BR112020025140A2 - MONOFILAMENT OF REFORMABLE RESINS AND FORMED COMPOSITE MATERIALS - Google Patents

Abstract

the present teachings contemplate the formation of a resettable epoxy resin material in a monofilament having a denier of about 50 to about 5000 and a glass transition temperature of less than about 200 ° c; load one or more monofilaments on a spool; co-weaving one or more monofilaments with a reinforcing fiber to form a woven material, the reinforcing fiber having a glass transition temperature greater than 200 ° c; heat the woven material to form a compound at a temperature so that only one or more monofilaments soften, but the reinforcing fiber does not.

Description

“MONOFILAMENT OF REFORMABLE RESINS AND FORMED COMPOSITE MATERIALS” FIELD OF THE INVENTION

[001] The present invention relates, in general, to resettable epoxy resins for use in monofilament fibers and, more specifically, to moldable materials formed using said fibers and composite structures formed with them.

TECHNICAL STATUS

[002] Industrial fiber materials often require means to maintain or bond the materials. Often, thermoplastic materials (for example, fibers) are used to sew or join the materials. However, such current methods include a number of disadvantages, including, but not limited to, the incompatibility of typical thermoplastics with secondary materials (in particular epoxy based materials), lack of sufficient mixing, wire showing through composite surfaces, behavior of thermoplastics after sanding or cutting secondary materials, rigidity of typical thermoplastics and lack of reformability of typical thermoplastics.

[003] Reformible thermoplastic polymers having at least one epoxide group have been described in USS115075; US4438254; US6011111; and WO 98/14498 (see for example, pages 3-8) together with illustrative synthetic conditions, all of which are incorporated by reference (see also, US3317471 and US4647648, also incorporated by reference). Examples of such materials (for example, resettable resin materials) can also be found, without limitation, in paragraphs 15-25 of Published Patent Application US20070270515 (Chmielewski et al), incorporated by reference for all purposes.

[004] The use of such thermoplastic polymers in a composite material was disclosed in PCT Publication number WO / 2008/010823 (addressing the in situ reaction of an epoxy and an amine after impregnation), incorporated herein by reference.

[005] Yarns using these resealable epoxy resin materials were disclosed in PCT publication number WO2016 / 065104. However, this disclosure fails to identify monofilaments with the necessary denier for use in the composite structures described here.

[006] There is, therefore, a need for materials that have certain thermoplastic capacities and a small desirable denier in a single monofilament, in which they can be woven with fibers having a much greater glass transition to promote the constant thickness of a composite structure. formed by the woven material.

SUMMARY OF THE INVENTION

[007] The teachings in this document are directed to a method that comprises forming a resettable epoxy resin material in a monofilament with a denier of about 50 to about 1000 and a glass transition temperature below about 200ºC, carrying one or more monofilaments on a spool, co-weave the monofilaments with a reinforcing fiber to form a woven material, the reinforcing fiber having a glass transition temperature greater than 200ºC, heating the woven material to form a composite at a temperature so that only one or more monofilaments soften but the reinforcing fiber does not.

[008] The reinforcement fiber can be selected from the group consisting of glass fibers, carbon fibers, aramid fibers, polymeric fibers (for example, polyethylene, polypropylene, polyamide, polyester) and their combinations. The resulting compound can have a constant thickness as a result of the failure of the structural fibers to soften. The resulting compound can be used to form an armature material (for example, a composite armature material or a composite ballistic armature material). The resulting compound can be used to form a helmet, a jacket, a shield or the like. One or more denier or diameter of the monofilament may be substantially similar to that of the reinforcement fiber. One or more denier or diameter of the monofilament may be smaller than that of the reinforcement fiber. One or more denier or diameter of the monofilament may be larger than that of the reinforcement fiber. The resulting composite can be an epoxy laminate. The resulting compound can be substantially free of any film layer.

[009] The method can be substantially free of surface treatment to form class A surfaces. The resulting compound can be painted. Monofilament can develop adhesive properties after softening. The service life of the monofilament can be at least about 3 months, at least about 6 months, at least about 1 year, or even at least about 5 years. Monofilament can be recyclable. The resulting compound can be foldable.

[010] The teachings here are also directed to a monofilament with a denier of about 5 to 5000, or about 200 to 3200 and a glass transition temperature of less than about 200ºC and comprising a resettable epoxy resin material. The resettable epoxy resin material can be formed as a reaction product of a bifunctional epoxy resin and a primary amine. The resettable epoxy resin material can be formed as a reaction product of bisphenol A diglycidyl ether (BADGE) and monoethanolamine. The monofilament can be foldable. The monofilament can be woven to form a foldable product.

[011] The teachings here are also directed to a fibrous material product formed from the monofilament described here, fabric with one or more reinforcement fibers having a glass transition temperature of 200ºC or higher. The fibrous material product can be foldable.

[012] In addition, ballistic composite materials are provided, including one or more layers comprising a woven material formed from a plurality of resettable epoxy resin monofilaments and a plurality of reinforcement fibers. The composite material can be used to form a helmet. The composite material can be used to form body armor. The composite material can be used to form a shield. The composite material can be formed in a press heated to a temperature below about 200ºC.

[013] The teachings in this document provide a resettable resin monofilament having a particular denier and glass transition temperature so that it can be woven with a reinforcing fiber to form a composite having a substantially constant thickness after exposure to heat to form the composite.

DETAILED DESCRIPTION

[014] The present teachings address one or more of the above needs by the improved composite structures and methods described in this document. The explanations and illustrations presented in this document are intended to familiarize others versed in the technique with the teachings, their principles and their practical application. Those skilled in the art can adapt and apply the teachings in their numerous forms, as they may be more suited to the requirements of a particular use. Consequently, the specific modalities of the present teachings, as established, are not intended to be exhaustive or limiting the teachings. The scope of the teachings should therefore be determined not with reference to the above description, but should instead be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible, as will be compiled from the following claims, which are also incorporated herewith by reference to this written description.

[015] This order is related to and claims the benefit of the filing date of United States Provisional Order Serial No. 62/683229, filed on June 11, 2018, the contents of that order being incorporated herein by reference for all purposes.

[016] The teachings in this document make advantageous use of a resettable epoxy filament (eg monofilament) that adheres when cooled. The teachings in this document contemplate a method for providing composite structures or other molded structures that are assembled (for example, sewn, woven, or formed with a web or mesh) with the filaments (for example, weavable retreadable epoxy resin filaments) described in this document . The resulting structures are formable and moldable after the reformable epoxy monofilament is heated and subsequently falls below its glass transition temperature. Retreadable epoxy filaments are particularly compatible with different reinforcing fibers and secondary epoxy-based materials, so that compatibility is improved over typical thermoplastic fibers (for example, polyester). The glass transition temperature of the reinforcement fibers can be higher than that of the reformable epoxy filaments, it can be heated and softened, while the reinforcement fibers do not soften.

[017] The teachings in this document provide a number of uses for resettable epoxy monofilaments. In one embodiment, the resettable epoxy filaments can be woven with reinforcing fibers. Examples of which include, but are not limited to, glass, carbon, aramid and / or polyamide fibers. Retreadable epoxy filaments may be more compatible with reinforcement fibers compared to typical thermoplastic fibers. This may be due to the similarity in size, diameter and / or denier of the resettable epoxy filaments and reinforcement fibers. For example, resettable epoxy monofilaments can have a denier of about 5 to about 6000, about 30 to about 4000, about 175 to about 3800, or even about 200 to about 3200. Reformable epoxy monofilaments can have a denier of about 100 to about 1000, from about 150 to about 500, or even from about 200 to about 400. When weaving the reformable epoxy monofilaments with a reinforcing fiber, these woven structure fibers can be used to produce collapsible and composite materials that maintain desired consistent thickness, strength and adhesion. The flexible nature of the resulting structures is easier to form than rigid composites, allows for more complex shapes, requires less heat / energy to process and has a higher modulus than typical thermoplastic fibers.

[018] In another embodiment, the resettable epoxy filament can be combined with additional monofilaments to a desired thickness and these combined filaments can be woven with a reinforcing fiber. This allows for the specific customization of the size of the resealable epoxy material, so that the epoxy filaments are compatible with a selected reinforcement fiber.

[019] The materials and methods taught in this document include possible uses for resettable epoxy filaments. It is possible that the reformable epoxy materials can be supplied initially in the form of granules and then formed in a spool filament. The spool filament and a spool reinforcement fiber can be located adjacent to each other for simplified weaving.

[020] The resettable epoxy monofilaments described in this document can be used to form composite structures that can be shaped to form helmets, body armor, shields or protective armor (for example, a composite armor material or a composite ballistic armor material. ) of any kind. It is desirable that these composites (or the composite layer formed with the resettable epoxy monofilaments) have a consistent cross section and / or thickness. This is possible by weaving the filaments with a reinforcement fiber, whereby, when exposed to elevated temperatures, the resettable epoxy filaments soften and adhere and the reinforcement fibers do not soften and are therefore able to maintain the desired consistent cross section and / or thickness.

[021] The processing temperature can affect the yarn formation process in which the viscosity of the reformable epoxy materials may require adjustment to form the desired monofilaments. Specifically, materials may require processing at a temperature of at least 150 ° C, at least 170 ° C, at least 190 ° C or even at least about 200 ° C. At lower processing temperatures, the viscosity of materials can be too high for formation in monofilaments. In one embodiment, it is possible for the material to be formulated to have a lower viscosity (sufficient to form filaments), even at temperatures below 200ºC, below

170ºC or even below 150ºC. However, the temperature for processing retreadable epoxy materials can remain below the temperature required to process fibers formed from other materials, such as typical thermoplastics. The use of lower processing temperatures reduces the risk of thermal stability of the filaments during processing and allows for easier cooling of the filaments. The cooled filaments minimize any unwanted stickiness of the fiber so that the filaments are not sticky when wound.

[022] A key advantage of the present teachings on existing commonly used fibers (for example, polyester fibers) is improved compatibility with other materials, including epoxy-based thermoset epoxy resin matrix materials (commonly used in composite structures) . Specifically, the reformable monofilament can be an amine-terminated resin that can potentially react with a thermoset resin. In addition, the low glass transition temperature of the filaments described in this document is beneficial in that the disclosed filaments can be easily softened at a low temperature without softening the reinforcing fibers woven with the resettable epoxy filaments. The additional benefits of resealable epoxy filaments include rapid adhesion and the ability to reform and remodel the filaments with the addition of heat. Adhesion and return to a solid state after cooling the retreadable epoxy filaments starts almost immediately after heating is stopped and full adhesion can occur within about 10 seconds to about 60 seconds (for example, about 30 seconds ). In addition, retreadable epoxy filaments may be desirable because of their long service life. It may also not require refrigerated temperature storage, unlike some alternative materials.

[023] As an example, the resettable epoxy material to form the filaments may be and / or may include a product (for example, a thermoplastic condensation reaction product)] from a reaction of a mono or multifunctional species (i.e., respectively, a species having one or two reactive groups, such as an amide-containing species), with an epoxide-containing fraction, such as a diepoxide (ie, a compound having two epoxide functionalities), reacted under conditions to make the hydroxyl fractions reacted with the epoxy portions to form a polymer chain of generally general structure with ether bonds.

Exemplary refillable epoxy materials can be made with a bifunctional epoxy resin and a primary amine which can be bisphenol A diglycidyl ether (BADGE) and monoethanolamine.

For some applications that may require a higher glass transition temperature (Tg), it is considered that BADGE can be replaced by an epoxy monomer with less mobility.

Such epoxy monomers can include fluorodiphenol diglycidyl ether or 1.6 diepoxy naphthalene.

Furthermore, it is contemplated that, where fire resistance is desired, BADGE can be replaced by a brominated bisphenol A epoxy resin.

Alternatively, the resettable epoxy materials disclosed in this document can also be known as poly (hydroxyaminoether) (PHAE), as illustrated in US Patents 5,644,472; US5275853; USS401814 and US5464924, all of which are incorporated herein by reference for all purposes.

These polyethers can be prepared by the reaction of a diglycidyl ether of aromatic dihydric compounds, such as bisphenol A diglycidyl ether, or a poly (alkylene oxide) functionalized with diepoxy or a mixture of them with a primary amine or a secondary diamine or a poly functionalized with monoamine (alkylene oxide) or a mixture thereof.

Such a material generally has a relatively high flexural strength and modulus - often much higher than typical polyolefins (ie polyethylene and polypropylene) - and has the added benefit of being melt processable at temperatures of 150 to 200ºC.

Although other epoxide-containing fractions may be employed, as taught in Patent US6011111 (incorporated by reference; see, for example, Cols. 5-6) and WO 98/14498 (incorporated by reference; see, for example, page 8) such fractions they may include at least one monofunctional epoxide and / or a difunctional epoxide (“diepoxide”). An example of a diepoxide that can be used in the teachings includes a dihydric phenol diglycidyl ether (for example, resorcinol, biphenol or bisphenol A). Any fraction containing epoxide here can be an aliphatic and / or aromatic epoxide.

[024] Other examples of illustrative materials, functional species and diepoxides are described in USS115075; US4438254; and WO 98/14498 (see for example, pages 3-8) together with illustrative synthetic conditions, all of which are incorporated by reference (see patent US3317471 and US4647648, also incorporated by reference). Examples of such materials can also be found, without limitation, in paragraphs 15-25 of Published Patent Application US20070270515 (Chmielewski et al), incorporated by reference for all purposes.

[025] The formation of resettable epoxy materials in the desired monofilament format may require particularly high temperatures during the extrusion process. Therefore, it may be necessary to reduce the viscosity of the RER, as heat tends to increase viscosity to an undesirable range. This can be achieved by modifying the ratio of the bifunctional epoxy resin and primary amine so that the length of the molecular chain is reduced, thereby reducing viscosity.

[026] As used in this document, unless appropriate. These are just examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value listed should be considered expressly stated in this application in a similar manner. As can be seen, the teaching of quantities expressed as "parts by weight" also includes the same ranges expressed in terms of percentage by weight. Thus, an expression on a strip in terms of "'xX' parts by weight of the resulting polymer blend composition" also contemplates teaching bands of the same recited amount of "x" as a percentage by weight of the resulting polymer blend composition. "

[028] Unless otherwise specified, all ranges include terminals and all numbers between terminals. The use of "about" or "approximately" in connection with an interval applies to both ends of the interval. Thus, "about 20 to 30" is intended to cover "about 20 to about 30", including at least the specified end points.

[029] Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term "consisting essentially of describing a combination should include the identified elements, ingredients, components or steps, and such other ingredient elements, components or steps that do not materially affect the basic and new characteristics of the combination. The use of the terms" comprising "or "including" to describe combinations of elements, ingredients, components or steps in this document also contemplates modalities that consist of, or consist essentially of, elements, ingredients, components or steps.

[030] Elements, ingredients, components or steps in the plural can be provided by a single element, ingredient, component or single integrated step. Alternatively, a single integrated element, ingredient, component or step can be divided into several separate elements, ingredients, components or steps. The disclosure of "one" to describe an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.

[031] It is understood that the description above is intended to be illustrative and not restrictive. Many modalities, as well as many applications in addition to the examples provided, will be evident to those skilled in the art after reading the above description. The scope of the invention must, therefore, be determined not with reference to the above description, but instead, it must be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of the matter disclosed in this document is not a waiver of such matter, nor should it be considered that the inventors did not consider such matter to be part of the disclosed inventive matter.

Claims (28)

REINVENTIONS 1. The method characterized by the fact that it comprises: - forming an epoxy resin material that can be reformed in a monofilament having a denier of about 50 to about 4000 and a glass transition temperature below about 200ºC; - load one or more monofilaments on a spool; - co-weave one or more monofilaments with a reinforcement fiber to form a woven material, the reinforcement fiber having a glass transition temperature above 200ºC; - heating the woven material to form a compound at a temperature so that only one or more monofilaments soften, but the reinforcing fiber does not. 2. Method according to claim 1, characterized by the fact that the reinforcing fiber is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, polymeric fibers, metallic fibers and their combinations. Method according to claim 1 or claim 2, characterized by the fact that the resulting composite has a constant thickness as a result of the failure of the structural fibers to soften. Method according to any one of claims 1 to 3, characterized in that the resulting compound is used to form an armature material. Method according to any one of claims 1 to 4, characterized in that the resulting compound is used to form a helmet, a jacket, a shield or the like. Method according to any one of claims 1 to 5, characterized in that one or more denier or diameter of the monofilament is substantially similar to that of the reinforcing fiber. Method according to any one of claims 1 to 6, characterized by the fact that one or more denier or diameter of the monofilament is smaller than that of the reinforcing fiber. Method according to any one of claims 1 to 6, characterized by the fact that one or more denier or monofilament diameter is greater than that of the reinforcing fiber. Method according to any one of claims 1 to 8, characterized in that the resulting composite is an epoxy laminate. Method according to any one of claims 1 to 9, characterized in that the resulting composite is substantially free of any film layer. 11. Method according to any one of claims 1 to 10, characterized in that the method is substantially free of surface treatment to form class A surfaces. 12. Method according to any one of claims 8 to 11, characterized in that the resulting compound can be painted. 13. Method according to any one of claims 1 to 12, characterized in that the monofilament develops adhesive properties after softening. 14. Method according to any one of claims 1 to 13, characterized in that the useful life of the monofilament is at least about 3 months, at least about 6 months, at least about 1 year, or even at least about 5 years. 15. Method according to any one of claims 1 to 14, characterized in that the monofilament is recyclable. 16. Method according to any one of claims 1 to 15, characterized in that the resulting composite is collapsible. 17. Monofilament characterized by the fact that it has a denier of about 200-3200 and a glass transition temperature below about 200ºC and comprising a resealable epoxy resin material. 18. Monofilament according to claim 17, characterized by the fact that the resettable epoxy resin material is formed as a reaction product of a bifunctional epoxy resin and a primary amine. 19. Monofilament according to claims 17 or 18, characterized by the fact that the reformable epoxy resin material is formed as a reaction product of bisphenol A diglycidyl ether (BADGE) and monoethanolamine. 20. Monofilament according to any one of claims 17 to 19, characterized in that the monofilament is collapsible. 21. Monofilament according to any one of claims 17 to 19, characterized in that the monofilament is woven to form a product that can be folded. 22. Product of fibrous material formed from the monofilament, according to any one of claims 17 to 21, characterized by the fact that the fabric with one or more reinforcement fibers having a glass transition temperature of 200ºC or higher. 23. The fibrous material product according to claim 22, characterized by the fact that the product is foldable. 24. Ballistic composite material characterized by the fact that it includes one or more layers comprising a woven material formed from a plurality of resettable epoxy resin monofilaments and a plurality of reinforcement fibers. 25. Composite material according to claim 24, characterized by the fact that the material is used to form a helmet. 26. Composite material according to claim 24, characterized by the fact that the material is used to form body armor. 27. Composite material according to claim 24, characterized in that the material is used to form a shield. 28. Composite material according to claim 24, characterized by the fact that the composite is formed in a press heated to a temperature below about 200ºC.