoxy resins useful in epoxy compositions according to the present disclosure are commercially available. For example, several epoxy resins of various classes and epoxy equivalents are available from the following suppliers: dow chemical company, Midland, michigan, usa (Dow chemical company, Midland, Mich.); hansen, Columbus, Ohio, USA; huntsman advanced materials, The woods, Tex, of woodland, texas, usa; CVC specialty Chemicals inc, Akron, Ohio, usa (purchased by emerald performance Materials); and southern Asia plastics Industrial Co., Ltd, Taibei, Taiwan, China. Examples of commercially available glycidyl ethers include diglycidyl ethers of bisphenol a (e.g., those available under the trade names "EPON 828", "EPON 1001", "EPON 1310", and "EPON 1510" from vash corporation of columbic, ohio, those available under the trade name "d.e.r." from dow chemical company (e.g., d.e.r.331, 332, and 334), those available under the trade name "EPICLON" from dainip Ink and Chemicals, Inc. (e.g., EPICLON 840 and 850), and those available under the trade name "YL-980" from Japan epoxy resins, Inc. (Japan epoxy resins co., Ltd.); diglycidyl ether of bisphenol F (for example, those available under the trade name "EPICLON" from japan ink chemical industries co., ltd. (for example, "EPICLON 830")); polyglycidyl ethers of phenolic resins (e.g., novolac epoxy resins such as those available from dow chemical company under the trade designation "d.e.n." (e.g., d.e.n.425, 431, and 438)); and flame retardant epoxy resins (e.g., "d.e.r.580", available from dow chemical company as brominated bisphenol type epoxy resins). Examples of commercially available non-aromatic epoxy resins include the glycidyl ether of cyclohexanedimethanol, which is available under the trade designation "HELOXY modifer 107" from the vasion company of columbic city, ohio.
In some embodiments, the epoxy composition of the present disclosure may comprise an amount of epoxy resin that is between 5 and 40 weight percent, between 10 and 30 weight percent, between 15 and 30 weight percent, or between 20 and 30 weight percent (or possibly even higher (up to 95%, 99%, or 100%) for epoxy compositions that do not comprise a filler), based on the total weight of the epoxy composition (including any filler). In some embodiments, the epoxy composition of the present disclosure may comprise an epoxy resin in an amount of at least 10 weight percent, at least 20 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent, based on the total weight of the epoxy composition.
In some embodiments, the polyamide composition may comprise a first polyamide component and optionally a second polyamide component.
In some embodiments, the first polyamide component may comprise one or more polyamides comprising one or more tertiary amides in its backbone. In some embodiments, the tertiary polyamide may be present in the backbone of the polyamide in an amount of 50 to 100 mole%, 70 to 100 mole%, 90 to 100 mole%, 50 to 99 mole%, 70 to 99 mole%, 90 to 99 mole%, 95 to 100 mole%, or 95 to 99 mole%, or 99 to 100 mole%, based on the total amide content present in the backbone of the polyamide. In some embodiments, the tertiary polyamide may be present in the backbone of the polyamide in an amount of at least 50 mole%, at least 70 mole%, at least 90 mole%, at least 95 mole%, or at least 99 mole%, based on the total amide content present in the backbone of the polyamide. Generally, the presence of such tertiary amides is believed to enhance elongation at break at room temperature by reducing the bulk density of hydrogen bonding and crosslinking while maintaining good adhesion to the metal substrate.
The polyamide of the first polyamide component may also contain secondary amides in its backbone in addition to the tertiary amides. The polyamide of the first polyamide component may be amine terminated, including primary amine terminated and secondary amine terminated.
In some embodiments, the polyamide of the first polyamide component may be a liquid at room temperature (e.g., a viscous liquid having a viscosity of about 500 to 50,000 cP).
In some embodiments, the polyamide of the first polyamide component may comprise the reaction product of a diacid component and a diamine component (e.g., by condensation polymerization).
In some embodiments, the diacid component can include any long chain diacid (e.g., diacids comprising greater than 15 carbon atoms). The diacid component can also include short chain diacids (e.g., diacids comprising between 2 and 15 carbon atoms). In some embodiments, the long chain diacid may be present in an amount between 80 and 100 mole percent, between 85 and 100 mole percent, between 90 and 100 mole percent, between 95 and 100 mole percent, between 80 and 99 mole percent, or between 80 and 95 mole percent, based on the total moles of diacid component; or at least 80 mole%, at least 90 mole%, or at least 95 mole% is present in the diacid component. In some embodiments, the short chain diacid may not be present in the diacid component or may be present in the diacid component in an amount between 1 and 20 mole percent, between 1 and 15 mole percent, between 1 and 10 mole percent, or between 1 and 5 mole percent, based on the total moles of the diacid component.
In some embodiments, the diacid component may include a dicarboxylic acid (e.g., in the form of a dicarboxydinic acid). In some embodiments, the dicarboxylic acid may comprise at least one alkyl or alkenyl group, and may contain 3 to 30 carbon atoms, and may be characterized as having two carboxylic acid groups. The alkyl or alkenyl group may be branched. The alkyl group may be cyclic. Useful dicarboxylic acids may include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid (decanoic acid), undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, (Z) -butenedioic acid, (E) -butenedioic acid, penta-2-enedioic acid, dodec-2-enedioic acid, (2Z) -2-methylbut-2-enedioic acid, (2E,4E) -hex-2, 4-dienedioic acid, and sebacic acid (sebac acid). Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2, 6-naphthalenedicarboxylic acid may be used. Mixtures of two or more dicarboxylic acids may be used because mixtures of different dicarboxylic acids may help disrupt the structural regularity of the polyamide, thereby significantly reducing or eliminating the crystallinity of the resulting polyamide component.
In some embodiments, the dicarboxydig acid may comprise at least one alkyl or alkenyl group and may contain 12 to 100 carbon atoms, 16 to 100 carbon atoms, or 18 to 100 carbon atoms and be characterized as having two carboxylic acid groups. The dimer acid may be saturated or partially unsaturated. In some embodiments, the dimer acid may be a dimer of fatty acids. As used herein, the phrase "fatty acid" means an organic compound consisting of an alkyl or alkenyl group containing from 5 to 22 carbon atoms and characterized by having a terminal carboxylic acid group. Useful Fatty Acids are disclosed in "Fatty Acids in Industry: Processes, Properties, Derivatives, Applications (Fatty Acids in Industry: methods, Properties, Derivatives, Applications)", Chapter 7, pp.153 to 175, Marcel Dekker, Inc., 1989. In some embodiments, the dimer acid may be formed from dimerization of unsaturated fatty acids having 18 carbon atoms (such as oleic acid or tall oil fatty acid). Dimer acids are typically at least partially unsaturated and typically contain 36 carbon atoms. Dimer acid may have a relatively high molecular weight and consist of a mixture containing various ratios of a large or relatively high molecular weight substituted cyclohexene carboxylic acid (primarily 36-carbo-xydimer acid). The component structures may be acyclic, cyclic (monocyclic or bicyclic), or aromatic, as shown below.
Dimer acids can be prepared by condensation of unsaturated monofunctional carboxylic acids (such as oleic acid, linoleic acid, soy acid, or tall oil acid) via their ethylenically unsaturated groups in the presence of a catalyst (such as an acidic clay). Dimer acid (nominally C)36Dibasic acids) depends on the unsaturated acid used in its manufacture. Typically, oleic acid produces a dicarboxydinic acid containing about 38% acyclic compounds, about 56% monocyclic and bicyclic compounds, and about 6% aromatic compounds. Soy acid production contains about 24% acyclic compounds, about 58% monocyclic and bicyclic compounds, and about 18% aromatic dicarboxylic dimer acid. Tall oil acid produces a dicarboxydinic acid containing about 13% acyclic compounds, about 75% monocyclic and bicyclic compounds, and about 12% aromatic compounds. The dimerization process also produces trimer acid. Commercial dimer acid products are typically purified by distillation to produce a range of dicarboxylic acid contents. Useful dimer acids contain at least 80% dicarboxylic acid, more preferably 90% dicarboxylic acid content, even more preferably at least 95% dicarboxylic acid content. For certain applications, it may be advantageous to further purify the dimer acid by color reduction techniques, including hydrogenation of unsaturation, as disclosed in U.S. patent 3,595,887, which is incorporated herein by reference in its entirety. Hydrogenated dimer acids may also provide enhanced oxidative stability at elevated temperatures. Other useful Dimer Acids are disclosed in Kirk-Othmer encyclopedia of Chemical Technology, Organic Chemicals: Dimer Acids (ISBN 9780471238966) copyright ownership 1999-2014, John Wiley and Sons, Inc. Commercially available dicarboxydiacid is available, for example, from BASF, Florham Park, New Jersey, both under the trade names EMPOL1008 and EMPOL1061, and PRIPOL 1006, PRIPOL 1009, PRIPOL 1013, PRIPOL 1017, and PRIPOL1025, all from proca inc (Edison, New Jersey), New Jersey, of Edison, nj.
In some embodiments, the number average molecular weight of the dicarboxydidimer acid may be between 300g/mol and 1400g/mol, between 300g/mol and 1200g/mol, between 300g/mol and 1000g/mol, or even between 300g/mol and 800 g/mol. In some embodiments, the number of carbon atoms in the dicarboxydig acid may be between 12 and 100, between 20 and 100, between 30 and 100, between 12 and 80, between 20 and 80, between 30 and 80, between 12 and 60, between 20 and 60, or even between 30 and 60. The mole fraction of dicarboxydic acid contained as dicarboxylic acid may be between 0.10 and 1.00 based on the total moles of dicarboxylic acid used to form the polyamide component. In some embodiments, the mole fraction of dicarboxydidimer acid included as dicarboxylic acid is between 0.10 and 1.00, between 0.30 and 1.00, between 0.50 and 1.00, between 0.70 and 1.00, between 0.80 and 1.00, between 0.90 and 1.00, between 0.10 and 0.98, between 0.30 and 0.98, between 0.50 and 0.98, between 0.70 and 0.98, between 0.80 and 0.98, or even between 0.90 and 0.98, based on the total moles of dicarboxylic acid used to form the polyamide component. In some embodiments, the mole fraction of dicarboxydic acid contained as dicarboxylic acid is 1.00 based on the total moles of dicarboxylic acid used to form the polyamide component. Mixtures of two or more dimer acids may be used.
In some embodiments, the reactants of the first polyamide component may comprise one or more triacids in addition to the diacid component.
In some embodiments, the diamine component may comprise one or more secondary diamines or one or more secondary/primary mixed diamines, and optionally one or more primary diamines.
In some embodiments, suitable secondary amines or secondary/primary mixed amines may have the formula: R1-NH-R2-NH-R1
Wherein R2 is:
alkylene (e.g. -CH2CH2CH2-)
Branched alkylene (-CH2CH (Me) CH2-),
Cycloalkylene radicals (e.g. -cyclohexylene-CH 2-cyclohexylene-),
substituted or unsubstituted arylene radicals (e.g. -1, 4-phenylene-),
heteroalkylene (e.g., -CH2CH2-O-CH2CH 2-or any other Jeffamine), or
Heterocycloalkylene (e.g., -CH 2-furan ring-CH 2-)
And each R1 is independently:
straight or branched chain alkyl groups (e.g. -Me, -isopropyl),
Cycloalkyl radicals (e.g. cyclohexyl),
Aryl radicals (e.g. phenyl),
Heteroalkyl (e.g., -CH2CH2-O-CH3),
Heteroaryl (e.g., -2-substituted pyridyl), or
A hydrogen atom, and a nitrogen atom,
with the proviso that both R1 are not hydrogen atoms, or
The R1 radical being alkylene or branched and forming a heterocyclic compound (e.g. piperazine)
Suitable secondary diamines may include, for example, piperazine, 1, 3-bis-4-piperidinylpropane, cyclohexylamine, and 4,4' -methylenebis [ N- (1-methylpropyl). In some embodiments, suitable secondary/primary mixed diamines (i.e., diamines having secondary and primary amines) include, for example, aminoethylpiperazine. In some embodiments, the secondary/primary mixed diamine may not be present, or may be present in an amount less than 50 mole%, less than 30 mole%, less than 10 mole%, or less than 5 mole%, based on the total moles of secondary or secondary/primary mixed amines. In some embodiments, suitable secondary diamines or secondary/primary mixed diamines may have a number average molecular weight of 30g/mol to 5000g/mol, 30g/mol to 500g/mol, or 50g/mol to 100 g/mol.
In some embodiments, the diamine component may include a primary diamine, such as an aliphatic or aromatic primary amine, in addition to a secondary amine or a secondary/primary mixed amine. Suitable primary amines include, for example, ethylenediamine, m-xylylenediamine, 1, 6-hexamethylenediamine, o-toluidine or 1, 3-xylylenediamine. In some embodiments, suitable primary diamines may have a number average molecular weight of 30g/mol to 5000g/mol, 30g/mol to 500g/mol, or 50g/mol to 100 g/mol.
In some embodiments, the secondary diamine or secondary/primary mixed diamine, alone or in combination, may be present in the diamine component in an amount of from 50 to 100 mole%, 70 to 100 mole%, 90 to 100 mole%, 50 to 99 mole%, 70 to 99 mole%, 90 to 99 mole%, 95 to 100 mole%, or 95 to 99 mole%, or 99 to 100 mole%, based on the total moles of the diamine component. In some embodiments, the secondary diamine or secondary/primary mixed diamine, alone or in combination, may be present in the diamine component in an amount of at least 50 mole%, at least 70 mole%, at least 90 mole%, at least 95 mole%, or at least 99 mole%, based on the total moles of the diamine component.
In some embodiments, the primary amine may not be present in the diamine component, or may be present in the diamine component in an amount between 1 mole% and 10 mole%, or between 1 mole% and 5 mole%, based on the total moles of the diamine component. In some embodiments, the molar ratio of diamine to diacid in the first polyamide component may be between 1 and 5, 1 and 4, 1.1 and 4, or 1.2 and 3.
In some embodiments, the polyamide of the first polyamide component may be formed according to conventional condensation reactions between at least one of the foregoing diacids and at least one of the foregoing diamines. Mixtures of at least two diacid types with at least one diamine, mixtures of at least two diamine types with at least one diacid type, or mixtures of at least two diacid types with at least two diamine types may be used. The polyamide of the first polyamide component may be amine terminated or contain amine end groups. Amine termination can be achieved by using the appropriate stoichiometric ratio of amine groups to acid groups (e.g., the appropriate stoichiometric ratio of diamine to diacid) during polyamide synthesis.
In some embodiments, the reactants of the first polyamide component may comprise one or more triamines in addition to the diamine component.
As discussed above, the polyamide composition of the present disclosure may comprise a second polyamide component. In some embodiments, the second polyamide component may be different from the first polyamide component. In some embodiments, the second polyamide component may comprise a polyfunctional polyamidoamine or a hot melt dimer acid-based polyamide, such as those described in US 3,377,303(Peerman et al). In some embodiments, suitable polyfunctional polyamidoamines include those described in U.S. Pat. No. 2,705,223 (Renfew et al), which is incorporated herein by reference in its entirety. Commercially available polyfunctional polyamidoamines are available, for example, from Gabriel Chemicals, Akron, Ohio under the trade names VERSAMID 150 and VERSAMID 115, both available from Calbuiel chemical, Akron, Ohio. Commercially available hot melt polyamides are available, for example, from Arizona chemical, Jacksonville, Florida, under the trade names UNI-REZ2651 and UNI-REZ 2671, both of which are available from Arizona chemical, Jacksonville, Florida. In some embodiments, the polyamide of the second polyamide component may be a liquid at room temperature (e.g., a viscous liquid of 500 to 50,000 cP). It will be appreciated that the polyamide of the second polyamide component alone was found to be insufficient to enhance the elongation at break of the curable composition while maintaining good adhesion to metal substrates. In contrast, polyamides having tertiary amides in the backbone have been found to provide these desirable attributes.
In some embodiments, the polyamide compositions of the present disclosure may comprise the first polyamide component in an amount between 50 weight% and 100 weight%, between 75 weight% and 100 weight%, between 95 weight% and 100 weight%, between 50 weight% and 95 weight%, or between 75 weight% and 95 weight%, based on the total weight of polyamides in the polyamide composition. In some embodiments, the polyamide compositions of the present disclosure may comprise the first polyamide component in an amount of at least 50 weight percent, at least 70 weight percent, at least 90 weight percent, or at least 95 weight percent, based on the total weight of polyamides in the polyamide composition. The polyamide composition of the present disclosure may comprise the second polyamide component in an amount between 0.01 wt% and 50 wt%, between 0.1 wt% and 25 wt%, between 0.5 wt% and 10 wt%, or between 1 wt% and 5 wt%, based on the total weight of polyamides in the polyamide composition.
In some embodiments, the polyamide compositions of the present disclosure may comprise polyamide in an amount between 5 and 40 weight percent, 10 and 30 weight percent, 15 and 30 weight percent, or 20 and 30 weight percent (or possibly even higher (up to 95%, 99%, or 100%) for curable compositions that do not comprise filler) based on the total weight of the polyamide composition.
In some embodiments, the curable compositions of the present disclosure may comprise one or more amino-functional compounds having at least two amino groups. In some embodiments, the amino group can be a primary, secondary, or tertiary amino group. In some embodiments, the amino-functional compound may comprise 2 to 20, 3 to 18, or 4 to 15 carbon atoms. In some embodiments, the amino-functional compound may include aliphatic, cycloaliphatic, or aromatic diamines. In exemplary embodiments, the diamine may include a diprimary amine having an average molecular weight of 30 to 600 or 60 to 400. In some embodiments, suitable diamines may include alkylene polyamines such as 1, 3-diaminopropane, 1, 6-hexamethylenediamine, ethylenediamine, 1, 10-decamethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, 2-methylpentamethylenediamine; alicyclic diamines such as 1,4-, 1, 3-and 1, 2-diaminocyclohexane, 4,4'-, 2' -diaminodicyclohexylmethane, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, 1, 4-and 1, 3-diaminomethylcyclohexane, 3(4),8(9) -bis (aminomethyl) -tricyclo [5.2.1.0(2.6) ] decane, bicyclo [2.2.1] heptanedi (methylamine); aromatic diamines such as m-xylylenediamine; and other amine curing agents such as ethanolamine, methylimino-bis (propyl) amine, aminoethyl-piperazine, polyoxyethylene diamine, or polyoxypropylene diamine or triamine.
In some embodiments, the cured composition may comprise one or more triamines in addition to the diamine.
In some embodiments, the curable compositions of the present disclosure may comprise one or more multifunctional (meth) acrylate components. In some embodiments, a multifunctional (meth) acrylate component may be used as a crosslinker. In various embodiments, the multifunctional (meth) acrylate may comprise a plurality of (meth) acryloyl groups, including di (meth) acrylates, tri (meth) acrylates, tetra (meth) acrylates, or penta (meth) acrylates. Multifunctional (meth) acrylates can be formed, for example, by reacting (meth) acrylic acid with a polyol (i.e., an alcohol having at least two hydroxyl groups). The polyol may have two, three, four or five hydroxyl groups.
In some embodiments, the multifunctional (meth) acrylate component may comprise at least two (meth) acryloyl groups. Exemplary multifunctional acrylates of this type may include 1, 2-ethanediol diacrylate, 1, 3-propanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 12-dodecanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, butanediol diacrylate, bisphenol A diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene/polypropylene copolymer diacrylate, polybutadiene di (meth) acrylate, propoxylated glycerol tri (meth) acrylate, and neopentyl glycol hydroxypivalate diacrylate-modified caprolactone. In some embodiments, the multifunctional acrylate component may comprise three or four (meth) acryloyl groups. Exemplary multifunctional acrylates of this type may include trimethylolpropane triacrylate (e.g., commercially available from Cytec Industries, Inc., Smyrna, GA, and under the trade designation SR-351 from Sartomer), pentaerythritol triacrylate (e.g., commercially available from Sartomer under the trade designation SR-444), tris (2-hydroxyethylisocyanurate) triacrylate (e.g., commercially available from Sartomer under the trade designation SR-368), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (e.g., commercially available from Zhan Mitsubishi company (Allnex) under the trade designation PETIA), pentaerythritol tetraacrylate (e.g., commercially available from Sartomer under the trade designation SR-295), Di-trimethylolpropane tetraacrylate (e.g., commercially available from sartomer under the tradename SR-355), or ethoxylated pentaerythritol tetraacrylate (e.g., commercially available from sartomer under the tradename SR-494). In some embodiments, the multifunctional acrylate component may comprise five (meth) acryloyl groups. Exemplary multifunctional acrylates of this type may include dipentaerythritol pentaacrylate (e.g., commercially available from sartomer company under the trade designation SR-399).
In some embodiments, the epoxy composition may be present in the curable composition in an amount between 0.2 wt% and 50 wt%, between 0.5 wt% and 40 wt%, between 1 wt% and 30 wt%, between 1.5 wt% and 20 wt%, or between 2 wt% and 10 wt%, based on the total weight of the curable composition of the present disclosure. In some embodiments, the epoxy composition may be present in the curable composition in an amount of at least 0.2 weight percent, at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 5 weight percent, or at least 10 weight percent based on the total weight of the curable composition of the present disclosure. In some embodiments, the polyamide composition may be present in the curable composition in an amount between 1 and 50 weight percent, between 2 and 40 weight percent, between 4 and 30 weight percent, or between 5 and 20 weight percent based on the total weight of the curable composition of the present disclosure. In some embodiments, the polyamide composition may be present in the curable composition in an amount of at least 2 weight percent, at least 5 weight percent, at least 10 weight percent, or at least 20 weight percent based on the total weight of the curable composition of the present disclosure.
In some embodiments, the epoxy composition and the polyamide composition may be present in the curable composition in a stoichiometric ratio based on the functional groups of the respective components. For example, the relative amounts of the epoxy composition and the polyamide composition can be based on a stoichiometric ratio of amine hydrogen (N-H) groups or amine groups of the polyamide composition to ethylene oxide groups of the epoxy composition (1:1) to (1:2), or (1:1) to (1:1.5), or (1:1) to (1: 1.02). Using such relative amounts may be advantageous because the amount of residual unreacted polyamide or epoxide in the cured composition may be reduced, which residual components may migrate or present environmental or health challenges.
In some embodiments, the short-chain diamine may be present in the curable composition in an amount between 0.2 wt% and 30 wt%, between 0.5 wt% and 20 wt%, between 1 wt% and 15 wt%, between 1.5 wt% and 10 wt%, or between 2 wt% and 5 wt%, based on the total weight of the curable composition of the present disclosure. In some embodiments, the short-chain diamine may be present in the curable composition in an amount of at least 0.2 wt.%, at least 0.5 wt.%, at least 1 wt.%, at least 1.5 wt.%, at least 2 wt.%, or at least 10 wt.%, based on the total weight of the curable composition of the present disclosure. In some embodiments, the multifunctional acrylate may be present in the curable composition in an amount between 0.5 wt% and 50 wt%, between 1 wt% and 40 wt%, between 2 wt% and 30 wt%, or between 4 wt% and 20 wt%, based on the total weight of the curable composition of the present disclosure. In some embodiments, the multifunctional acrylate may be present in the curable composition in an amount of at least 0.5 wt-%, at least 1 wt-%, at least 2 wt-%, at least 4 wt-%, at least 10 wt-%, or at least 20 wt-%, based on the total weight of the curable composition of the present disclosure.
In some embodiments, the curable composition of the present disclosure may be provided (e.g., packaged) as a two-part composition, wherein the first part comprises the above-described epoxy composition and multifunctional acrylate, and the second part comprises the above-described polyamide composition and short-chain diamine. Other components of the curable adhesive composition (e.g., inorganic fillers, toughening agents, dispersants, catalysts, antioxidants, etc.) (described in further detail below) may be included in one or both of the first and second portions. The present disclosure also provides a dispenser comprising a first chamber and a second chamber. The first chamber includes a first portion and the second chamber includes a second portion.
The curable compositions of the present disclosure comprise one or more inorganic fillers (e.g., thermally conductive inorganic fillers) in an amount of at least 25 weight percent, at least 35 weight percent, at least 45 weight percent, at least 50 weight percent, at least 55 weight percent, at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, based on the total weight of the curable composition. In some embodiments, the inorganic filler loading may be between 25 wt% and 95 wt%, between 35 wt% and 90 wt%, between 55 wt% and 85 wt%, or between 70 wt% and 85 wt%, based on the total weight of the curable composition.
Generally, any known thermally conductive filler may be used, but electrically insulating fillers may be preferred where breakdown 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, for example, silica (e.g., fused silica), alumina, aluminum hydroxide (ATH), boron nitride, silicon carbide, and beryllium oxide. In some embodiments, the thermally conductive filler comprises ATH. It will be appreciated that while ATH is not typically used in polyurethane-based compositions typically employed in thermal management materials due to its reactivity with isocyanate species and the resulting formulation difficulties, the curable compositions of the present disclosure can incorporate such inorganic fillers without drawbacks. In some embodiments, the thermally conductive filler comprises fused silica. Other thermally conductive fillers include carbon-based materials (such as graphite) and metals (such as aluminum and copper).
Thermally conductive filler particles are available in a variety of shapes, such as spheres, irregular shapes, plates, and needles. In some applications, through-plane thermal conductivity may be important. Thus, in some embodiments, a generally symmetrical (e.g., spherical or hemispherical) filler may be employed. To facilitate dispersion and increase filler loading, in some embodiments, the thermally conductive filler may be surface treated or coated. Generally, any known surface treatment and coating may be suitable, including those based on silane, titanate, zirconate, aluminate, and organic acid chemistries. In some embodiments, the thermally conductive filler particles may include silane surface treated particles (i.e., particles having surface-bonded organosilanes). Many fillers may be used as polycrystalline agglomerates or aggregates, with or without a binder, for powder handling purposes. To facilitate high thermal conductivity formulations, some embodiments may include mixtures of particles and agglomerates of various sizes, as well as mixtures.
In some embodiments, the thermally conductive filler particles comprise spherical alumina, hemispherical alumina, or irregular alumina. In some embodiments, the thermally conductive filler particles comprise spherical alumina and hemispherical alumina.
In some embodiments, the curable compositions of the present disclosure may further comprise one or more epoxy toughening agents in addition to the polyamides of the present disclosure (which may be considered toughening agents). Such toughening agents can be used, for example, to improve the properties (e.g., peel strength) of some cured epoxies, for example, such that they do not brittle fracture when broken. The toughening agent (e.g., an elastomeric resin or elastomeric filler) may or may not be covalently bonded to the curable epoxy, and ultimately to the crosslinked network. In some embodiments, the toughening agent can include an epoxy-terminated compound that can be incorporated into the polymer backbone. Examples of useful toughening agents (which may also be referred to as elastomer modifiers) include polymeric compounds having both a rubber phase and a thermoplastic phase, such as: graft copolymers having a polymerized diene rubber core and a polyacrylate or polymethacrylate shell; graft copolymers having a rubber core and a polyacrylate or polymethacrylate shell; elastomer particles polymerized in situ in the epoxide from a free-radically polymerizable monomer and a co-stabilizer; elastomer molecules such as polyurethanes and thermoplastic elastomers; an isolated elastomer precursor molecule; a composite molecule comprising an epoxy segment and an elastomeric segment; and mixtures of such separation molecules and combination molecules. These composite molecules can be prepared by reacting an epoxy material with an elastomer segment; this reaction leaves reactive functional groups, such as unreacted epoxy groups, on the reaction product. The use of tougheners in epoxy Resins is described in the Series of chemical advancements (Advances in Chemistry Series) entitled "rubber-Modified Thermoset Resins", edited by c.k.riew and j.k.gilham, proceedings, the american chemical Society, Washington,1984 (american chemical Society, Washington, 1984). The amount of toughening agent to be used depends in part on the final physical characteristics desired of the cured resin.
In some embodiments, the toughening agents in the curable compositions of the present disclosure may include a compound havingGraft copolymers of a polymerized diene rubber backbone or core onto which is grafted a shell comprising an acrylate or methacrylate, a monovinylarene, or a mixture of these, such as those disclosed in U.S. Pat. No. 3,496,250 (Czerwinski). The rubber backbone may comprise polymerized butadiene, or a polymerized mixture of butadiene and styrene. The shell comprising polymerized methacrylate may be a lower alkyl (C) methacrylate1-4) The monovinyl aromatic hydrocarbon may be styrene, α -methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene and ethylchlorostyrene.
Another example of a useful toughening agent is an acrylate core-shell graft copolymer where the core or backbone is the glass transition temperature (T)g) Polyacrylate polymers, such as T grafted thereon, at temperatures below about 0 deg.CgPoly (butyl acrylate) or poly (isooctyl acrylate) of a polymethacrylate polymer shell such as poly (methyl methacrylate) at about 25 ℃. For acrylic core/shell materials, "core" will be understood to be Tg<Acrylic polymer at 0 ℃ and "shell" will be understood as Tg>Acrylic polymer at 25 ℃. Some core/shell toughening agents (e.g., including acrylic core/shell materials and methacrylate-butadiene-styrene (MBS) copolymers where the core is a crosslinked styrene/butadiene rubber and the shell is a polymethacrylate) are commercially available, for example, under the trade designation "PARALOID" from Dow Chemical Company.
Another useful core-shell rubber is described in U.S. patent application publication 2007/0027233(Yamaguchi et al). Core-shell rubber particles as described in this document comprise a crosslinked rubber core (in most cases a crosslinked copolymer of butadiene), and a shell, preferably a copolymer of styrene, methyl methacrylate, glycidyl methacrylate and optionally acrylonitrile. The core-shell rubber may be dispersed in a polymer or epoxy resin. Examples of useful core-shell rubbers include those sold by the Kaneka Kane ACE Corporation (Kaneka Corporation) under the name Kaneka KANE ACE, including
Other useful toughening agents include carboxyl-terminated and amine-terminated acrylonitrile/butadiene elastomers, such as those available under the trade designation "hypo" (e.g., CTBN grade and ATBN grade) from emerald performance materials, akron, ohio, usa; carboxyl-terminated and amine-terminated butadiene polymers such as those available under the trade designation "hypo" (e.g., CTB grade) from emerald performance materials; amine-functionalized polyethers, such as any of those described above; and amine functionalized polyurethanes such as those described in U.S. patent application 2013/0037213(Frick et al).
In some embodiments, the toughening agent may include an acrylic core/shell polymer; styrene-butadiene/methacrylate core/shell polymers; a polyether polymer; carboxy-terminated or amino-terminated acrylonitrile/butadiene; carboxylated butadiene, polyurethane, or combinations thereof.
In some embodiments, the toughening agent (not including the polyamide) may be present in the curable composition (or epoxy composition) in an amount of between 0.1 and 10 weight percent, between 0.1 and 5 weight percent, between 0.5 and 5 weight percent, between 1 and 5 weight percent, or between 1 and 3 weight percent based on the total weight of any or all of the epoxy composition or curable composition.
In some embodiments, curable compositions according to the present disclosure may include one or more dispersants. Generally, the dispersant may act to stabilize the inorganic filler particles in the composition, and in the absence of the dispersant, these particles may aggregate, thereby adversely affecting the benefits of the particles in the composition. Suitable dispersants may depend on the specific characteristics and surface chemistry of the filler. In some embodiments, suitable dispersants according to the present disclosure may comprise at least a binding group and a compatible segment. The binding group may be ionically bonded to the particle surface. Examples of binding groups for the alumina particles include phosphoric acid, phosphonic acid, sulfonic acid, carboxylic acid, and amine. The compatible segment may be selected to be miscible with the curable matrix. For epoxy and amide matrices, useful compatibilizers may include polyalkylene oxides (e.g., polypropylene oxide, polyethylene oxide), and polycaprolactone, as well as combinations thereof. Commercially available examples include BYK W-9010 (BYK Additives and Instruments), BYK W-9012 (BYK Chemicals and Instruments), Disberbyk 180 (BiKYK Chemicals and Instruments), and Solplus D510 (Lubrizol corporation). In some embodiments, the dispersant may be present in the curable composition (or the epoxy composition or the amide composition) in an amount between 0.1 weight% and 10 weight%, between 0.1 weight% and 5 weight%, between 0.5 weight% and 3 weight%, or between 0.5 weight% and 2 weight%, based on the total weight of any or all of the epoxy composition, the polyamide composition, or the curable composition.
In some embodiments, the dispersant may be pre-mixed with the inorganic filler prior to incorporation into any or all of the epoxy composition, polyamide composition, or curable composition. Such premixing may facilitate the filled system to behave like a newtonian fluid or be capable of achieving shear thinning effect behavior.
In some embodiments, curable compositions according to the present disclosure may comprise one or more catalysts. Generally, the catalyst may function to accelerate curing of the curable composition. In some embodiments, the catalyst may include a lewis acid. Such lewis acids may include metal salts, triorganoborates, including trialkylborates (including those represented by the formula b (or)3, wherein each R is independently an alkyl group), and the like, as well as combinations thereof. Useful metal salts include those comprising at least one metal cation that acts as a lewis acid. Preferred metal salts include metal salts of organic acids (metal carboxylates including both aliphatic and aromatic carboxylates), metal salts of sulfonic acids (e.g., trifluoromethanesulfonic acid), metal salts of inorganic acids (e.g., nitric acid), and combinations thereof. In some embodiments, the catalyst may comprise calcium triflate or calcium nitrate. Alternatively or additionally, in some embodiments, the catalyst may comprise phosphoric acid; or a combination of N- (3-aminopropyl) piperazine and salicylic acid which has a synergistic effect in accelerating the curing of polyglycidyl ethers of polyhydric phenols cured with polyoxyalkylene polyamines as discussed in U.S. patent 3,639,928(Bentley et al) and incorporated herein by reference in its entirety. In some embodiments, the catalyst may be present in the curable composition (or the epoxy composition or the amide composition) in an amount between 100ppm and 10,000ppm, or between 200ppm and 5,000ppm, based on the total weight and total volume of any or all of the epoxy composition, the polyamide composition, or the curable composition.
In addition to the additives discussed above, additional additives may be included in one or both of the first and second parts. For example, any or all of antioxidants/stabilizers, colorants, abrasive particles, thermal degradation stabilizers, light stabilizers, conductive particles, adhesion promoters, leveling agents, base agents, matting agents, inert fillers, binders, blowing agents, fungicides, bactericides, surfactants, plasticizers, and other additives known to those skilled in the art. If present, these additives are added in amounts effective for their intended use.
In some embodiments, after curing (i.e., the cured composition is the reaction product of the curable composition), the curable compositions of the present disclosure may exhibit thermal, mechanical, and rheological properties that make the compositions particularly useful as thermally conductive gap fillers. For example, it is believed that the curable compositions of the present disclosure provide the best mix of tensile strength, elongation at break, and lap shear strength for certain EV battery component applications.
In some embodiments, the cured composition may have the following elongation at break: for a fully cured system, in the range from 0.1% to 200%, 0.5% to 175%, 1% to 160%, or 5% to 160% at a draw rate between 0.8mm/min and 1.5mm/min (for the purposes of this application, elongation at break values are measured according to astm d638-03 "Standard Test Method for Tensile Properties of Plastics)"; or at least 5%, at least 5.5%, at least 6%, at least 7%, at least 10%, at least 50%, at least 100%, or at least 150% at a draw rate between 0.8mm/min and 1.5mm/min for a fully cured system.
In some embodiments, the cured composition may have the following lap shear strength on bare aluminum substrates: for a fully cured system, in the range of 1-30N/mm2、2-30N/mm2、1-25N/mm2、4-20N/mm2、6-20N/mm2、2-16N/mm2Or 3-8N/mm2(for the purposes of this application, lap shear strength values are measured on untreated aluminum substrates (i.e., aluminum substrates without a surface treatment or coating other than a natural oxide layer) in accordance with EN1465 additives-Determination of tensile lap-shear of tensile cord-shear of bonded assemblies).
In some embodiments, the cured composition may have the following tensile strength: for a fully cured system, at a draw rate between 1% strain/min and 10% strain/min, at 0.5-16N/mm2、1-10N/mm2Or 2-8N/mm2In the scope of (for the purposes of this application)For the purposes of this application, Tensile strength values are measured in accordance with EN ISO 527-2Tensile Test).
In some embodiments, the cure rate of the composition may range from 10 minutes to 240 hours, from 30 minutes to 72 hours, or from 1 hour to 24 hours for complete curing at room temperature; or may range from 10 minutes to 6 hours, 10 minutes to 3 hours, or 30 minutes to 60 minutes for complete cure at 100 ℃; or may range from 1 hour to 24 hours for complete curing at room temperature; or may range from 10 minutes to 6 hours, 10 minutes to 3 hours, or 30 minutes to 60 minutes for complete cure at 120 ℃.
In some embodiments, the green strength cure rate of the composition at room temperature may be less than 10 minutes, less than 11 minutes, less than 15 minutes, less than 20 minutes, or less than 30 minutes. For the purposes of this application, green strength cure rate means that it can be approximated from the lap shear strength build-up rate. In this regard, in some embodiments, the composition may have an overlap shear strength of at least 0.2MPa, at least 0.3MPa, at least 0.5MPa, or at least 0.8MPa after 10 minutes of curing at room temperature. For the purposes of this application, lap shear strength values are measured according to EN 1465.
In some embodiments, after curing, the curable composition of the present disclosure may have a Thermal conductivity in the range of 1.0W/(m × K) to 5W/(m × K), 1.0W/(m × K) to 2W/(m × K), or 1.4W/(m × K) to 1.8W/(m × K) (for purposes of this application, the Thermal conductivity value is determined by first measuring the Diffusivity according to ASTM E1461-13 "Standard Test Method for Thermal Diffusivity by flash Method (Standard Test Method for Thermal Diffusivity by the flash Method)", and then calculating the Thermal conductivity from the measured Thermal Diffusivity, Thermal capacity, and density measurements according to the following formula:
k is α cp ρ, where k is the thermal conductivity in W/(m K) and α is in mm2Thermal diffusivity in units of/s, cp is the specific heat capacity in units of J/K-g, and ρ is in g/cm3Is the density in units. The sample thermal diffusivity can be measured according to ASTM E1461-13 using Netzsch LFA 467 "HYPERFLASH "was measured directly and against a standard, respectively. Sample density can be measured using geometric methods, while specific heat capacity can be measured using differential scanning calorimetry. )
In some embodiments, the viscosity of the curable/partially cured composition, measured at room temperature, may range from 100 to 50000 poise and the viscosity measured at 60 ℃ may range from 100 to 50000 poise within 10 minutes after mixing the epoxy composition with the amide composition. Further to the viscosity, the viscosity of the epoxy composition (prior to mixing) measured at room temperature may be in the range of from 100 to 100000 poise, and the viscosity measured at 60 ℃ may be in the range of from 10 to 10000 poise; and the viscosity of the amide composition (prior to mixing) measured at room temperature may be in the range of from 100 to 100000 poise, and the viscosity measured at 60 ℃ may be in the range of from 10 to 10000 poise (for purposes of this application, the viscosity values are measured on an ARES rheometer equipped with a forced convection oven accessory (TA Instruments, Wood Dale, IL, US) using a 40mm parallel plate geometry at 1% strain and an angular frequency of from 10 to 500 rad/s.)
The present disclosure also relates to methods of making the above curable compositions, as well as certain components of the above curable compositions. For example, in some embodiments, the first polyamide component described above may be prepared by reacting one or more of the diacids described above with one or more of the diamines described above. In some embodiments, the reaction may be carried out at a temperature in the range of from 50 ℃ to 300 ℃, 75 ℃ to 250 ℃, or 100 ℃ to 225 ℃, in some embodiments, the reaction may be carried out at atmospheric pressure (760 torr) or at a pressure of less than 300 torr, less than 100 torr, less than 50 torr, or less than 30 torr. The end of the reaction can be determined by no more release of water by-product. The reaction can also be carried out using heterogeneous aqueous azeotropes (such as toluene, xylene) as solvents to remove water by-products. In this case, it may be advantageous to distill off the azeotropic solvent from the product mixture once the reaction no longer produces water. As mentioned above, this distillation can be carried out at atmospheric pressure or under vacuum. It is also known to those skilled in the art that polyamides can be formed by the reaction of the corresponding acid chloride of the carboxylic acid discussed above with the diamine discussed above. In such cases, the reaction may be carried out in a non-reactive anhydrous solvent (such as toluene, xylene, tetrahydrofuran, triethylamine) at a temperature below 50 ℃. In such cases, it may be advantageous to distill off the solvent at the end of the reaction. It may sometimes be desirable to include a catalyst, defoamer or antioxidant. Phosphoric acid can be used as a catalyst in a concentration of 5 to 500ppm based on the total mass of the reactants. Silicone defoamers may be employed at concentrations of 1 to 100ppm, such as those sold by dow corning corporation (midland, michigan, usa). It may also be advantageous to use antioxidants such as octylated diphenylamine or phenolic antioxidants such as those sold under the trade name IRGANOX (e.g. IRGANOX 1010 or IRGANOX 1035) by BASF (Ludwigshafen, Germany).
In some embodiments, the curable compositions of the present disclosure may be prepared by first mixing the components of the epoxy composition (including any additives), and then separately mixing the components of the amide composition (including any additives). The components of both the epoxy composition and the amide composition can be mixed using any conventional mixing technique, including by using a flash mixer. In embodiments in which a dispersant is employed, the dispersant may be pre-mixed with the inorganic filler prior to incorporation into the composition. Next, the epoxy composition and the amide composition can be mixed to form a curable composition using any conventional mixing technique.
In some embodiments, the curable compositions of the present disclosure may be capable of curing without the use of a catalyst or other curing agent. Generally, the curable composition can be cured under typical application conditions, such as at room temperature, without the need for elevated temperatures or actinic radiation (e.g., ultraviolet light). In some embodiments, the first curable composition is cured at a temperature no greater than room temperature. In some embodiments, flash heating (e.g., IR light) may be used.
In some embodiments, the curable composition of the present disclosure may be provided as a two-part composition. Generally, the two components of the two-part composition may be mixed prior to application to the substrate to be bonded. After mixing, the two-part composition can achieve the desired handling strength and ultimately achieve the desired final strength. Applying the curable composition can be performed, 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 portion, wherein the second chamber comprises the second portion, and wherein the first chamber and the second chamber are coupled to the mixing tip to allow the first portion and the second portion to flow through the mixing tip.
The curable compositions of the present disclosure may be used in 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 encapsulation compounds, impregnating and coating compounds, conductive adhesives for electronic devices, protective coatings for electronic devices, as primers or adhesion promoting layers, and other applications known to those skilled in the art. In some embodiments, the present disclosure provides an article comprising a substrate having a cured coating of the curable composition thereon.
In some embodiments, the curable composition may be used as a structural adhesive, i.e., the curable composition is capable of bonding a first substrate to a second substrate after curing. Generally, the bond strength (e.g., peel strength, lap shear strength, or impact strength) of a structural adhesive is continuously developed after the initial cure time. In some embodiments, 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 a reaction product of a curable composition according to any of the curable compositions of the present disclosure. In some embodiments, the first substrate and/or the second substrate may be at least one of a metal, a ceramic, and a polymer (e.g., a thermoplastic).
These curable compositions may be coated onto a substrate at a useful thickness in a range from 5 micrometers to 10000 micrometers, 25 micrometers to 10000 micrometers, 100 micrometers to 5000 micrometers, or 250 micrometers to 1000 micrometers. Useful substrates may be of any nature and composition, and may be inorganic or organic. Representative examples of useful substrates include ceramics, siliceous substrates including glass, metals (e.g., aluminum or steel), natural and man-made stone, woven and non-woven articles, polymeric materials including thermoplastic and thermoset polymeric materials (such as polymethyl (meth) acrylate, polycarbonate, polystyrene, styrene copolymers such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), silicones, paints (such as those based on acrylics), powder coatings (such as polyurethane or mixed powder coatings), and wood; and composites of the foregoing materials.
In another aspect, the present disclosure provides a coated article comprising a metal substrate having a coating of an uncured, partially cured, or fully cured curable composition on at least one surface of the metal substrate. If the substrate has two major surfaces, the coating may be coated on one or both major surfaces of the metal substrate and may include additional layers such as tie layers, bonding layers, protective layers, and topcoat layers. The metal substrate can be, for example, at least one of an inner surface and an outer surface of a tube, container, conduit, rod, profile, sheet, or pipe.
In some embodiments, the present disclosure also relates to a battery module comprising the curable uncured, partially cured, or fully cured composition of the present disclosure. The components of a representative battery module during assembly are shown in fig. 1, and the assembled battery module is shown in fig. 2. The
The
In some embodiments, the
In some embodiments, the curable composition may need to accommodate dimensional changes of up to 2mm, up to 4mm, or even greater. Thus, in some embodiments, the first layer comprised of the first curable composition may be at least 0.05mm thick, such as at least 0.1mm, or even at least 0.5mm thick. Depending on the electrical properties of the material, a higher breakdown voltage may require a thicker layer, for example, in some embodiments, a layer that is at least 1mm, at least 2mm, or even at least 3mm thick. Generally, to maximize heat conduction through the curable composition and minimize cost, the curable composition layer should be as thin as possible while still ensuring good contact with the heat spreader. Thus, in some embodiments, the thickness of the first layer is no greater than 5mm, such as no greater than 4mm or even no greater than 2 mm.
As the first curable composition cures, the cells are held more firmly in place. When curing is complete, the cells are finally secured in their intended positions, as shown in fig. 2. Additional elements (e.g., straps 40) may be used to secure the units for transport and further processing.
Generally, it is desirable that the curable composition be cured under typical application conditions, e.g., without the need for elevated temperatures or actinic radiation (e.g., ultraviolet light). In some embodiments, the first curable composition is cured at room temperature, or at a temperature no greater than 30 ℃ (e.g., no greater than 25 ℃, or even no greater than 20 ℃).
In some embodiments, the cure time is not longer than 60 minutes, such as not longer than 40 minutes or even not longer than 20 minutes. While very rapid curing (e.g., less than 5 minutes or even less than 1 minute) may be suitable for some applications, in some embodiments, an open time of at least 5 minutes (e.g., at least 10 minutes or even at least 15 minutes) may be required, thereby allowing time for cell positioning and repositioning. In general, it is desirable to achieve the desired cure time without the use of expensive catalysts such as platinum.
As shown in fig. 3, a plurality of battery modules 50 (such as those illustrated and described with respect to fig. 1 and 2) are assembled to form a
Each
A
In some embodiments, the
The assembled battery sub-units may be combined to form additional structures. For example, as is known, battery modules may be combined with other elements (e.g., battery control units) to form battery systems, such as those used in electric vehicles. In some embodiments, additional layers comprised of curable compositions according to the present disclosure may be used to assemble such battery systems. For example, in some embodiments, a thermally conductive gap filler according to the present disclosure may be used to mount and help cool a battery control unit.
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