Solid polymer adhesive compositions having high use temperature and

Abstract

The teachings herein relate to solid polymeric adhesive compositions for adhering metal components, methods for compounding polymeric adhesive compositions, articles including components having polymeric adhesive compositions, methods for making articles including cured solid adhesives, and articles including cured adhesives. Preferred solid polymeric binder compositions include a plurality of one or more epoxy resins and one or more polysulfones. In a preferred aspect, the present teachings relate to a stator ring (e.g., for a hybrid motor) that includes a polymeric adhesive composition for adhering a component to the ring.

Description

Priority

[0001] This patent application claims priority to U.S. Provisional Patent Application 62 / 425,326, filed November 22, 2016, and U.S. Provisional Patent Application 62 / 341,786, filed May 26, 2016, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The teachings herein relate to solid polymer adhesive compositions for adhering metal components, methods for synthesizing polymer adhesive compositions, articles including components having a polymer adhesive composition, methods for producing articles, including curing the solid adhesive, and articles including the cured adhesive. Preferred solid polymer adhesive compositions include a plurality of one or more epoxy resins and one or more polysulfones. Background Art

[0003] There is a continuing need to provide multi-component parts adhered by adhesive compositions in order to reduce costs and / or improve performance. In many applications, such as under-the-hood automotive applications, the ability to use a particular adhesive is limited by the operating temperature. Improved adhesive compositions are still needed to adhere components in these demanding applications.

[0004] Examples of epoxy adhesive compositions and epoxy compositions for applications such as composite prepregs are described in U.S. Patent Application Publication No. US2011 / 0048637, published March 3, 2011, U.S. Patent No. 6,063,839A, issued May 16, 2000, and U.S. Patent Application Publication No. US2010 / 0280151, published November 4, 2010, U.S. Patent 3,817,472A, issued June 25, 1974, and U.S. Patent 3,530,087A, issued September 22, 1970, the entire contents of which are incorporated herein by reference. Some of the compositions described in these references include epoxy resins and polysulfones. In many compositions, a high concentration of liquid epoxy resin and / or a low concentration of polysulfone are included and thus may have limited use as solid adhesive components, which may be exposed to high temperatures during shipping and storage (e.g., due to the stickiness of the components). In some compositions, the thermoplastics include functional groups that can react with the epoxy groups over time and limit the shelf-life stability of the composition. Additionally, some compositions are applied to composite material applications having a large amount of fiber reinforcement, which provides stiffness at high temperatures. However, after impregnating the fibers, it is generally not possible to process (e.g., by extrusion or injection molding) the adhesive composition.

[0005] There is still a need for polymer adhesive compositions for adhering metal components used in high-temperature environments. There is also a need for polymer adhesive compositions that can be extruded, molded, or otherwise formed in a parts molding machine before the composition cures. There is also a need for polymer adhesive compositions that generally have high tensile strength at high temperatures after curing (e.g., the ratio of tensile strength at high temperature to tensile strength at room temperature is generally high). There is also a need for compositions with good shelf-life stability (e.g., before being formed into components and / or before being activated by curing and / or expansion). There is also a need for polymer adhesive compositions that can expand during the curing process of the composition. SUMMARY OF THE INVENTION

[0006] One aspect taught herein relates to a polymer adhesive composition for molding or extruding articles, comprising: one or more epoxy resins (present in an amount of about 25% (by weight) or more and / or about 85% (by weight) or less, based on the total weight of the polymer adhesive composition) (i.e., activatable materials); about 7% (by weight) - about 45% (by weight) of one or more high-temperature thermoplastic polymers (based on the total weight of the polymer adhesive composition), having a glass transition temperature of about 175 °C or higher; about 0.5% (by weight) - about 20% (by weight) of one or more impact modifiers (e.g., present in the form of an elastomeric polymer core in a core / shell polymer); one or more curing agents for curing the epoxy resin(s) (e.g., in an amount of about 0.4% (by weight) - about 15% (by weight), based on the total weight of the polymer adhesive composition); and optionally up to 40% (by weight) of one or more fillers; and optionally up to about 7% (by weight) of one or more blowing agents (e.g., about 0.1% (by weight) - about 4% (by weight)); wherein the one or more epoxy resins include one or more solid epoxy resins and one or more liquid epoxy resins, and the concentration of the solid epoxy resin is high enough such that the polymer adhesive composition is a solid at room temperature (e.g., the polymer adhesive composition has a tensile modulus of about 20 MPa or higher as measured at about 23 °C according to ISO 527).

[0007] Another aspect of the teachings relates to a pre-cured article comprising a polymer adhesive composition according to the teachings herein, the polymer adhesive composition comprising one or more thermoplastic resins with a high glass transition temperature and one or more epoxy resins.

[0008] Another aspect of the present teachings relates to a polymeric binder composition for molding or extruding articles, comprising: about 35% (wt.) - about 65% (wt.) of one or more epoxy resins, which include a solid unmodified bisphenol-A based epoxy resin having an epoxy equivalent of about 800 g / eq or higher as measured according to ISO 3001, an epoxy cresol novolac resin having a functionality of about 3.5 or greater, and a liquid epoxy phenol novolac resin having an epoxy equivalent of about 150 - about 300 g / eq as measured according to ISO 3001; about 12% (wt.) - about 30% (wt.) or more of one or more thermoplastic polysulfones having a glass transition temperature of about 175 °C or higher; about 1% (wt.) - about 15% (wt.) of one or more impact modifiers (e.g., an impact modifier including an elastomeric polymer core of a core / shell polymer, an impact modifier consisting essentially of an elastomeric polymer core of a core / shell polymer, or an impact modifier consisting entirely of an elastomeric polymer core of a core / shell polymer); about 2% (wt.) - about 9% (wt.) of one or more curing agents for curing the epoxy resin(s), wherein the one or more curing agents include a substituted urea; about 5% (wt.) - about 25% (wt.) of one or more fillers selected from calcium carbonate, clay, and silica; about 0.1% (wt.) - about 3% (wt.) of a rheological modifier (i.e., an organic or inorganic component that increases the viscosity of the activatable material, even when used at a concentration of about 3% (wt.) or lower), and about 0.1% (wt.) - about 3% (wt.) of one or more blowing agents; wherein the one or more epoxy resins include one or more solid epoxy resins and one or more liquid epoxy resins, and the concentration of the solid epoxy resin is high enough such that the polymeric binder composition is a solid at room temperature (e.g., as measured according to ISO 527 at about 23 °C, the polymeric binder composition has a tensile modulus of about 20 MPa or higher at room temperature). The rheological modifier can be an organic or inorganic material. The rheological modifier is preferably a plate-like or fibrous material having an aspect ratio of about 3 or greater, preferably 5 or greater, more preferably about 10 or greater. Examples of organic rheological modifiers are polymeric fibers that remain solid at conventional use temperatures and preferably remain solid at conventional processing temperatures. The organic rheological modifier can include polyaramid fibers (e.g., para-aramid fibers such as fibers), consisting essentially of polyaramid fibers, or consisting entirely of polyaramid fibers. The average length of the preferred fibers for the rheological modifier is about 50 mm or less (e.g., about 35 mm or less).

[0009] Another aspect of the present teachings relates to an apparatus that includes a first substrate (e.g., a metal substrate) attached to a second substrate (e.g., a metal substrate), where the first and second substrates are directly attached by a polymer adhesive assembly. The polymer adhesive assembly can be formed from a polymer adhesive composition that includes a composite of at least one or more solid epoxy resins and at least one or more high glass transition temperature thermoplastics having a glass transition temperature of about 175 °C or higher. Preferably, the polymer adhesive composition is a polymer adhesive composition according to the teachings herein. The polymer adhesive assembly can be formed by heating and curing the polymer adhesive composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A and 1B are diagrams of exemplary lap shear samples for testing activatable materials that include a blowing agent. Figure 1A shows the geometry before the activatable material is expanded, and Figure 1B shows the geometry after the activatable material is expanded (and excess material is trimmed).

[0011] Figure 2 are diagrams of exemplary lap shear samples for testing activatable materials that do not include a blowing agent.

[0012] Figure 3 is a diagram of an exemplary component that includes two or more components attached by a polymer adhesive assembly (e.g., formed by curing a polymer adhesive composition according to the teachings herein).

[0013] Figure 4 is a perspective view showing the features of an apparatus that includes a first component (e.g., a first substrate) adhered to two or more second components (e.g., a second substrate) by a polymer adhesive assembly (e.g., formed by curing a polymer adhesive composition according to the teachings herein).

[0014] Figure 5 is a side view showing the features of an apparatus that includes a first component attached to two or more teeth by a polymer adhesive assembly, where two adjacent teeth are in direct contact with and / or directly adhered to each other.

[0015] Figure 6 is a side view showing the features of an apparatus that includes a plurality of teeth laterally nested and attached to a substrate by a polymer adhesive assembly (e.g., formed by curing a polymer adhesive composition according to the teachings herein).

[0016] Figure 7is a perspective side view showing the features of an exemplary device including a cylindrical first substrate and a plurality of teeth attached to the inner surface of the first substrate by a polymeric adhesive assembly (e.g., formed by curing a polymeric adhesive composition according to the teachings herein).

[0017] Figure 8 is a side view showing Figure 7 a portion of the device shown in

[0018] Figure 9 is a perspective side view showing the features of an exemplary device including a cylindrical first substrate and a plurality of teeth attached to the inner surface of the first substrate by a polymeric adhesive assembly (e.g., formed by curing a polymeric adhesive composition according to the teachings herein). Detailed Description

[0019] The polymeric adhesive composition according to the teachings herein is an activatable material and includes one or more components capable of polymerizing and / or crosslinking upon heating. Additionally, the activatable material typically adheres to a substrate upon heating. The activatable material is also capable of expanding upon heating. Preferably, the adhesion is a permanent adhesion, (e.g., as desired during use) which remains after exposure to heat, environmental conditions, and / or mechanical forces.

[0020] Unless otherwise specified, the term "consisting essentially of" means a concentration of about 80% (weight) - 100% (weight), preferably about 90% (weight) - 100% (weight), more preferably about 95% (weight) - 100% (weight), even more preferably about 98% (weight) - 100% (weight), and most preferably 99.2% (weight) - 100% (weight).

[0021] The polymeric adhesive composition should be a solid material under environmental conditions. For example, as measured according to ISO 527 at 23 °C (and preferably at about 50 °C), the polymeric adhesive composition (i.e., in the uncured state) may have a tensile modulus of about 20 MPa or higher, preferably about 50 MPa or higher, more preferably about 100 MPa or higher, and most preferably about 200 MPa or higher. As measured according to ISO 527 at 23 °C, the polymeric adhesive composition may have a tensile modulus of about 1000 MPa or lower, about 600 MPa or lower, or about 450 MPa or lower.

[0022] The polymeric adhesive composition of the present invention preferably is capable of forming pellets or other particles and can be stored as pellets without agglomeration. Subsequently, the pellets or other particles can be fed into a part molding machine, such as an extruder or an injection molding machine. The particles can be applied to a surface using a spraying device

[0023] Thermoplastic polymers with high glass transition temperatures

[0024] Thermoplastic polymers with high glass transition temperatures can include any thermoplastic polymer having a glass transition temperature of about 175 °C or higher. Thermoplastic polymers with high glass transition temperatures can include one or more thermoplastic polymers selected from polysulfone, polyethersulfone, polyphenylsulfone, polyetheretherketone, polyetherimide, copolymers thereof, and combinations thereof. Preferably, the thermoplastic polymer with a high glass transition temperature includes a polysulfone homopolymer and / or a polysulfone copolymer. The preferred polysulfone homopolymer consists essentially of monomer repeating units having one or more sulfone bonds (e.g., about 99% (weight) or more, about 99.5% (weight) or more, about 99.6% (weight) or more, or about 100% (weight)), or consists entirely of monomer repeating units having one or more sulfone bonds. The preferred polysulfone copolymer includes a first monomer repeating unit having one or more sulfone bonds and one or more second monomers. Preferred monomer repeating units having sulfone bonds include bisphenol A polysulfone repeating units (Formula 1), polyethersulfone repeating units, polyphenylene sulfone repeating units, polyethersulfone repeating units, polyphenylene ether sulfone repeating units, or any combination thereof. Based on the total weight of the polymer binder composition, the amount of monomer repeating units containing sulfone bonds (e.g., bisphenol A polysulfone repeating units) can be present at a concentration of about 60% (weight) or higher, about 75% (weight) or higher, about 90% (weight) or higher, about 95% (weight) or higher, or about 97% (weight) or higher. Based on the total weight of the copolymer, the concentration of the first monomer repeating unit (e.g., bisphenol A polysulfone repeating unit) in the polysulfone copolymer can be about 99% (weight) or lower, or about 98% (weight) or lower.

[0025] Thermoplastic polymers with high glass transition temperatures can have a glass transition temperature of about 175 °C or higher, preferably about 180 °C or higher, even more preferably about 185 °C or higher, and most preferably about 190 °C or higher (e.g., measured by differential scanning calorimetry at a heating rate of about 10 °C / min). Thermoplastic polymers with high glass transition temperatures can have a glass transition temperature of about 280 °C or lower, preferably about 250 °C or lower, even more preferably about 240 °C or lower, and most preferably about 225 °C or lower. For example, the glass transition temperature of thermoplastic polymers with high glass transition temperatures can be about 175 °C - about 280 °C, about 175 °C - about 225 °C, about 185 °C - about 280 °C, or about 185 °C - about 225 °C.

[0026] While the polysulfone can be a functionalized polysulfone (e.g., having end groups such as amine groups capable of reacting with epoxy resins), some or all of the polysulfone polymer molecules are preferably free of such functionalized groups. Preferably, based on the total weight of the polysulfone, the concentration of polysulfone polymer molecules having at least one amine end group can be about 50% (by weight) or less, about 20% (by weight) or less, about 10% (by weight) or less, about 5% (by weight) or less, about 2% (by weight) or less, or about 1% (by weight) or less. The concentration of polysulfone polymer molecules having at least one amine end group can be about 0% (by weight) or higher. For example, the polymer adhesive compositions taught herein can be substantially free or completely free of block copolymers that include polysulfone molecules grafted with epoxy molecules.

[0027] Preferably, some or all of the monomer repeating units of the polysulfone include ether bonds.

[0028] Preferably, the polysulfone does not have amine groups or other nitrogen atoms (e.g., terminal amine groups or others) that can react with epoxy groups.

[0029] The monomer repeating unit containing a sulfone bond can be a bisphenol A polysulfone repeating unit (or its derivative), such as the monomer repeating unit shown in Formula 1: (Formula 1)

[0030] The monomer repeating unit containing a sulfone bond can be a polyester sulfone repeating unit (or its derivative, such as the monomer repeating unit shown in Formula 2). (Formula 2) -[-O-Ph-SO2-O-Ph-]-

[0031] The monomer repeating unit containing a sulfone bond can be a polyphenylene sulfone repeating unit (or its derivative), such as the monomer repeating unit shown in Formula 3. (Formula 3) -[-Ph-SO2-]-

[0032] The monomer repeating unit containing a sulfone bond can be a polyethersulfone repeating unit (or its derivative), such as the monomer repeating unit shown in Formula 4 (e.g., POLYETHER SULFON Sulfon 200P commercially available from Imperial Chemical Industries TM ). (Formula 4) -[-Ph-SO2-Ph-O-]-

[0033] The monomer repeating unit containing a sulfone bond can have the structure shown in Formula 5 (or its derivative). (Formula 5) -[-O-C(O)-Ph(CH3)-C(O)-O-Ph-O-Ph-SO2-Ph-O-Ph(CH3)-]-

[0034] The monomeric repeating unit containing a sulfone bond can be a polyphenylene ether sulfone repeating unit (or its derivative), such as the monomeric repeating unit shown in Formula 6. (Formula 6) -[-Ph-Ph-O-Ph(R) x -SO2-Ph(R) x -O-]- x is 0, 1, 2, 3, or 4; each R is H, alkyl, aryl, alkylaryl, alkoxy, halogen, or any combination thereof.

[0035] As used herein, derivatives of the monomeric repeating unit include structures in which one or more Ph units are replaced by Ph(R) x T, where x is 0, 1, 2, 3, or 4; each R is independently H, alkyl, aryl, alkylaryl, alkoxy, halogen, or a combination thereof.

[0036] The monomeric repeating unit of the polysulfone polymer can include one or more sulfone bonds, and optionally one or more bonds selected from the group consisting of one or more ester bonds, one or more phenyl bonds, and one or more propylene bonds. For example, the monomeric repeating unit can include two aryl sulfone bonds.

[0037] Properties of polymers with a high glass transition temperature (e.g., polysulfones):

[0038] Polymers with a high glass transition temperature (e.g., polysulfones) preferably have a viscosity in the molten or liquid state (e.g., at about 343 °C) sufficient to allow the polymer to be mixed with at least a portion of the filler and / or at least one partial epoxy resin. For example, the melt flow rate (in g / 10 min, measured according to ASTM D 1238 at 343 °C / 2.16 kg) of a thermoplastic polymer with a high glass transition temperature can be about 0.5 or higher, preferably about 1 or higher, even more preferably about 2 or higher, and most preferably about 3 or higher. The melt flow rate of the polymer with a high glass transition temperature should be low enough to enable the polymer and / or the activatable material to have good mechanical properties (e.g., at high temperatures). The melt flow rate (in g / 10 min, measured according to ASTM D 1238 at 343 °C / 2.16 kg) of a thermoplastic polymer with a high glass transition temperature is preferably about 500 or lower, more preferably about 100 or lower, even more preferably about 55 or lower, even more preferably about 38 or lower, and most preferably about 25 or lower.

[0039] Preferably, the activatable material includes a sufficient amount of a thermoplastic polymer having a high glass transition temperature such that upon heating the cured material (e.g., curing at 175° C. for 30 minutes) from about 23° C. to about 150° C. and / or from about 23° C. to about 170° C., the tensile modulus is reduced by less than about 50%. Preferably, based on the total weight of the polymer binder composition, the content of the thermoplastic polymer having a high glass transition temperature is about 5% (by weight) or higher, more preferably about 7% (by weight) or higher, even more preferably about 10% (by weight) or higher, even more preferably about 12% (by weight) or higher, and most preferably about 14% (by weight) or higher. The thermoplastic polymer having a high glass transition temperature (e.g., polysulfone) is difficult to process and / or degrade at high processing temperatures. Preferably, based on the total weight of the polymer binder composition, the polymer binder composition comprises about 50% (by weight) or less, more preferably about 45% (by weight) or less, even more preferably about 40% (by weight) or less, even more preferably about 35% (by weight) or less, and most preferably about 30% (by weight) or less of the thermoplastic polymer having a high glass transition temperature (e.g., polysulfone).

[0040] The polymer binder composition according to the teachings herein includes one or more epoxy resins that are used to provide a durable adhesion to a substrate after curing.

[0041] The epoxy resin used herein refers to any conventional dimeric, oligomeric or polymeric epoxy material containing at least one epoxy functional group. Additionally, the term "epoxy resin" can be used to denote a single epoxy resin or a combination of multiple epoxy resins. The polymer-based material can be an epoxy group-containing material having one or more oxirane rings that can be polymerized by a ring-opening reaction. In a preferred embodiment, the polymer adhesive composition comprises at most about 85% (by weight) or more of the epoxy resin. Preferably based on the total amount of polymers in the polymer adhesive composition, more preferably based on the total weight of the polymer adhesive composition, the total amount of the epoxy resin(s) can be about 85% (by weight) or less, about 80% (by weight) or less, about 75% (by weight) or less, about 70% (by weight) or less, about 65% (by weight) or less, or about 60% (by weight) or less. Preferably based on the total weight of the polymer adhesive composition, more preferably based on the total weight of the polymers in the polymer adhesive composition, the total amount of the epoxy resin(s) can be about 20% (by weight) or more, about 25% (by weight) or more, about 30% (by weight) or more, about 35% (by weight) or more, about 40% (by weight) or more. For example, based on the total weight of the activatable material, the activatable material can include about 20% (by weight) - about 85% (by weight) of the epoxy resin, about 25% (by weight) - about 85% (by weight) of the epoxy resin, about 30% (by weight) - about 70% (by weight) of the epoxy resin, or even more preferably about 30% (by weight) - about 60% (by weight) of the epoxy resin. Of course, based on the intended application of the activatable material, the amount of the epoxy resin can be more or less. As an example, it can be envisioned that when other components (such as adducts, fillers, alternative polymers, and combinations thereof, etc.) are used in greater or lesser weight percentages, the weight percentages can be smaller or larger.

[0042] Epoxy resins can be aliphatic, cycloaliphatic, aromatic, etc. Epoxy resins can be provided in solid form (e.g., granules, blocks, flakes, etc.) or in liquid form (e.g., epoxy resin). As used herein, unless otherwise specified, if the resin is solid at a temperature of 23 °C, the resin is a solid resin, and if the resin is liquid at 23 °C, the resin is a liquid resin. Epoxy resins are added to the activatable material to increase the adhesiveness and / or fluidity of the material. Epoxy resins can include copolymers containing two or more monomers, or terpolymers containing three or more monomers. As homopolymers, copolymers or terpolymers, epoxy resins can include monomers having high chemical reactivity and capable of linking with similar molecules, resulting in an increase in chain length and / or grafting and / or crosslinking. Generally, epoxy resins have two or more functionalities, including a first reactive site spaced apart from a second reactive site (e.g., at different ends of the chain). The functionality of epoxy resins is typically about 10 or less, however, higher functionalities can be employed. Preferably, at least a portion of the epoxy resin includes polyfunctional epoxy resin (i.e., having a functionality greater than 2). Preferably, the polyfunctional epoxy resin has a functionality of about 2.2 or higher, about 2.5 or higher, about 3 or higher, about 3.5 or higher, or about 4 or higher. Preferably, based on the total weight of one or more epoxy resins in the activatable material, the polyfunctional epoxy resin is present in the activatable material at a concentration of about 20% (by weight) or higher, more preferably about 40% (by weight) or higher, even more preferably about 50% (by weight) or higher, and most preferably about 55% (by weight) or higher. Based on the total weight of one or more epoxy resins, the amount of polyfunctional epoxy resin in the activatable material can be about 100% (by weight) or less, preferably about 95% (by weight) or less, more preferably about 90% (by weight) or less, even more preferably about 85% (by weight) or less, and most preferably about 80% (by weight) or less. An exemplary epoxy resin can be a phenolic resin, which can be a novolac type or other type of resin. For example, the polyfunctional epoxy resin can include one or more epoxy cresol novolac resins and / or one or more epoxy phenol novolac resins, consist essentially of one or more epoxy cresol novolac resins and / or one or more epoxy phenol novolac resins, or consist entirely of one or more epoxy cresol novolac resins and / or one or more epoxy phenol novolac resins. Another preferred epoxy resin is bisphenol-F epoxy resin. Other preferred epoxy resin-containing materials can include bisphenol-A epichlorohydrin ether polymers, or bisphenol-A epoxy resins, which can be modified with butadiene or another polymer additive. In addition, various mixtures of several different epoxy resins can also be employed. In addition, examples of suitable epoxy resins are available under the trade name (e.g., CT 6060, GT 6097, ECN 9699, and EPN 9850) are sold and commercially available from Huntsman Corporation, EPALLOY TM (e.g., 8250), are commercially available from CVC Thermoset Specialties, Inc. in the United States, and (e.g., DER 331, DER 661, DER 662), are commercially obtained from The Dow Chemical Company in Midland, Michigan.

[0043] Preferably, the polymeric binder composition comprises one or more liquid epoxy resins and one or more solid epoxy resins.

[0044] The amount of the liquid epoxy resin can be sufficient such that the thermoplastic with a high glass transition temperature can be easily compounded in an extruder. For example, the weight ratio of the liquid epoxy resin to the thermoplastic resin with a high glass transition temperature (e.g., polysulfone according to the teachings herein) can be about 0.4 or higher, about 0.7 or higher, about 1.0 or higher, about 1.3 or higher, or about 1.6 or higher. If the amount of the liquid epoxy resin is too high, the activatable material may be difficult to handle (e.g., the activatable material may become sticky or even flow at room temperature). The ratio of the liquid epoxy resin to the thermoplastic resin with a high glass transition temperature is preferably about 7 or lower, more preferably about 5 or lower, and even more preferably about 4 or lower. Preferably, based on the total weight of the polymers in the composition (e.g., based on the total weight of the epoxy resin, high-temperature thermoplastic resin, and any core / shell polymer), the content of the liquid epoxy resin in the activatable material is about 65% (by weight) or lower, more preferably about 60% (by weight) or lower, even more preferably about 55% (by weight) or lower, and most preferably about 50% (by weight) or lower. Preferably, the liquid epoxy resin comprises one or more polyfunctional epoxy resins, or consists essentially of one or more polyfunctional epoxy resins, or consists entirely of one or more polyfunctional epoxy resins. For example, the liquid may include one or more epoxy novolac resins and / or one or more epoxy cresol novolac resins. Preferably, based on the total weight of the one or more liquid epoxy resins, the amount of the polyfunctional liquid epoxy resin (e.g., having a functionality of about 2.1 or higher, 2.3 or higher, 2.5 or higher, or 3.0 or higher) is about 30% (by weight) or higher, more preferably about 50% (by weight) or higher, even more preferably about 70% (by weight) or more, and most preferably about 80% (by weight) or more. Preferably, based on the total weight of the activatable material, the concentration of the liquid epoxy resin in the activatable material is about 63% (by weight) or lower, more preferably about 56% (by weight) or lower, even more preferably about 52% (by weight) or lower, and most preferably about 45% (by weight) or lower. Preferably, based on the total weight of the activatable material, the concentration of the liquid epoxy resin in the activatable material is about 5% (by weight) or higher, more preferably about 10% (by weight) or higher, even more preferably about 20% (by weight) or higher, and most preferably about 26% (by weight) or higher.

[0045] The amount of solid epoxy resin in the polymer binder composition should be sufficient such that the composition is solid at room temperature. As discussed herein, the solid epoxy resin can also contribute to the high temperature properties of the cured composition. Preferably, based on the total weight of the activatable materials, the content of the solid epoxy resin is about 4% by weight or more, more preferably about 6% by weight or more, even more preferably about 8% by weight or more, and most preferably about 10% by weight or more. The weight ratio of the solid epoxy resin to the liquid epoxy resin can be about 0.00 or higher, about 0.05 or higher, about 0.10 or higher, about 0.15 or higher, about 0.2 or higher, or about 0.25 or higher. Preferably, the weight ratio of the solid epoxy resin to the liquid epoxy resin is about 1.0 or lower, about 0.8 or lower, about 0.6 or lower, or about 0.5 or lower. The solid epoxy resin can include any chemical structure as described herein (e.g., homopolymers, copolymers, terpolymers, bisphenol-A, bisphenol-F, epoxy phenol novolac resin, epoxy cresol novolac resin, etc.). Preferably, the solid epoxy resin comprises bisphenol-F epoxy resin, consists essentially of bisphenol-F epoxy resin, or consists entirely of bisphenol-F epoxy resin. The solid epoxy resin is characterized by a molecular weight of type 3, type 4, type 5, type 6, type 7, type 8, type 9, or type 10 epoxy resin. Preferred solid epoxy resins are type 4 or higher, more preferably type 5 or higher, even more preferably type 6 or higher, and most preferably type 7 or higher. Preferred solid epoxy resins are type 10 or lower, more preferably type 9 or lower, and most preferably type 8 or lower.

[0046] Impact modifier

[0047] Generally, the polymer binder composition preferably comprises at least one impact modifier. As used herein, like any other component of the present invention, the term "impact modifier" can include one impact modifier or a plurality of impact modifiers. A variety of impact modifiers can be used in the practice of the present invention and generally include one or more elastomers. Generally, the impact modifier is preferably about 0.5% by weight or higher, more preferably about 1% by weight or higher, even more preferably about 1.5% by weight or higher, even more preferably about 2% by weight or higher, even more preferably about 2.5% by weight or higher, and most preferably about 3.0% by weight or more, based on the total weight of the activatable materials. The content of the impact modifier is preferably about 20% by weight or lower, more preferably about 16% by weight or lower, even more preferably about 15% by weight or lower, even more preferably about 9% by weight or lower, and most preferably about 7% by weight or lower, based on the total weight of the activatable materials. Higher or lower amounts can be used in specific embodiments.

[0048] In one embodiment of the present invention, the impact modifier comprises at least one core / shell impact modifier, and the impact modifier preferably comprises a majority of the core / shell impact modifier. In a preferred embodiment, the impact modifier comprises at least 60%, more typically at least 80%, even more typically at least 97% of the core / shell impact modifier. As used herein, the term "core / shell impact modifier" refers to an impact modifier in which a majority (e.g., about 30% (weight) or more, about 50% (weight) or more, or about 70% (weight) or more) thereof is composed of a first polymer material (i.e., the first or core material), and the first polymer material is substantially completely coated with a second polymer material (i.e., the second or shell material). As used herein, the first and second polymer materials may comprise one, two, three, or more polymers (or polymer blocks), which polymers (or polymer blocks) are combined and / or react together (e.g., sequential polymerization) or may be part of different or the same core / shell system.

[0049] The first and second polymer materials of the core / shell impact modifier may include elastomers, polymers, thermoplastics, copolymers, other components, and combinations thereof, etc. In a preferred embodiment, the first polymer material and / or the second polymer material of the core / shell impact modifier includes one or more thermoplastics and / or one or more elastomers, or is substantially completely composed of one or more thermoplastics and / or one or more elastomers (e.g., at least 70% (weight), 80% (weight), 90% (weight) or more). The core / shell impact modifier most preferably includes one or more thermoplastics and one or more elastomers. Exemplary thermoplastics include, but are not limited to: styrenics, acrylonitriles, acrylates, acetates, polyamides, polyethylenes, etc.

[0050] The core / shell impact modifier can be prepared in an emulsion. For example, the core and / or the shell can be prepared in an emulsion. After the core / shell impact modifier is prepared, the core / shell impact modifier can be removed from the emulsion. In one method, the matrix fluid of the emulsion is replaced with a replacement fluid (e.g., a polymer resin, a polymerizable monomer, or a polymerizable prepolymer). For example, some or all of the matrix fluid of the emulsion can be replaced with an epoxy resin (e.g., a liquid epoxy resin). The process can include the step of removing some or all of the original matrix fluid. Preferably, agglomeration of the core / shell polymer is avoided during the fluid exchange process. Preferably, the core / shell impact modifier obtained in the replacement fluid has a sufficient amount of the replacement fluid so as to reduce, minimize, or completely avoid agglomeration. Preferably, some or all of the surfactant (i.e., from the emulsion) can be removed during the process of replacing the matrix fluid with the replacement fluid. This can be particularly beneficial when improved adhesion and / or improved mechanical properties are desired after thermal aging, or after humidity aging, or after other environmental aging. The core / shell impact modifier can be formed by emulsion polymerization followed by coagulation or spray drying. Here, it may be necessary to deagglomerate the core / shell impact modifier before, during, or after preparing the composition. Preferably, the impact modifier is formed of a core / shell graft copolymer or at least includes a core / shell graft copolymer. Preferably, the first or core polymer material of the graft copolymer has a glass transition temperature that is substantially lower (i.e., at least 10, 20, 40, or more degrees Celsius) than the glass transition temperature of the second or shell polymer material. Additionally, it may be desirable for the glass transition temperature of the first or core polymer material to be below 23 °C while the glass transition temperature of the second or shell polymer material is above 23 °C, although this is not required.

[0051] Examples of useful core / shell graft copolymers are core / shell graft copolymers in which a relatively hard polymer or polymer block (e.g., a polymer or polymer block including styrene, acrylonitrile, or methyl methacrylate, consisting essentially of styrene, acrylonitrile, or methyl methacrylate, or consisting entirely of styrene, acrylonitrile, or methyl methacrylate) is grafted onto a polymer core made of a relatively soft polymer (e.g., an elastomer or an elastomer-containing polymer or polymer block such as butadiene or butyl acrylate). For example, the relative hardness of a polymer can be determined on a separate polymer or a separated polymer block by the flexural modulus (e.g., measured according to ASTM D790). Useful core / shell polymers are described in U.S. Patent No. 3,985,703, incorporated herein by reference, the core of which is made of butyl acrylate, but may be based on ethyl isobutyl, 2-ethylhexyl, or other acrylic alkyl esters or mixtures thereof. The core polymer may also include other copolymerizable compounds, e.g., compounds containing styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene, derivatives thereof, or any combination thereof, or compounds consisting of styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene, derivatives thereof, or any combination thereof. The core polymer material may also include crosslinking monomers having two or more non-conjugated double bonds with approximately equal reactivity, e.g., ethylene glycol diacrylate, butanediol dimethacrylate, etc. The core polymer material may also include graft-linking monomers having two or more non-conjugated double bonds with unequal reactivity, e.g., diallyl maleate and allyl methacrylate.

[0052] The shell portion can be polymerized from methyl methacrylate and optionally other alkyl methacrylates (e.g., ethyl, butyl, or a mixture thereof methacrylate). Up to 40% (by weight) or more of the shell monomers can be styrene, vinyl acetate, vinyl chloride, etc. Additional core / shell graft copolymers useful in the embodiments of the present invention are described in U.S. Patent Nos. 452251, 3984497, 4096202, 4034013, 3944631, 4306040, 4495324, 4304709, and 4536436, the entire contents of which are incorporated herein by reference. Examples of core / shell graft copolymers include, but are not limited to: "MBS" (methacrylate-butadiene-styrene) polymers, which are prepared by polymerizing methyl methacrylate in the presence of polybutadiene or a polybutadiene copolymer rubber. MBS graft copolymer resins typically have a polybutadiene rubber core and a shell of an acrylic polymer or copolymer. Examples of other useful core / shell graft copolymer resins include: ABS (acrylonitrile-butadiene-styrene), MABS (methacrylate-acrylonitrile-butadiene-styrene), ASA (acrylate-styrene-acrylonitrile), all acrylics, SAEPDM (styrene-acrylonitrile grafted onto an elastomeric backbone of ethylene-propylene-diene monomer), MAS (methacrylic acid-acrylic rubber-styrene), etc., and mixtures thereof.

[0053] Preferably, the impact modifier is provided as core / shell particles. In core / shell particles (e.g., having an elastomeric core), the concentration of the impact modifier generally refers to the amount of the core portion. Preferably, the impact modifier is provided as a particle dispersion comprising core / shell particles dispersed in a matrix material (and most preferably a carrier liquid). The preferred matrix material has a melting temperature of about 90 °C or lower (more preferably about 60 °C or lower), and the melting temperature of the preferred carrier liquid is about 20 °C or lower, about 10 °C or lower, or about 5 °C or lower. Preferably, the carrier liquid is a liquid epoxy resin, e.g., a liquid epoxy resin having the properties and / or structure as described herein. Based on the total weight of the dispersion (i.e., including the matrix material and the particles), the amount of the matrix material (e.g., the carrier liquid) is preferably about 25% (by weight) or more, more preferably about 50% (by weight) or more, and most preferably about 60% (by weight) or more. Based on the total weight of the dispersion, the amount of the matrix material (e.g., the carrier liquid) is preferably about 95% (by weight) or lower (although higher amounts can be employed), more preferably about 90% (by weight) or lower, and most preferably about 85% (by weight) or lower. Preferably, the carrier liquid comprises a liquid novolak resin, a liquid bisphenol-A epoxy resin, a liquid bisphenol-F epoxy resin, or any combination thereof, consists essentially of a liquid novolak resin, a liquid bisphenol-A epoxy resin, a liquid bisphenol-F epoxy resin, or any combination thereof, or consists entirely of a liquid novolak resin, a liquid bisphenol-A epoxy resin, a liquid bisphenol-F epoxy resin, or any combination thereof. The diameter of the dispersed particles is preferably about 25 nm or greater, more preferably about 50 nm or greater, even more preferably about 75 nm or greater, and most preferably about 100 nm or greater. The diameter of the dispersed particles is preferably about 10 μm or smaller, more preferably about 2 μm or smaller, even more preferably about 900 nm or smaller, even more preferably about 600 nm or smaller, and most preferably about 400 nm or smaller.

[0054] Examples of useful impact modifiers include, but are not limited to, those sold under trade names, such as Kane ACE commercially available from Kaneka Corporation (Japan). TM , and PARALOID commercially available from Rohm and Haas Company. A particularly preferred grade of PARALOID impact modifier is a polymethyl methacrylate shell and an MBS core modifier sold under the name EXL-2691A. A particularly preferred grade of Kane ACE impact modifier is a core / shell dispersion comprising about 37% (by weight) of core / shell particles having a polybutadiene rubber core dispersed in a liquid bisphenol-F carrier liquid. This grade has core / shell particles comprising about 80% (by weight) - about 90% (by weight) of the core and about 10% (by weight) - about 20% (by weight) of the shell.

[0055] While it is conceivable that various polymer / elastomer adducts can be used in accordance with the present invention, one preferred adduct is an epoxy / elastomer adduct. Preferably, an elastomer-containing adduct is used in the activatable material of the present invention. The content of the epoxy / elastomer hybrid or adduct can be at most about 30% (by weight) of the activatable material. If present, the adduct (e.g., an elastomer-containing adduct) is preferably about 0.1% (by weight) or more of the activatable material. The adduct (e.g., an elastomer-containing adduct) is preferably about 20% (by weight) or less, more preferably about 10% (by weight) or less, and most preferably about 4% (by weight) or less of the activatable material. Of course, the elastomer-containing adduct can be a combination of two or more specific adducts, and the adduct can be a solid adduct or a liquid adduct at a temperature of 23°C, or it can also be a combination thereof. In a preferred embodiment, the activatable composition is substantially or completely free of polymer / elastomer adducts.

[0056] The activatable material can optionally include one or more other polymers (e.g., homopolymers or copolymers), which can include a variety of different polymers, such as thermoplastics, elastomers, plastomers, and combinations thereof, etc. For example, but not limited to, polymers that can be suitably incorporated into the polymer mixture include halogenated polymers, polycarbonates, polyketones, polyurethanes, polyesters, silanes, allyls, olefins, styrenes, acrylates, methacrylates, epoxy resins, siloxanes, phenolic resins, rubbers, polyphenylene oxides, terephthalates, acetates (e.g., EVA), acrylates, methacrylates (e.g., ethylene methyl acrylate polymer), or mixtures thereof. Other potential polymer materials can be or can include, but are not limited to: polyolefins (e.g., polyethylene, polypropylene), polystyrene, polyacrylates, poly(ethylene oxide), poly(ethyleneimine), polyesters, polyurethanes, polysiloxanes, polyethers, polyphosphazines, polyamides, polyimides, polyisobutylene, polyacrylonitrile, polyvinyl chloride, poly(methyl methacrylate), poly(vinyl acetate), poly(vinylidene chloride), polytetrafluoroethylene, polyisoprene, polyacrylamide, polyacrylic acid, polymethacrylates. If used, based on the total weight of the polymers in the composition, any such other polymer or copolymer is preferably present at a concentration of about 10% (by weight) or less (in total), and based on the total weight of the activatable material, the concentration is preferably about 5% (by weight) or less (more preferably about 1.5% (by weight) or less, and most preferably about 0.5% (by weight) or less). If present, one or more other polymers (each or in total) can be about 0.1% (by weight) or more of the weight of the activatable composition.

[0057] Thermoplastic polyethers generally include side-chain hydroxyl moieties. The thermoplastic polyethers may also include aromatic ether / amine repeating units in their main chains. The melt index of the thermoplastic polyethers of the present invention is preferably from about 5 to about 100 g / 10 min, more preferably from about 25 to about 75 g / 10 min, and even more preferably from about 40 to about 60 g / 10 min (measured using a 2.16 kg mass at a temperature of about 190 °C). Of course, the thermoplastic polyethers may have higher or lower melt indices depending on their intended applications. The thermoplastic polyethers preferably include, but are not limited to: polyetheramines, poly(amino ethers), copolymers of monoethanolamine and diglycidyl ether, combinations thereof, and the like. Preferably, the glass transition temperature of the thermoplastic polyethers is preferably about 180 °C or lower, about 140 °C or lower, or about 100 °C or lower. The thermoplastic polyethers preferably have a glass transition temperature of about 30 °C or higher, about 40 °C or higher, or about 50 °C. The glass transition temperature can be measured by kinetic analysis (e.g., see ISO 6721-11:2012).

[0058] Preferably, the thermoplastic polyethers are formed by reacting an amine having an average functionality of 2 or less (e.g., a difunctional amine) with a glycidyl ether (e.g., diglycidyl ether). As used herein, the term "difunctional amine" refers to an amine having an average of two reactive groups (e.g., reactive hydrogens).

[0059] According to one embodiment, the thermoplastic polyethers are formed by reacting a primary amine, a bis(secondary) diamine, a cyclo diamine, combinations thereof, etc. (e.g., monoethanolamine) with diglycidyl ether, or by reacting an amine with a poly(alkylene oxide) functionalized with epoxy to form a poly(amino ether). According to another embodiment, the thermoplastic polyethers are prepared by reacting a difunctional amine with diglycidyl ether or a di-epoxy functionalized poly(alkylene oxide) under conditions sufficient to react the amine moiety with the epoxy moiety to form a polymer main chain having amine bonds, ether bonds, and side-chain hydroxyl moieties. Optionally, the polymer can be treated with a monofunctional nucleophile, which may or may not be a primary or secondary amine. Additionally, it is contemplated that an amine having one reactive group (e.g., one reactive hydrogen) (e.g., a cyclic amine) can be used to form the thermoplastic polyethers. Advantageously, such amines can contribute to controlling the molecular weight of the thermoplastic ethers formed. Examples of preferred thermoplastic polyethers and their formation methods are disclosed in U.S. Patent Nos. 5275853, 5464924, and 5962093, which are incorporated herein by reference for all purposes. Advantageously, the thermoplastic polyethers can provide various desired properties to the activatable materials, e.g., the physical and chemical properties required for various applications as further described herein. Foaming agent

[0060] One or more blowing agents can be added to the activatable material to generate an inert gas, which forms open and / or closed honeycomb structures within the activatable material as needed, and / or is used to adhere two substrates separated by a gap (e.g., by compensating for gap changes). In this way, the density of the article made of this material can be reduced. In addition, the expansion of the material helps to improve the adhesion ability.

[0061] The blowing agent can include one or more nitrogen-containing groups, such as amides, amines, etc. Examples of suitable blowing agents include azodicarbonamide, dinitrosopentamethylenetetramine, 4,4 i -oxybis-(benzenesulfonylhydrazide), trihydrazinotriazine, and N,N i -dimethyl-N,N i -dinitroterephthalamide.

[0062] A promoter for the blowing agent can also be provided in the activatable material. Various promoters can be used to increase the rate at which the blowing agent forms a gas (e.g., an inert gas) and / or reduce the temperature at which the blowing agent forms a gas. A preferred blowing agent promoter is a metal salt or an oxide, such as a metal oxide (e.g., zinc oxide). Other preferred promoters include modified and unmodified thiazoles or imidazoles.

[0063] The amounts of the blowing agent and the blowing agent promoter can vary widely within the activatable material, depending on the type of porous structure desired, the desired amount of expansion of the activatable material, the desired expansion rate, etc. If used, the exemplary range of the amounts of the blowing agent and the blowing agent promoter in the activatable material is from about 0.001% (by weight) to about 7% (by weight), and they can even be present in the activatable material in weight percentage ratios. For example, based on the total weight of the activatable material, the amount of the blowing agent can be about 7% (by weight) or less, about 4% (by weight), about 3% (by weight) or less, or about 2% (by weight) or less. If used in the activatable material, based on the total weight of the activatable material, the content of the blowing agent is preferably about 0.001% (by weight) or higher, more preferably about 0.01% (by weight) or higher, even more preferably about 0.1% (by weight) or higher, and most preferably about 0.4% (by weight) or higher.

[0064] Curing agent

[0065] One or more curing agents and / or curing agent accelerators can be added to the activatable material. Like blowing agents, the amounts of curing agents and curing agent accelerators can vary widely within the activatable material, depending on the type of porous structure desired, the desired expansion amount of the activatable material, the desired expansion rate, the structure of the epoxy resin (e.g., molecular weight, chemical structure, and functionality), the structural properties desired of the activatable material, etc. Exemplary ranges of curing agents or curing agent accelerators present in the activatable material are from about 0.001% (by weight) to about 20% (by weight). For example, based on the total weight of the activatable material, the content of the curing agent, the curing agent accelerator, or all of the curing agents and curing agent accelerators can be i) about 0.01% (by weight) or more, about 0.1% (by weight) or more, about 0.4% (by weight) or more, about 0.8% (by weight) or more, about 1.4% (by weight) or more, or about 2.0% (by weight) or more, and / or ii) about 18% (by weight) or less, about 15% (by weight) or less, about 12% (by weight) or less, or about 9% (by weight) or less.

[0066] Preferably, the curing agent aids in the curing of the activatable material by crosslinking of the polymer and / or epoxy resin. The curing agent also preferably contributes to the thermal curing of the activatable material. Useful types of curing agents are materials selected from aliphatic or aromatic amines or their corresponding adducts, amidoamines, polyamides, cycloaliphatic amines, acid anhydrides, polycarboxylic acid polyesters, isocyanates, or mixtures thereof. Particularly preferred curing agents include modified and unmodified polyamines or polyamides (e.g., triethylenetetramine), diethylenetriamine, tetraethylenepentamine, cyanoguanidine, dicyandiamide, etc. Accelerators for the curing agent (e.g., modified or unmodified ureas (e.g., methylene diphenylbisurea), imidazoles, or combinations thereof) can also be provided for the preparation of the activatable material.

[0067] The present invention contemplates omitting blowing agents and curing agents. However, preferably, both curing agents and / or blowing agents are present in the activatable material and are thermally activated. Alternatively, other reagents can be employed to effect activation by other means, such as moisture, radiation, or other means.

[0068] Filler

[0069] The activatable material can also include one or more fillers, including but not limited to: particulate materials (e.g., powders), beads, microspheres, etc. Preferably, the filler includes materials that do not typically react with other components present in the activatable material. While fillers can generally be present in the activatable material to occupy space at relatively low weight and / or relatively low cost, it is contemplated that fillers can also impart one or more properties to the activatable material (e.g., leveling, strength, or impact resistance).

[0070] Examples of fillers include silica, diatomaceous earth, glass, clay (e.g., including nanoclay), talc, pigments, colorants, glass beads or bubbles, glass, carbon or ceramic fibers, polymeric fibers such as nylon or polyaramid fibers (e.g., fibers), etc. Such fillers, particularly clay, can help the activatable material level itself during the flow of the material. Clays that can be used as fillers can include clays from the kaolinite, illite, chlorite, hydromica or sepiolite groups, which can be calcined. Examples of suitable fillers include, but are not limited to: talc, vermiculite, pyrophyllite, zinc montmorillonite, soapstone, nontronite, montmorillonite or mixtures thereof. Clays can also contain small amounts of other components such as carbonates, feldspars, micas and quartz. Fillers can also include ammonium chlorides such as dimethyl ammonium chloride and dimethyl benzyl ammonium chloride. Titanium dioxide can also be used.

[0071] In a preferred embodiment, one or more mineral or stone fillers (e.g., calcium carbonate, sodium carbonate, etc.) can be used as fillers. In another preferred embodiment, silicate minerals (e.g., mica) can be used as fillers.

[0072] When used, based on the total weight of the activatable material, the content of the filler in the activatable material can be about 0.1% (by weight) or more, about 5% (by weight) or more, about 20% (by weight) or more, or about 30% (by weight) or more. Preferably, based on the total weight of the activatable material, the content of the filler is about 70% (by weight) or lower, more preferably about 55% (by weight) or lower, even more preferably about 50% (by weight) or lower, even more preferably about 40% (by weight) or lower, and most preferably about 25% (by weight) or lower. For example, the content range of the filler can be 5% (by weight) - 60% (by weight) of the activatable material, or about 10% (by weight) - 55% (by weight) of the activatable material. It should be understood that the activatable material can be substantially free of clay and / or other layered silicates. For example, the activatable material can include about 0% (by weight) - about 3% (by weight), more preferably less than 1% (by weight) of clay and / or other layered silicates. The filler can exist as powder particles. The average particle size of such powder particles is preferably about 0.01 μm or larger, more preferably about 0.1 μm or larger, and most preferably about 1 μm or larger. The average particle size of the powder particles is preferably about 80 μm or smaller, more preferably about 50 μm or smaller, even more preferably about 25 μm or smaller, and most preferably about 15 μm or smaller. Based on the total weight of the activatable material, the amount of powdered mineral fillers in the activatable material is preferably about 1% (by weight) - about 40% (by weight), more preferably about 5% (by weight) - about 25% (by weight).

[0073] Rheology modifiers

[0074] Preferably, the activatable composition includes a rheology modifier. The rheology modifier is preferably a filler material. The rheology modifier can be an organic or inorganic material. The rheology modifier preferably remains solid at the normal use temperature and preferably remains solid at the normal processing temperature. Preferably, the rheology modifier is solid at a temperature of about 150 °C, more preferably at a temperature of about 175 °C, even more preferably about 200 °C, and most preferably about 225 °C. The rheology modifier is preferably a plate-like or fibrous material having an aspect ratio (i.e., the ratio of the longest dimension to the shortest dimension, such as the length-to-diameter ratio of a fiber) of about 3 or higher, preferably about 5 or higher, more preferably about 10 or higher, and most preferably about 20 or more. The organic rheology modifier can include polymer fibers, consist essentially of polymer fibers, or consist entirely of polymer fibers. Particularly preferred polymer fibers include polyaramid fibers (e.g., para-aramid fibers, such as fibers). The average length of the preferred fibers for the rheology modifier is about 50 mm or less (e.g., about 35 mm or less).

[0075] The viscosity modifier preferably increases the zero-shear viscosity of the composition (measured at about 100 °C) by about 10% or more, more preferably about 40% or more, and most preferably about 100% or more. For example, such a viscosity increase can be obtained with about 3% of the viscosity modifier, about 2% of the viscosity modifier, about 1% of the viscosity modifier, or even less than 1% of the viscosity modifier.

[0076] The composition can include one or more additives. Preferred additives include antioxidants, heat stabilizers, processing aids, flame retardants, and other stabilizers.

[0077] Compounding

[0078] Any method employed in polymer compounding can be used to compound the polymer binder compositions (i.e., activatable compositions) according to the present teachings. The components can be compounded together in a single step or multiple steps (e.g., by compounding at least a portion of the components together in an intermediate step). The compounding step can use a batch mixer and / or a continuous mixer. Examples of continuous mixers that can be used include extruders and kneaders, such as single-screw extruders and twin-screw extruders. Any compounding step can employ shear application, heating, cooling, or any combination thereof. For example, heating can be applied in the first stage of compounding (e.g., for melting or softening the polymer), and cooling can be applied in the second stage (e.g., for reducing or preventing premature reaction of the components). The compounding of the activatable composition is preferably carried out at a temperature low enough to substantially avoid curing of the epoxy resin. The compounding of the activatable composition is preferably carried out under specific conditions (e.g., a temperature low enough and / or a shear rate low enough) such that the particle size of the core / shell polymer is substantially maintained. The compounding of the activatable composition is preferably carried out with sufficient shear such that some or all of the agglomerated core / shell particles are deagglomerated during processing. This can be particularly advantageous when dry core / shell particles are employed.

[0079] In preparing an activatable material in accordance with the teachings herein, it is contemplated that an intermediate compounding step may be employed which includes compounding a high glass transition temperature thermoplastic polymer with at least a portion of a liquid epoxy resin prior to compounding the high glass transition temperature thermoplastic polymer with one or more other ingredients (impact modifier, filler, curing agent, blowing agent, solid epoxy resin or any combination thereof). This intermediate compound preferably comprises a high glass transition temperature thermoplastic polymer in an amount of about 5% (by weight) or more, more preferably about 15% (by weight) or more, even more preferably about 25% (by weight) or more, and most preferably about 35% (by weight) or more. For example, the intermediate compound can be a mixture which includes from about 30% (by weight) to about 80% (by weight) of a liquid epoxy resin and from about 20% (by weight) to about 70% (by weight) of a high glass transition temperature thermoplastic polymer, consists essentially of from about 30% (by weight) to about 80% (by weight) of a liquid epoxy resin and from about 20% (by weight) to about 70% (by weight) of a high glass transition temperature thermoplastic polymer, or consists entirely of from about 30% (by weight) to about 80% (by weight) of a liquid epoxy resin and from about 20% (by weight) to about 70% (by weight) of a high glass transition temperature thermoplastic polymer. The method can include the step of compounding the intermediate compound with one or more other ingredients (e.g., impact modifier, filler, curing agent, blowing agent, solid epoxy resin, other liquid epoxy resin or any combination thereof). The fully compounded polymer binder composition is preferably a multiphase material which includes one or more filler phases and a continuous polymer phase. The continuous polymer phase can also include multiple phases, including a first polymer phase containing an impact modifier and a second polymer phase containing a high glass transition temperature thermoplastic polymer. The epoxy resin can be present in the first or second polymer phase. Preferably, some or all of the epoxy resin is present in a third polymer phase.

[0080] The polymer binder composition is an activatable material and may need to be stored under conditions that minimize or reduce reaction during storage. For example, the polymer binder composition can be stored at a temperature of about 80 °C or lower (preferably about 60 °C or lower, even more preferably about 45 °C or lower, and most preferably about 40 °C or lower).

[0081] The polymeric binder composition is a solid material and can be stored as slabs, as shaped parts (e.g., preform parts or others), as pellets, etc. The polymeric binder composition can have a shape and / or size suitable for feeding into a screw and barrel assembly, such as for an extruder, an injection molding machine, or a blow molding machine. For example, the polymeric binder composition can be in the form of pellets or other particulate forms, having a mass of about 1 g or less and / or a mass of about 0.01 g or more. The polymeric binder composition can have a shape and / or size suitable for application to a surface using a spraying device (e.g., electrospray, compressed gas spray gun, or other spraying device with a nozzle). For example, the polymeric binder composition can be in the form of small particles (e.g., having a mass of about 0.05 g or lower, about 0.01 g or lower, or about 0.001 g or lower). The polymeric binder composition can be in the form of microparticles. It should be understood that particles with a high surface area to volume ratio may generally have a higher tendency to agglomerate compared to larger particles. Preferably, the composition is free of pellet blockage and powder agglomeration. Preferably, the ratio of the solid epoxy component(s) to the liquid epoxy component(s) is high enough such that the particles of the polymeric binder composition flow freely and avoid agglomeration before application to a surface.

[0082] The polymeric binder composition can be shaped into a part or assembly using any shaping method employed in polymeric material shaping. For example, the polymeric binder composition can be used with an injection molding machine, with an extruder (e.g., extruded through one or more dies to obtain a desired profile shape), with a compression molding machine, with a grinding machine, with a cutting device, with a thermoforming device, with a robotic extrusion device, etc. The step of shaping the polymeric binder composition can employ shear and heat. The polymeric binder composition can be directly extruded or molded onto a substrate to which it is to adhere. The polymeric binder composition can be shaped into a part for adhesion to a substrate at a later stage. It should be understood that the polymeric binder composition can be used in applications for adhering two or more substrates or assemblies. The polymeric material can be directly extruded or molded onto two assemblies to be adhered. The polymeric material can be directly extruded or molded onto one of the assemblies to be adhered and attached to the second assembly at a later time. The polymeric material can be shaped without contacting the assemblies to be adhered and can only contact the assemblies at one or more later times.

[0083] Although activatable materials can adhere to substrates and / or components, the materials require curing and / or activation with a foaming agent to increase adhesion. Curing can be carried out at one or more temperatures of about 140 °C or higher for a total time of about 5 minutes or longer. For example, the curing temperature is preferably about 150 °C or higher, more preferably about 160 °C or higher, and most preferably about 170 °C or higher. The curing time is preferably about 10 minutes or longer, more preferably about 20 minutes or longer, and most preferably about 25 minutes or longer. The curing temperature is preferably about 275 °C or lower, and more preferably about 225 °C or lower. The curing time is preferably about 12 hours or shorter, more preferably about 2 hours or shorter, and most preferably about 1 hour or shorter.

[0084] Applications

[0085] The activatable materials taught herein can be used in applications that require adhesion at high temperatures (e.g., high operating temperatures). For example, after activation (e.g., crosslinking and / or expansion), adhesion can be provided at high temperatures of about 100 °C or higher, about 120 °C or higher, about 140 °C or higher, or about 180 °C. Thus, these materials can be used in engine hood applications of vehicles with internal combustion engines. For example, the materials can be used in hybrid vehicles having an electric motor and an internal combustion engine. Such hybrid vehicles can advantageously use activatable materials to adhere one or more components that are exposed to an operating temperature of about 160 °C or lower (preferably about 140 °C or lower) and / or a peak temperature offset of about 200 °C or lower (preferably about 180 °C or lower). For example, activatable materials can be used to adhere components that are exposed to an operating temperature of about 100 °C or higher (or about 110 °C or higher, or about 120 °C or higher) and / or a peak temperature of about 140 °C or higher (or about 160 °C or higher, or about 170 °C or higher).

[0086] Devices

[0087] Polymer adhesive assemblies comprising a thermoplastic resin with a high glass transition temperature according to the teachings herein can be used in devices for adhering two or more components of a device. For example, the device can include a first component attached to one or more second components by a polymer adhesive assembly. The polymer adhesive assembly can be formed from a polymer adhesive composition (e.g., a polymer adhesive composition according to the teachings herein). Generally, the polymer adhesive composition crosslinks or otherwise reacts and / or expands (e.g., using one or more foaming agents) when forming the polymer adhesive assembly. The second component can be attached to a flat or curved surface of the first component. Preferably, the second component is attached to a curved surface of the first component. For example, the first component can have the surface of a cylindrical ring (or a part or section of a cylindrical ring). More preferably, the second component is attached to a concave surface of the first component. The first component can have a rotational axis and a length extending in the direction of the rotational axis.

[0088] The first component can be metal, polymer, ceramic, or any combination thereof. Preferably, the first component consists essentially or entirely of a metallic material.

[0089] The second component can be metal, polymer, ceramic, or any combination thereof. Preferably, the second component consists essentially or entirely of a metallic material. The first component or the second component can be formed of the same material or different materials. The second component can have a length. Preferably, the second component is arranged such that the length of the second component is parallel to the axis of rotation of the first component. The second component can have a width. Preferably, the width of the second component is aligned with the tangent direction of the curved surface of the first component. The second component can have a thickness. Preferably, the thickness of the second component extends from the polymer adhesive towards the axis of rotation of the first component, and / or extends in a direction parallel to the normal direction of the curved surface of the first component (e.g., in the radial direction). One or more (e.g., each) of the second components can have a side surface that contacts or attaches to the side surface of an adjacent second component. For example, the second component can have opposite first and second side surfaces, where the first side surface contacts or attaches to the side surface of a first adjacent second component, and the second side surface contacts or attaches to the side surface of a second adjacent second component. The second component can be described as a tooth protruding from the first component. Two adjacent second components are preferably nested or interlocked with each other. Thus, the side surface can include features such as one or more grooves and / or one or more ridges that allow such nesting and / or interlocking. It should be understood that the side surface can alternatively be a substantially flat surface. The device can include a sufficient number of second components (e.g., teeth) such that the second components substantially or entirely cover the circumference (e.g., the circumference of the concave surface) of the first component. For example, the first substrate can include or consist of a ring having an axis, and some or all of the circumference of the ring (e.g., the inner circumference or the outer circumference) can be covered by teeth. The teeth can have a length aligned with the axis of the ring. A polymer adhesive component can be used to attach the teeth in the stator ring. The teeth can form a magnetic field or include wire windings. Such a stator ring accommodating device can be particularly suitable for an electric motor, such as a hybrid motor in a vehicle.

[0090] The polymer adhesive component can have a uniform thickness (e.g., between the first and second components) or can have a varying thickness. The thickness of the polymer adhesive component can be sufficient such that the polymer adhesive component can provide mechanical durability to the device. Preferably, the thickness of the polymer adhesive component is about 0.1 mm or greater, more preferably about 0.4 mm or greater, and most preferably about 0.6 mm or greater. The thickness of the polymer adhesive component is preferably about 10 mm or less, more preferably about 5 mm or less, even more preferably about 2.5 mm or less, and most preferably about 1.8 mm or less. The polymer adhesive component can expand (e.g., having open pores and / or closed pores) or can substantially not expand. The expansion level is the ratio of the increased volume to the initial volume of the polymer adhesive composition before expansion, expressed as a percentage: V.E. = 100% × (Vexpanded -V initial ) / V initial 。 The swelling level of the polymer adhesive assembly can be about 0% or higher, about 10% or higher, about 20% or higher, or about 40% or higher. The swelling level of the polymer adhesive assembly is preferably about 400% or lower, more preferably about 220% or lower, even more preferably about 130% or lower, and most preferably about 70% or lower.

[0091] The first and second components can be attached by disposing a polymer adhesive composition between the first and second components and then heating the material to cure and / or swell the polymer adhesive composition to form a polymer adhesive assembly. The polymer adhesive composition can be supplied as a separate component, such as a pre-cured component that is molded, extruded, or otherwise formed, or can be attached to the first or second component before heating (e.g., before curing and / or swelling). Heating can include heating to a temperature of about 100°C or higher, about 140°C or higher, about 150°C or higher, or about 170°C. The heating can be continued for a sufficient time to cause the composition to swell and / or cure. The heating temperature should be low enough to reduce, minimize, or eliminate any degradation of the polymer adhesive composition. The heating temperature is preferably about 320°C or lower, more preferably about 260°C or lower, even more preferably about 210°C or lower, and most preferably about 190°C or lower.

[0092] The device taught herein can be particularly useful for applications that typically have a high operating temperature, such as an operating temperature of about 130°C or higher, about 150°C or higher, about 163°C or higher, or about 170°C. The operating temperature is preferably about 280°C or lower, more preferably about 220°C or lower, and most preferably about 200°C or lower.

[0093] It should be understood that, in addition to the first component, the second component(s), and the component formed from the polymer adhesive composition, a useful device can include one or more other components. For example, the device can include one or more components that contain windings for carrying an electric current, and / or one or more components that are axially aligned with the rotational axis of a cylinder of the first substrate (e.g., for rotating about a rotational axis or for supporting rotation), such as having the same rotational axis as the rotational axis of the cylinder.

[0094] Figure 3 The features of device 10 are shown, which device 10 includes a first component 12 (i.e., a first substrate) attached to a second component 16 (i.e., a second substrate) by a polymer adhesive 14. As Figure 3As shown, the polymeric binder 14 can cover the gap between the first component 12 and the second component 16 and / or can directly attach the first component 12 and the second component 16. Figure 4 The features of the device 10' are shown, which device 10' has two or more second components. The components 16, 16' are each connected to the first component 12. As Figure 5 shown, the second component 16 can contact and / or attach to another second component 16' along the side surface 18. As Figure 6 shown, the device 20 can include a plurality of nested second components 22, 22', 22". For example, the second component can have a side surface 28 that mates with the side surface of an adjacent second component.

[0095] Reference Figures 7 - 9 , the first component 32 can have a curved surface 38. For example, the first component 32 can have a cylindrical ring shape. In this way, the first component can have a rotational axis (e.g., the axis of the cylinder). The second component 36 can be attached to the first component 32 by a layer of polymeric binder 34 that substantially or completely covers the circumference of the surface 38 of the first component 32. Adjacent second components can contact or be directly attached (e.g., as Figure 7 and Figure 8 shown), or can be spaced apart (e.g., as Figure 9 shown).

[0096] Testing method

[0097] The volume expansion is calculated by first measuring the initial volume (at about 25 °C) of a sample of the polymeric binder composition that is 23 mm × 25 mm × 1 mm, curing the composition at 175 °C for 30 minutes, and then measuring the volume after the cured material has cooled to about 23 °C. The volume expansion is the ratio of the increased volume to the initial volume.

[0098] Unless otherwise stated, density measurements are made at 23 °C.

[0099] The lap shear test is carried out on a tensile testing apparatus at a crosshead speed of 10 mm / min. All samples are cured at 175 °C for 30 minutes and then cooled to room temperature before testing. The initial sample dimensions are 25 × 25 × 1 mm, as shown in Figures 1 and 2. For materials containing a blowing agent, the amount of blowing agent is selected to produce a volume expansion of 150% - 350% (e.g., see Figure 1A the polymeric binder composition 6 before expansion and Figure 1B the polymeric binder composition 6' after expansion). When testing materials that include a blowing agent, a bond line thickness of 2 mm is used ( Figure 1A and 1B)。When testing material 8 without a blowing agent (or with minimal expansion), a bondline thickness equal to the thickness of the uncured sample is used (i.e., 1 mm), as Figure 2 shown. Refer to Figure 1A , 1B and 2, the lap shear test is conducted on substrate 4, which is preferably a 1.8 mm thick oil-free hot-dip galvanized alloy. The maximum stress (MPa) is measured. The lap shear is tested at a crosshead rate of 10 mm / min, and the distance between the fixtures is approximately 112.5 mm.

[0100] Characterize and record the type of failure (according to PSA Peugeot Citroen, Materials Test Method, D41 1108, Adhesive Tensile Shear Strength (Scale Method) “PSA Peugeot Citroen, Méthode d'essai matériaux, D41 1108, ADHESIFS RESISTANCE EN TRACTION-CISAILLEMENT (METHODE DES CALES)”, June 10, 2008, the entire content of which is incorporated herein by reference). Unless otherwise stated, the failure mode is characterized by cohesive failure within the surface layer, which is considered cohesive failure.

[0101] Unless otherwise stated, the hot-dip galvanized alloy is HDG HX420LAD+Z100MBO and is cleaned and dried with acetone before preparing the samples.

[0102] Lap shear tests are conducted at various temperatures (e.g., at 23 °C, 90 °C, 120 °C, 150 °C, 180 °C, and 210 °C) on samples cured at 175 °C for 30 minutes.

[0103] Tensile tests are measured using JIS K6301-1-MET type samples according to ISO 527. The sample has a dog-bone shape with a total length of approximately 120 mm, a width of approximately 25 mm in the wide fin portion, and a width of approximately 10 mm in the narrow test area. The test speed (crosshead rate) is approximately 10 mm / min, the distance between the fixtures is approximately 75 mm, and the extensometer distance is approximately 35 mm. Tensile properties are tested at approximately 23 °C on uncured samples (cured at 175 °C for 30 minutes); on cured samples, tensile properties are tested under controlled temperature conditions of 23 °C, 120 °C, 150 °C, 180 °C, or 210 °C. Examples

[0104] Formulations

[0105] OMICURE TM 52M is an aromatic substituted urea commercially available from Emerald Performance Materials, LLC, of Moorestown, New Jersey, and includes 95 - 100% (by weight) of methylene diphenyl bis(dimethylurea).

[0106] Epoxy Resin A: is a solid unmodified bisphenol-A based epoxy resin (type 7) with a softening point of about 125 - 135 °C, an epoxy equivalent of about 1695 - 1885 (measured according to ISO 3001), a density of about 1.20 g / cm 3 (measured at 25 °C), a viscosity of about 1800 - 2600 mPas (falling ball method measured at 25 °C according to ISO 12058-1, 40% in butyl carbitol), a Mettler softening point of about 121 - 132 °C (measured according to DIN 51920), and a hydroxyl content of about 3.2 eq / kg (measured according to ISO / DIS 4629), and is commercially available from Huntsman Advanced Materials, The Woodlands, Texas, USA.

[0107] Epoxy B: 9699 is an epoxy cresol novolak resin with a functionality of about 5.5, a viscosity of about 7000 - 10000 mPas (measured at 130 °C), an epoxy equivalent of 205 - 225 g / equivalent, a Mettler softening point of about 80 - 100 °C, and is commercially available from Huntsman Advanced Materials, The Woodlands, Texas, USA.

[0108] Epoxy 9850 is an epoxy phenol novolak resin with an epoxy equivalent of about 168 - 178, a density of about 1.2 g / cm at 25 °C 3 , and a viscosity of about 20000 - 26000 cP at 25 °C.

[0109] Epoxy is an epoxy phenol novolak resin with an epoxy equivalent of about 165 - 178, a viscosity of about 18000 - 28000 cps at 25 °C, a functionality of about 2.65, and a residual epichlorohydrin concentration of about 10 ppm, and is commercially available from Emerald Performance Materials, LLC, Mount Laurel, New Jersey.

[0110] Kane Ace 267 is a core / shell polymer particle having a core of poly(butadiene) rubber dispersion (about 37% (by weight)) and a core of liquid bisphenol F (about 63% (by weight)), and is commercially available from Kaneka Texas Corporation (Pasadena, Texas). The diameter of the particles is about 100 nm - about 300 nm.

[0111] Epoxy D: is a liquid bisphenol F epoxy resin with an epoxy equivalent of about 171.

[0112] It is an azodicarbonamide preparation with an average particle size of about 3.1 - 4.5 microns, and the concentration of azodicarbonamide is about 57 - 63% (by weight), and it is commercially available from LANXESS (Pittsburgh, Pennsylvania, USA).

[0113] Masterbatch A is a masterbatch containing about 20% (by weight) of a branded aromatic polyamide fiber pulp and about 80% (by weight) of bisphenol - A solid epoxy resin.

[0114] Dyhard 100S - - is a micronized dicyandiamide curing agent.

[0115] It is a thermoplastic polysulfone, measured at 343 °C / 2.16 kg according to ASTM D1238, with a melt flow rate of about 6.5 g / 10 min, a specific gravity measured according to ASTM D792 of about 1.24, a tensile modulus measured according to ASTM D638 of about 2480 MPa, an elongation at break measured according to ASTM D638 of about 50 - 100%, a flexural modulus measured according to ASTM D790 of about 2690 MPa, a heat distortion temperature measured at an unannealed 1.8 MPa load according to ASTM D648 of about 174 °C, a glass transition temperature of about 185 °C - about 215 °C, and a notched Izod impact strength measured according to ASTM D256 of about 69 J / m, and it is commercially available from Solvay Group.

[0116] Example 1

[0117] Example 1 is carried out by mixing the thermoplastic polysulfone with a part of epoxy resin C in a weight ratio of about 1:1 to form an epoxy resin / sulfone mixture. Then the epoxy resin / sulfone mixture is compounded with epoxy resin A, epoxy resin B, pigments, other epoxy resin C1, core / shell polymer A, masterbatch A, Calibrite OG, zinc oxide, Dyhard 100S, Omicure 52M, and Genitron LE, and the proportions are as shown in Table 1. The compounding temperature is maintained below 100 °C. The density and tensile properties of the activatable composition are measured at about 23 °C. The tensile properties of the cured material are measured at about 23 °C and about 150 °C. The volume expansion of the material is measured after curing at 175 °C for 30 minutes. As Example 1 includes a foaming agent for expansion, a lap - shear test is carried out using samples with an initial thickness of about 1 mm and an adhesive line of about 2 mm. During the curing at 175 °C for 30 minutes, the material expands and adheres to two metal sheets. The lap - shear is measured at about 23 °C, 90 °C, 120 °C, 150 °C, 180 °C, and 210 °C. The test results are shown in Table 1.

[0118] Except for changing the amounts of some components, the preparation and testing of Example 2 were the same as those of Example 1.

[0119] The preparation of Example 3 was the same as that of Example 2, except that the sample did not contain a blowing agent or zinc oxide, and the amount of calcium carbonate was increased. Since there was no blowing agent, the bond line for the lap shear test was set to the sample thickness so that the material contacted two metal pieces.

[0120] Measured according to ASTM D648 under a load of 1.8 MPa, Examples 1, 2, and 3 should have a heat distortion temperature greater than 60 °C. Measured according to ASTM D648 under a load of 1.8 MPa, after curing at 175 °C for 30 minutes, Examples 1, 2, and 3 should have a heat distortion temperature greater than 160 °C.

[0121] The preparation of the comparative example was the same as that of Example 2, except that the sample did not include polysulfone and core / shell polymer. Therefore, the amounts of other composition components were increased (including the amounts of epoxy resin A, epoxy resin D, and calcium carbonate). The comparative example lost most of its strength from 23 °C to 150 °C. This material was not dry to the touch and could not be granulated. SCF: Surface Cohesive Failure CF: Cohesive Failure AF: Adhesive Failure.

Claims

1. A polymer binder composition for molding or extruding articles, comprising: i) one or more epoxy resins in an amount of 25% to 85% by weight, based on the total weight of the polymer binder composition; ii) one or more high-temperature thermoplastic polymers in an amount of 7% to 45% by weight, based on the total weight of the polymer binder composition, having a glass transition temperature of 175 °C or higher; wherein the melt flow rate of the one or more high-temperature thermoplastic polymers, measured according to ASTM D 1238 at 343 °C / 2.16 kg, is 0.2 g / 10 min to 100 g / 10 min; iii) one or more impact modifiers in an amount of 0.5% to 20% by weight, wherein the impact modifier comprises an elastomeric polymer core of a core / shell polymer; iv) one or more curing agents for curing the epoxy resin; and v) one or more fillers in an amount of 0.1% to 25% by weight; and vi) optionally, one or more blowing agents in an amount of up to 7% by weight; wherein the one or more epoxy resins comprise one or more solid epoxy resins and one or more liquid epoxy resins, and the concentration of the solid epoxy resin is high enough such that the polymer binder composition is a solid at room temperature; the one or more fillers comprise polyaramid fibers having a length of 35 mm or less; and the polymer binder composition is an activatable material and is cured at a temperature of 150 °C; wherein the one or more high-temperature thermoplastic polymers comprise polysulfone, and the polysulfone is provided as a mixture with a part of the one or more liquid epoxy resins; wherein the mixture comprises 30% to 80% by weight of the liquid epoxy resin and 20% to 70% by weight of the high-temperature thermoplastic polymer.

2. The polymer binder composition according to claim 1, wherein the one or more high-temperature thermoplastic polymers comprise a polymer having a repeating unit, and the repeating unit has a sulfone group along a main chain having two arylsulfone bonds.

3. The polymer binder composition according to claim 2, wherein the repeating unit comprises one or more ether bonds.

4. The polymer binder composition according to claim 3, wherein the repeating unit is:

5. The polymer binder composition according to claim 4, wherein, based on the total weight of the high-temperature thermoplastic polymer, the concentration of the repeating unit is 90% by weight or higher.

6. The polymer binder composition according to claim 5, wherein the polymer binder composition comprises one or more polymer fibers, and the length of any fiber in the polymer binder composition is 50 mm or less.

7. The polymer binder composition according to any one of claims 1 to 6, wherein the elastomeric polymer comprises polybutadiene, a copolymer comprising (a) butadiene and (b1) styrene and / or (b2) acrylonitrile, a random copolymer comprising two or more α-olefins, polyisoprene, or any combination of the foregoing polymers, or a block copolymer comprising blocks of the foregoing polymers; wherein the elastomeric polymer is provided as discrete particles of a core / shell polymer.

8. The polymer binder composition according to any one of claims 1 to 6, wherein measured at 23 °C according to ISO 527, the polymer binder composition is a solid at a temperature of 50 °C, and / or the polymer binder composition has a tensile modulus of 50 MPa or higher.

9. The polymer binder composition according to any one of claims 1 to 6, wherein the concentration of the high-temperature thermoplastic polymer is high enough such that the polymer binder composition is characterized by a heat distortion temperature of 60 °C or higher as measured according to ASTM D648 under a load of 1.8 MPa.

10. The polymer binder composition according to claim 1, wherein the one or more high-temperature thermoplastic polymers comprise a polysulfone that does not contain an amino group that can react with an epoxy resin.

11. A pre-cured article comprising the polymer binder composition according to any one of claims 1 to 10, wherein the pre-cured article is an extruded article or a molded article.

12. The pre-cured article according to claim 11, wherein the pre-cured article comprises a first portion comprising the polymer binder composition attached to a second portion, the second portion being metal.

13. The article according to claim 11, wherein the pre-cured article consists essentially of or consists entirely of the polymer binder composition.

14. The pre-cured article according to claim 13, wherein the pre-cured article comprises a first surface for adhering to a first metal component and an opposite second surface for adhering to a second metal component.

15. A post-cured article comprising a polymer assembly formed by curing the polymer binder composition according to any one of claims 1 - 10, wherein the polymer assembly comprises a first surface attached to a first metal component and a second surface attached to a second metal component.

16. The post-cured article according to claim 15, wherein the thickness of the post-cured article is 0.3 mm - 10 mm; wherein the glass transition temperature of the polymer assembly is 150 °C or higher; and the polymer assembly is characterized by a heat distortion temperature of 120 °C or higher as measured according to ASTM D648 under a load of 1.8 MPa.

17. A method of preparing the post-cured article according to any one of claims 15 or 16, comprising the steps of: mixing a polysulfone with one or more liquid epoxy resins to form a polysulfone / epoxy resin mixture; At a sufficiently low temperature and a sufficiently low shear rate, at least mix a polysulfone / epoxy resin mixture, a core / shell polymer comprising an elastomeric polymer, one or more solid epoxy resins, a masterbatch comprising polymer fibers and a liquid epoxy resin, and a curing agent, the curing agent, wherein the temperature is sufficiently low such that curing of the epoxy resin is substantially avoided, and the shear rate is sufficiently low such that the particle size of the core / shell polymer is substantially maintained; Form a pre-cured article; Heat the pre-cured article such that the polymer binder composition cures into a cured polymer assembly having a first surface adhered to a first metal component and a second surface adhered to a second metal component.

18. Use of the polymer binder composition according to any one of claims 1 to 10 in an under-hood vehicle component having a continuous operating temperature of 120 °C or higher and / or a peak operating temperature of 180 °C or higher.

19. A polymer binder composition for molding or extruding articles, comprising: i) 35% to 65% by weight of one or more epoxy resins, including a solid unmodified bisphenol-A based epoxy resin having an epoxy equivalent of 800 g / equivalent or higher as measured according to ISO 3001, an epoxy cresol novolak resin having a functionality of 3.5 or higher as measured according to ISO 3001, and a liquid epoxy phenol novolak resin having an epoxy equivalent of 150 - 300 grams / equivalent as measured according to ISO 3001; ii) 12% to 30% by weight or more of one or more thermoplastic polysulfones having a glass transition temperature of 175 °C or higher; the thermoplastic polysulfone includes a polysulfone that does not contain an amino group that can react with the epoxy resin; wherein as measured according to ASTM D 1238 at 343 °C / 2.16 kg, the melt flow rate of the one or more high-temperature thermoplastic polymers is 0.2 g / 10 min - 100 g / 10 min; iii) 1% to 15% by weight of one or more impact modifiers, including an elastomeric polymer core of a core / shell polymer; iv) 2% to 9% by weight of one or more curing agents for curing the epoxy resin, wherein one or more curing agents include a substituted urea; v) 5% to 25% by weight of one or more fillers selected from calcium carbonate, clay, silica, talc, glass, carbon or ceramic fibers, polymer fibers, and any combination thereof; vi) 0.1% to 3% by weight of polyaramide fibers having an average length of 35 mm or less; and vii) 0.1% to 3% by weight of one or more blowing agents; wherein the one or more epoxy resins include one or more solid epoxy resins and one or more liquid epoxy resins, wherein the concentration of the solid epoxy resin is high enough such that the polymer binder composition is a solid at room temperature; wherein the polymer binder composition cures at a temperature of 150 °C; wherein the polysulfone is provided as a mixture with a part of the one or more liquid epoxy resins; The mixture therein comprises 30%-80% by weight of a liquid epoxy resin and 20%-70% by weight of a high-temperature thermoplastic polymer.

20. An apparatus comprising: i) a first substrate; ii) one or more second substrates attached to the first substrate by: i) the polymer binder composition for molding or extruding articles according to any one of claims 1-10.

21. The apparatus according to claim 20, wherein the first substrate is a cylindrical ring and the second substrate is attached to the inner surface of the cylindrical ring.

22. The apparatus according to claim 20, wherein the solid epoxy resin is cured by heating the polymer binder composition to a temperature of 150°C or higher for a sufficient time, and both the first substrate and the second substrate adhere to the polymer binder assembly.

23. The apparatus as claimed in claim 20, wherein i) the polymer binder assembly is in an expanded state, including open cells and / or closed cells; and / or ii) the thickness of the polymer binder assembly is 0.1 mm - 10 mm.

24. A method of operating an electric motor comprising the apparatus according to any one of claims 20-23, the method comprising the step of maintaining the adhesion between the first substrate and the one or more second substrates when operating at a temperature of 150°C or higher.

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