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NASA Technical Reports Server (NTRS) 20170001263: Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof PDF

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Preview NASA Technical Reports Server (NTRS) 20170001263: Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof

1111111111111111111inmuuu~ (12) United States Patent (io) Patent No.: US 9,550,911 B2 Wohl et al. (45) Date of Patent: Jan. 24, 2017 (54) FLUORINATED ALKYL ETHER EPDXY C08K 3/36 (2006.01) RESIN COMPOSITIONS AND C08G 59/06 (2006.01) APPLICATIONS THEREOF C08G 59/14 (2006.01) C08G 59/50 (2006.01) (71) Applicant: The United States of America C08K 3130 (2006.01) represented by the Administrator of (52) U.S. Cl. the National Aeronautics and Space CPC ........... C09D 163/00 (2013.01); C08G 59/066 Administration, Washington, DC (US) (2013.01); C08G 59/1438 (2013.01); C08G 59/504 (2013.01); C08G 2650150 (2013.01); (72) Inventors: Christopher J. Wohl, Portsmouth, VA C08K 200313009 (2013.01); YIOT 428130 (US); John W. Connell, Yorktown, VA (2015.01); YIOT 428/31511 (2015.04); YIOT (US); Joseph G. Smith, Smithfield, VA 428131529 (2015.04) (US); Emilie J. Siochi, Newport News, (58) Field of Classification Search VA (US); John M. Gardner, Newport CPC . C08G 59/066; C08G 59/1438; C08G 59/504; News, VA (US); Frank M. Palmieri, C08G 2650/50; C09D 163/00; C08K Hampton, VA (US) 2003/3009; YIOT 428/30; YIOT 428/31511; YIOT 428/31529 (73) Assignee: The United States of America as USPC ........ 428/421, 408, 413, 418; 427/299, 386, represented by the Administrtor of 427/512; 523/400; 525/533 the National Aeronautics and Space See application file for complete search history. Administration, Washington, DC (US) (56) References Cited (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 391 days. PUBLICATIONS Wohl et al. (Copolyimide Surface Modifying Agents for Particle (21) Appl. No.: 14/310,997 Adhesion Mitigation, 242nd American Chemical Society National (22) Filed: Jun. 20, 2014 Meeting and Exposition; Aug. 28-Sep. 1, 2011; Denver, CO; United States).* (65) Prior Publication Data * cited by examiner US 2015/0344748 Al Dec. 3, 2015 Primary Examiner Ling Choi Related U.S. Application Data Assistant Examiner Chun-Cheng Wang (74) Attorney, Agent, or Firm Jennifer L. Riley (60) Provisional application No. 61/984,528, filed on Apr. 25, 2014, provisional application No. 61/868,267, (57) ABSTRACT filed on Aug. 21, 2013. Epoxy resin compositions prepared using amino terminated (51) Int. Cl. fluoro alkyl ethers. The epoxy resin compositions exhibit C09J 163/00 (2006.01) low surface adhesion properties making them useful as B05D 3/02 (2006.01) coatings, paints, moldings, adhesives, and fiber reinforced C08K 3/00 (2006.01) composites. B05D 5/08 (2006.01) C09D 163/00 (2006.01) 20 Claims, 1 Drawing Sheet U.R. Patent Jan.24,2017 US 9,330,911 G2 +2 2. ®` +y ƒ» +5 ++ +# +a +w +& +! ~ +7 *! \ 4» 2 »» «a !+a °°\ » ; ® +k m\ a 0-4 o» \ G G G Aerial Ccs U ,mm2 US 9,550,911 B2 2 FLUORINATED ALKYL ETHER EPDXY all oft he requirements needed for laminar flow maintenance. RESIN COMPOSITIONS AND Such an approach could involve modification of a material's APPLICATIONS THEREOF surface energy either chemically or topographically or by using combinations thereof. CROSS-REFERENCE TO RELATED 5 Any surface material needs to meet the requirements of its APPLICATIONS application. High performance polymeric materials have been developed to address various requirements for This patent application claims the benefit of and priority mechanical, thermal, and optical properties. Modification of to 61/868,267, filed on Aug. 21, 2013 and 61/984,528, filed the chemical constituency of these polymeric materials can on Apr. 25, 2014, the contents of each of the foregoing 10 alter their properties. Often there is a trade-off, for example, applications is hereby incorporated by reference in its increasing the stiffness or modulus of a polymeric material entirety. typically comes with a sacrifice in toughness. Thus, modi- fication of high performance polymeric materials is often STATEMENT REGARDING FEDERALLY hampered due to degradation of the desired characteristic SPONSORED RESEARCH OR DEVELOPMENT 15 properties. Modifying a polymeric material to change prop- erties of the surface is problematic as addition of sufficient The invention described herein was made in the perfor- modifier to the bulk chemical composition to achieve the mance of work under a NASA contract and by employees of desired surface modification could also result in the dimi- the United States Government and is subject to the provi- sions of Public Law 96-517 (35 U.S.C. §202) and may be 20 nution of important properties of the polymeric material. If manufactured and used by or for the Government for gov- the modifier is well dispersed within the polymer matrix, a ernmental purposes without the payment of any royalties majority of the modifier will be contained within the interior thereon or therefore. In accordance with 35 U.S.C. §202, the of the polymeric structure and will not contribute to modi- contractor elected not to retain title. fication of the polymer or coating surface. This is of greater 25 consequence if the modifier is expensive, provides no FIELD OF THE INVENTION advantage, or diminishes bulk properties. Polymeric mate- rials with low adhesion surface properties have been dem- The present invention generally relates to epoxy resin onstrated to be effective in a wide variety of applications. compositions prepared using fluorinated alkyl ether oligom- Low surface energy polymeric materials, i.e., those exhib- ers or polymers terminated with amino groups and their 30 iting a high water contact angle, have been used to reduce applications as low surface energy paints, films, coatings, biofouling, water and ice adhesion, and biofilm formation; to moldings, fiber reinforced composites, foams, adhesives, improve oxidation, corrosion and stain resistance; to mini- and the like. mize dust adhesion; and to modify the performance of microfluidic systems and biomedical devices. The ability to BACKGROUND OF THE INVENTION 35 selectively modify the surface energy of high performance polymeric materials without sacrificing their superior It has long been known that a wide range of surfaces on mechanical, thermal, or optical properties would be of aircraft, automobiles, ship hulls, oil drilling rigs, water significant utility. intakes in power plants, and the like could benefit from A number of approaches have been suggested to provide engineered coatings that minimize drag and adhesion of a 40 polymeric materials with low surface energy. Some of the variety of substances such as insect residue, dirt, ice, bio- most well-known polymeric materials having low surface organisms, deposits such as mineral deposits, etc. For energy are fluorinated, aliphatic polymers such as those example,f uture designs of aircraft want to take advantage of available under the trade name TEFLON®. The presence of laminar flow to improve fuel efficiency. Studies have shown both aliphatic carbon species and fluorine atoms contributes that for long haul flights, increases in fuel efficiency as high 45 to the low surface energy of this class of materials. These as 12% are possible with hybrid laminar flow control and polymeric materials have an approximate homogeneous natural laminar flow (Kirchner, M. E. NASA CP-2487, composition. These polymeric materials do not use a con- 1987, Part 1, pp. 24-44). In order to maintain laminar flow trolled modification and thus cannot be readily tailored for operationally, however, the aerodynamic surfaces must be the introduction of further surface features. Moreover, they relatively smooth and not allow accumulation of any sub- 50 are difficult to adhere to substrates, and generally the poly- stances that can interrupt laminar flow, such as insect residue mer is available only as a powder and must be sintered or or ice. In particular, a number of approaches have been melted to coat the desired surface. With these difficulties in attempted to reduce insect residue adhesion to aircraft coating surfaces, delamination can become an issue during surfaces such as, mechanical scrapers, sacrificial coatings or use. Another approach is to vapor deposit highly fluorinated covers, and continual wetting of the surfaces during take-off 55 carbonaceous materials to various substrates. and landing. All of these suffer from problems such as Another approach to provide low surface energy poly- adding significant weight, complexity or were simply meric materials is to incorporate surface modifying agents impractical in the industry (Coleman, W. S. `Boundary into the materials. These surface modifying agents are Layer and Flow Control", ed. G. V. Lachman, Pergamon thermodynamically driven to the surface of the polymeric Press, 1961, pp. 682-747. Lachman, G. V. Ministry of 60 material due to more favorable interactions at the air inter- Aviation Aeronautical Research Council, A.R.C. Technical face as compared with interactions within the bulk poly- Report, 1960, C.P. No. 484). Passive strategies for minimiz- meric matrix. ing fouling or contamination of surfaces are beneficial Fluorine-containing oxetane derivatives have been used especially in environments where active mitigation of the extensively as surface modification agents for modification fouling or contamination is impractical or impossible. One 65 of urethanes. See, for instance, Malik, et al., United States approach with promise has been the use of coatings, how- patent application publication No. US 2004/0087759. ever, no coatings developed to date have been able to satisfy Omnova Solutions Inc. offers a family of hydroxyl termi- US 9,550,911 B2 3 4 nated oxetane-derived oligomers under the trade name polymer or oligomer( ATPAE). The amino end groups of the POLYFOX® fluorochemicals. ATPAE can react with the epoxide groups and the fluorine- Epoxy is a term used for both the basic component and the containing segments of the ATPAE are available to migrate cured end product of epoxy resins, as well as a generic name to the exterior surface of the epoxy resin during cure such for the epoxide functional group. Epoxy resins, also known 5 that low surface energies are exhibited. as polyepoxides, are a class of reactive monomers, prepoly- Unique epoxy compositions were prepared from the mers and polymers which contain epoxide groups. Epoxy ATPAEs that had unexpected combination of bulk and resins may be reacted (cross-linked) either with themselves surface properties making them useful in aircraft coating, through catalytic homopolymerization, or with a wide range paint, adhesive, and composite formulations. of co-reactants including polyfunctional amines, acids, 10 It is an object of the present invention to provide fluori- anhydrides, phenols, alcohols, and thiols. These co-reactants nated alkyl ether modified epoxy compositions. are often referred to as hardeners or curatives, and the It is an object of the present invention to provide a cross-linking reaction is commonly referred to as curing. synthetic method for the preparation of fluorinated alkyl Reaction of polyepoxides with themselves or with polyfunc- tional hardeners forms a thermosetting polymer, often with 15 modified ether epoxy compositions. It is an object of this invention to provide coating, paint, high mechanical properties and temperature and chemical adhesive and matrix resin compositions comprised of the resistance. The range of chemistry and property combina- fluorinated alkyl ether epoxy compositions. tions in epoxies is extensive, consequently a diverse array of epoxy formulations are available. Thus they have a wide It is an object of this invention to provide coating, paint, range of applications such as coatings and paints, fiber- 20 adhesive and matrix resin compositions comprised of the reinforced composites, and functional and structural adhe- fluorinated alkyl ether epoxy compositions that exhibit good sives. adhesion to a variety of substrates while simultaneously Epoxy resins are among the most important industrial minimizing adhesion to the air surface of a variety of polymers in the world and are used in large quantities in the biological agents, organic and inorganic contaminants, and production of adhesives, paints and coatings, and matrix 25 surface particle contamination. The fluorinated alky ether resins. The core substrate in the production of epoxy resins moieties may migrate to the surface resulting in a polymer may include 2,2-bis(4-hydroxyphenyl)isopropylidiene (his- matrix that is chemically anisotropic relative to the thickness phenol A). The main monomer used in the epoxy resin direction. industry is the diglycidyl ether of bisphenol A, 2,2-Bis(4- According to one embodiment, the present invention glycidyloxyphenyl)propane (DGEBA), which represents 30 provides a composition including at least one epoxy resin, at more than 75% of the resin used in industrial applications. least one fluorinated alkyl ether, and, optionally, at least one 2,2-Bis(4-glycidyloxyphenyl)propane is usually prepared curing agent. from 2,2-Bis(4-hydroxyphenyl)isopropylidiene (bisphenol Suitable epoxy resin may include resins containing at A)a nd epichlorohydrin using a strong base such as sodium least one glycidyl group, alicyclic epoxy group, or a similar hydroxide ether. DGEBA resins normally contain some 35 epoxy group (i.e., oxirane or ethoxyline group). In certain distribution of molecular weight and exhibit a viscosity in embodiments, the epoxy resin may have two or more epoxy the range of 5-15 Pascal-second at 25° C. Alternative groups. Such epoxy resins are well known in the art and synthetic methods to prepare DGEBA have been developed include, but are not limited to, novolac-type epoxy resin, such as allylating bisphenol A followed by epoxidization. Another common epoxy is N,N,N',N'-tetraglycidyl-4,4'- 40 cresol-novolac epoxy resin, triphenolalkane-type epoxy methylenedianiline (TGMDA) prepared from 4,4'-methyl- resin, aralkyl-type epoxy resin, aralkyl-type epoxy resin enedianiline and epichlorohydrin using a strong base. having a biphenyl skeleton, biphenyl-type epoxy resin, TGMDA epoxies are characterized by high cross-link den- dicyclopentadiene-type epoxy resin, heterocyclic-type sities, which results in a high modulus of elasticity and a epoxy resin, epoxy resin containing a naphthalene ring, a high glass transition temperature. Aerospace structural 45 bisphenol-A type epoxy compound, a bisphenol-F type epoxy matrix resins are typically based on TGMDA. epoxy compound, stilbene-type epoxy resin, trimethylol- Accordingly, a desire exists to provide a polymeric mate- propane type epoxy resin, terpene-modified epoxy resin, rial that has the mechanical, thermal, chemical, and optical linear aliphatic epoxy resin obtained by oxidizing olefin properties associated with epoxies yet achieve a low energy bonds with peracetic acid or a similar peracid, alicyclic surface. 50 epoxy resin, sulfur-containing epoxy resin, and any combi- nation of the foregoing. In some embodiments, the epoxy SUMMARY OF THE INVENTION resin may be composed of two or more epoxy resins of any of the aforementioned types. In particular embodiments, the In view of the above discussion, there is a need for epoxy epoxy resins may be aralkyl-type epoxy resins, such as compositions that can provide the desirable bulk mechanical 55 epoxy resins derived from bisphenol A or 4,4'-methylene- properties of conventional coatings, adhesives or structural dianiline (MDA). The epoxy may also contain one or more matrix resins while simultaneously exhibiting surface prop- additional components such as, for example, a benzoxazine erties that minimize or mitigate surface fouling. Therefore, compound or resin, and in some embodiments, the fluori- epoxy compositions to satisfy this need are disclosed in the nated alkyl ether diamino terminated oligomers or polymers instant invention. 60 may be used as modifiers, chain extenders or crosslinkers for In accordance with this invention, compositions compris- epoxy resins, or epoxy hardeners in epoxy resin polymer ing fluorinated alkyl ether epoxy resins are provided that can compositions. possess the mechanical, thermal, chemical, and/or optical In the way of an overview, the fluorinated alkyl ethers properties associated with epoxies yet achieve a low energy include those containing divalent radicals of a polymer or surface (e.g., about 25 mN/m or less). By this invention, 65 oligomer derived from a fluorine-containing oxetane, pref- fluorinated alkyl ether epoxy resins are prepared using a erably derived from oxetanes containing a perfluorinated minor amount of amino terminated perfluorinated alkyl ether carbon on a substituent on the beta carbon of the oxetane. US 9,550,911 B2 5 T The ATPAEs utilized in the invention can be represented There are no particular restrictions on the hardener or by formula (I): curing agent. Specific examples of hardeners that can be used include 4,4'-methylenedianiline (MDA), various iso- (E)YR'—C(O)—O [CHZ—CRZR3—CHZ-0lm—C mers of diaminodiphenylsulfone (DDS), various isomers of (0) R'(E)Y M 5 diaminodiphenylether (DDE), imidazole, hexamethylenedi- wherein: amine, polyamidoamine, dicyan diamide, phenol novolak, E is predominately NHz, and any combinations thereof. In particular, from the stand- y is 1, point of reaction stability, amine-based hardeners and phe- Ri is aliphatic or aromatic hydrocarbon moiety of 1 to 10 nol-based hardeners are preferred, with amine-based hard- carbon atoms, preferably Ri is a divalent phenyl group; io eners being particularly preferred. In some cases, it is R2 is H, F, or alkyl of 1 to 6 carbon atoms, and preferable to use an imidazole that will serve as the epoxy preferably is alkyl of 1 to 3 carbon atoms, and most often resin polymerization catalyst in conjunction with a hardener. methyl; A curing accelerator may be used in conjunction as neces- R3 is F, R4H( -a)Fa Rs O R4H( -a)Fa, and sary with these hardeners. O R4H( -a)Fa, wherein R4 is an alkyl or ether moiety of 15 In some embodiments, the epoxy compositions may fur- 1 to 30 carbons, R5 is an alkyl moiety of 1 to 30 carbons, a ther include additional components such as, but not limited is an integer of 3 to n, and n is twice the number of carbon to, fillers (e.g., silica, molybdenum disulfide, iron oxide, atoms in the alkyl moiety plus 1; and inorganic oxides), chopped or continuous fibers, metal m is between 4 to 500, preferably between about 6 and 100. fibers, aramid fibers, carbon fibers, ceramic fibers, surfac- Preferably, the omega carbon of R4 has three fluoride 20 tants, organic binders, polymeric binders, crosslinking substituents. Preferably, R5 is MHz O C(X)z CF3, agents, diluents, coupling agents, thermal stability agents wherein X is H or F. such as boron nitride, boron nitride nanosheets, nanorib- Preferred oligomers are represented by formula (II): bons, and nanomeshes, boron nitride nanotubes, flame retar- dant agents such as phosphates, phosphinates and phospho- (E)YRi—C(O)—O-[Q]_ C(0) R'(E)Y (1I) 25 nates, and oligomers or polymers thereof, anti-dripping agents such as fluorinated polyolefins, silicones, and lubri- wherein: cants, mold release agents such as pentaerythritol tetrastear- E is predominately NHz, ate, nucleating agents, anti-static agents such as conductive y is 1, blacks, carbon nanotubes, graphite, graphene, oxidized gra- Ri is aliphatic or aromatic hydrocarbon moiety of 1 to 10 30 phene, and organic antistatics such as polyalkylene ethers, carbon atoms, and preferably is alkyl of 1 to 3 carbon atoms, alkylsulfonates, perfluorosulfonic acid, perfluorobutane and most often methyl; sulfinic acid potassium salt, and polyamide-containing poly- Q is derived from the oligomerization of an oxetane mers, catalysts, colorants, inks, dyes, antioxidants, UV sta- monomer bilizers, and the like and any combinations of the foregoing wherein at least 40 mole percent of the oxetane monomer is 35 additional components. In some embodiments, these addi- substituted at the beta carbon with at least one substituent tional components may or may not chemically react with the containing at least one perfluorinated carbon atom; and epoxy and become chemically incorporated into the com- m is between 4 to 500, preferably between about 6 and 100. position. The substituted oxetane monomer from which Q is In such embodiments, the one or more additional com- derived can be represented by formula (III): 40 ponents or additives may make up from about 0.01 wt.% to about 50 wt. % based on the total composition. In other embodiments, additional components such as glass fiber, carbon fiber, organic fiber, ceramic fiber or other fillers may /C be provided at much higher concentrations of up to about 70 R3R4C\ % 45 volume (vol.) %. For example, in some embodiments the CHz novel epoxy compositions may include up to about 70 vol. % glass fiber, carbon fiber, organic fiber and/or ceramic wherein: fiber, and in other embodiments, they may include from R3 is F, R4H( -a)F RS O R4H( -a)Fa, and about 5 vol. % to about 70 vol. %,f rom about 10 vol. % to O R4H( -a)Fa, wherein R4 is an alkyl or ether moiety of 5o about 60 vol. %,o r about 20 vol. % to about 50 vol.% glass 1 to 30 carbons, and preferably is alkyl of 1 to 3 carbon fiber, carbon fiber, organic fiber and/or ceramic fiber. atoms, and most often methyl, R5 is an alkyl moiety of 1 to For example, in some embodiments, the epoxy composi- 30 carbons, a is an integer of 3 to n, and n is twice the tions of the invention may be used as coatings on plastics, number of carbon atoms in the alkyl moiety plus 1. metals, glass, carbon, ceramic, or fiber reinforced compos- In some embodiments, the compositions may contain an 55 ites or wood products which can be in a variety of forms, for epoxy, an amino terminated fluorinated alkyl ether oligomer example as a fiber, woven mat, nonwoven mat, cloth, or polymer, and a curing agent. Suitable curing agents may broadgood, fabric, molding, laminate, foam, extruded shape be any monomers, oligomers, copolymers and/or co-oligom- or the like, and in other embodiments, the epoxy composi- ers that contain one or more functional groups that react with tions of the invention can be used to fabricate coatings, the epoxide ring system. These functional groups may 60 free-standing films, fibers, foams, molded articles, adhesive include but are not limited to amines, phenols, anhydrides, formulations and fiber reinforced composites. In some thiols, alcohols, organic carboxylic acids and salts, acyl embodiments, the epoxy compositions of the invention can chlorides, aldehydes, ketones, Grignard reagents, water, be used to formulate paints or coatings. In some embodi- sodium hydroxide, inorganic acids and their salts, or any ments, the epoxy compositions of the invention can be used combination thereof. The groups may be present in a ter- 65 to fabricate adhesive bonds between one or more substrates. minal, pendant, or backbone configuration or any combina- The novel epoxy compositions of the invention, due to tion thereof. their unique morphology, may exhibit outstanding adhesion US 9,550,911 B2 7 8 to a variety of substrates while simultaneously having sur- ally, one or more curing agents, and, optionally, one or more face properties that resist adhesion of a variety of materials additional components. The epoxy composition may include that come into contact with the surface exposed to the air. In a reaction product of the one or more epoxy resins and the addition, the epoxy compositions comprised of the fluori- one or more amino terminated fluorinated alkyl ether oli- nated alkyl ether oligomers and polymers exhibit good 5 gomers or polymers. processability by a variety of techniques commonly used in Epoxy Resins) the fabrication of films, coatings, foams, moldings, adhe- Any epoxy resin can be used for the purpose(s) of the sives, and composites making these materials useful in invention provided that the resin contains at least one applications, for example, in the aerospace, automotive, glycidyl group, alicyclic epoxy group, and/or a similar medical, nautical, preservation/restoration, energy harvest- io epoxy group (e.g., oxirane or ethoxyline group). Such epoxy ing, desalination, water treatment, rail and construction resins are well known in the art and include, but are not sectors that require low adhesion surfaces. In addition, these limited to, novolac-type epoxy resin, cresol-novolac epoxy articles are well suited for a variety of applications that resin, triphenolalkane-type epoxy resin, aralkyl-type epoxy require the low energy surface properties while maintaining resin, aralkyl-type epoxy resin having a biphenyl skeleton, bulk properties consistent with those of cured functional and 15 biphenyl-type epoxy resin, dicyclopentadiene-type epoxy structural epoxy resins. resin, heterocyclic-type epoxy resin, epoxy resin containing a naphthalene ring, a bisphenol-A type epoxy compound, a BRIEF DESCRIPTION OF DRAWING bisphenol-F type epoxy compound, stilbene-type epoxy resin, trimethylol- propane type epoxy resin, terpene-modi- FIG. 1 depicts a graphical representation of the results of 20 lied epoxy resin, linear aliphatic epoxy resin obtained by aerial coverage on the x-axis and residue height on the y-axis oxidizing olefin bonds with peracetic acid or a similar presented in Table 4 and described in the Examples. peracid, alicyclic epoxy resin, sulfur-containing epoxy resin, and any combinations of one or more of the foregoing. DETAILED DESCRIPTION OF THE In some embodiments, the epoxy resin may have two or INVENTION 25 more epoxy groups. In other embodiments, the epoxy resin is a di-functional epoxy resin including two or more epoxy For purposes of description herein, the terms "upper," groups. In still further embodiments, the epoxy resin may be "lower,"" right," "left," "rear," "front," "vertical," "horizon- composed of two or more epoxy resins of any of the tal," and derivatives thereof shall relate to the invention as aforementioned types. In particular embodiments, the epoxy oriented in FIG. 1. However, it is to be understood that the 3o resins may include aralkyl-type epoxy resins, such as epoxy invention may assume various alternative orientations and resins derived from bisphenol A and/or 4,4'-methylenediani- step sequences, except where expressly specified to the line (e.g., a reaction product of epichlorohydrin and bisphe- contrary. It is also to be understood that the specific devices nol A). In some embodiments, the epoxy resin comprises and processes illustrated in the attached drawings, and 2,2-bis(4-hydroxyphenyl)isopropylidiene (bisphenol A). described in the following specification, are simply exem- 35 The epoxide equivalent weight (g/eq) of the epoxy resin plary embodiments of the inventive concepts defined in the may range from about 100 to about 1000, about 100 to about appended claims. Hence, specific dimensions and other 500, about 100 to about 300, or about 100 to about 200. physical characteristics relating to the embodiments dis- Epoxide equivalent weight refers to the number average closed herein are not to be considered as limiting, unless the molecular weight of the epoxide moiety in grams per claims expressly state otherwise. 40 equivalent (g/eq) divided by the average number of epoxide The present invention pertains to compositions compris- groups present in the molecule. Preferably, the epoxide ing fluorinated alkyl ether epoxy resins and their applica- equivalent weight ranges from about 180 to about 200, or tions. The compositions are prepared by reacting amino about 182 to about 192. The epoxide percentage oft he epoxy terminated fluoro alkyl ether oligomers or polymers with resin may range from about 5% to about 50%, about 10% to any epoxy compound, oligomer or polymer. Other com- 45 30%, about 20% to about 25%, about 22% to about 24%, or pounds, chemicals, components, materials and additives about 22.4% to about 23.6%. may be included in these compositions. These compositions The epoxy may also contain one or more additional exhibit a unique and unexpected combination of properties components such as, for example, a benzoxazine compound in that the surface properties are much different from those or resin and in some embodiments, the novel fluorinated of the bulk resin. This unique combination of properties 5o alkyl ether diamino terminated oligomers or polymers may enables applications that require high mechanical and adhe- be used as modifiers, chain extenders or crosslinkers for sion properties of the bulk resin, but low adhesion properties epoxy resins, or epoxy hardeners in epoxy resin polymer on the surface. compositions. Preferred epoxies are those derived from As used herein and in the claims, the terms "comprising" 2,2-bis(4-hydroxyphenyl)isopropylidiene (bisphenol A)a nd and "including" are inclusive or open-ended and do not 55 4,4'-methylenedianiline (MDA), e.g., DGEBA and exclude additional unrecited elements, compositional com- TGMDA. ponents, or method steps. Accordingly, the terms "compris- The epoxy resin may be of any suitable form and may be ing" and "including" encompass the more restrictive terms curable under any suitable conditions. Preferably, the epoxy "consisting essentially of and "consisting of." Unless speci- resin is a liquid epoxy resin and may be effectively cured at fied otherwise, all values provided herein include up to and 60 ambient temperatures with a wide variety of curing agents. including the endpoints given, and the values of the con- Fluorinated Alkyl Ether(s) stituents or components oft he compositions are expressed in The fluorinated alkyl ethers of this invention are charac- weight percent or % by weight of each ingredient in the terized as containing divalent radicals of a polymer or composition. oligomer derived from a fluorine-containing oxetane, pref- According to one embodiment, the present invention 65 erably oxetanes containing a perfluorinated carbon on a includes an epoxy composition comprising one or more substituent on the beta carbon of the oxetane. The amine- epoxy resins, one or more fluorinated alkyl ethers, option- terminated alkyl ethers contain at least one fluorinated US 9,550,911 B2 9 10 pendant group with a degree of fluorination ranging from a Ri is aliphatic or aromatic hydrocarbon moiety of 1 to 10 single trifluoromethyl functionality up to a perfluorinated carbon atoms, and preferably is alkyl of 1 to 3 carbon atoms, butane moiety. The fluorinated pendant group generally and most often methyl; refers to any substituent that includes at least one fluorine Q is derived from the oligomerization of an oxetane atom. The fluorinated pendant group preferably includes 5 monomer, fluorinated alkyl groups. wherein at least 40 mole percent of the oxetane monomer The ATPAEs utilized in the invention can be represented is substituted at the beta carbon with at least one substituent by the formula (I): containing at least one perfluorinated carbon atom; and (E)yRi—C(O)—O [CHz—CR2R3—CHz-0lm—C m is between 4 to 500, preferably between about 6 and (0) R'(E)y M 10 100. wherein: The substituted oxetane monomer from which Q is E is predominately NH21 meaning the moiety is an amine mostly comprised of NH2, but which optionally derived can be represented by the formula (III): contains a minor amount of another moiety, y is 1, 15 Ri is aliphatic or aromatic hydrocarbon moiety of 1 to 10 /C~ carbon atoms, preferably Ri is a divalent phenyl group; R3R4C\ R2 is H, F, or alkyl of 1 to 6 carbon atoms, and preferably is alkyl of 1 to 3 carbon atoms, and most often CH2 methyl; 20 R3 is F, R4H(n-a)F Rs O R4H(n-a)Fa, and wherein: O R4H(n-a)F wherein R4 is an alkyl or ether moiety of R3 is F, R4H(n-,)Fa, Rs O R4H(n-a)Fa, and 1 to 30 carbons, Rs is an alkyl moiety of 1 to 30 carbons, a O R4H(n-a)Fa, wherein R4 is an alkyl or ether moiety of is an integer of 3 to n, and n is twice the number of carbon 1 to 30 carbons, and preferably is alkyl of 1 to 3 carbon atoms in the alkyl moiety plus 1; and 25 atoms, and most often methyl, Rs is an alkyl moiety of 1 to m is between 4 to 500, preferably between about 6 and 30 carbons, a is an integer of 3 to n, and n is twice the 100. number of carbon atoms in the alkyl moiety plus 1. Preferably the omega carbon of R4 has three fluoride In some embodiments, more than one fluorinated alkyl substituents. Preferably, Rs is NH2 O C(X)2 CF3, ether oligomer or polymer may be used to prepare the epoxy wherein X is H or F. so composition. Suitable fluorinated alkyl ether oligomers and Preferred oligomers are represented by the formula (II): polymers terminated with amino groups are described in (E)yRi—C(O)—O-[Q]m C(0) R'(E)y (II) United States Publication No. 2012/0252968. wherein: In particular, the amino terminated fluorinated alkyl ether E is predominately NH21 oligomer or polymer may include one or more compounds y is 1, represented by formulas (IV), (V), (VI), and (VII): (IV) NH2 where x+y=6 to 20. (v) 0 H2N NH2 F3CF2CH2C where x+y=4 to 5. US 9,550,911 B2 11 12 (VI) NH2 F3C(F2C)3H2CH2C where x+y=6. (VII) 0 0 I \ 0 \ 0 0 o Y HZN / /0 /0 / NHZ F3CF2CH2C F3CF2CH2C where x+y=6 and z=33. 25 include aliphatic diamine such as trimethylenediamine, The amount of fluorinated alkyl ether oligomer or poly- tetramethylenediamine, pentamethylenediamine, hexameth- mer present in the final cured epoxy composition may range ylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4- from about 0.01 to 99% by weight. In particular, the amount trimethylhexamethylenediamine, octamethylenediamine and nonamethylenediamine; and an alicyclic diamine such of fluorinated alkyl ether oligomer or polymer may range 30 as bis(4-aminocyclohexyl)methane and bis(4-amino-3- from about 0.1 to 25%, about 0.1 to 10%, about 0.1 to 5%, methylcyclohexyl)methane; aromatic diamine, for example, about 0.5 to 5%, or about 1 to 5% by weight. phenylenediamine, diaminotoluene, 2,4-diaminomesitylene, The fluorinated alkyl ether oligomers and polymers con- 3,5-diethyl-2,6-diaminotoluene, xylylenediamine (in par- tain fluorocarbon moieties that enable the cured epoxy resin ticular, metaxylylenediamine, paraxylylenediamine), bis(2- to achieve low surface energy with a relatively low content 35 aminoethyl)benzene, biphenylenediamine, a diamine having of the fluorinated alkyl ether oligomers and polymers. a biphenyl backbone (e.g., 4,4'-diamino-3,3'-ethylbiphenyl), Curing Agent(s) adiamine having adiphenyl alkane backbone [e.g., diamino- In some embodiments, the compositions may contain an diphenylmethane, bis(4-amino-3-ethylphenyl)methane, his epoxy, an amino terminated fluorinated alkyl ether oligomer (4-amino-3-methylphenyl)methane, 3,3'-dichloro-4,4'-di- or polymer, and a curing agent. Suitable curing agents may 4o aminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane], be any monomers, oligomers, copolymers or co-oligomers bis(4-aminophenyl)ketone, bis(4-aminophenyl)sulfone, or that contain one or more functional groups that react with the 1,4-naphthalenediamine, and an N-substituted aromatic epoxy resin. diamine thereof; alicyclic diamine, such as 1,3-cyclopen- These functional groups may include, but are not limited tanediamine, 1,4-cyclohexanediamine, and bis(4-amino-3- to, amines, phenols, anhydrides, thiols, alcohols, organic 45 methylcyclohexyl)methane; an aliphatic amine, such as carboxylic acids and salts, acyl chlorides, aldehydes, trimethylenediamine, tetramethylenediamine, pentamethyl- ketones, Grignard reagents, water, sodium hydroxide, inor- enediamine, hexamethylenediamine, 2,2,4-trimethylhexam- ganic acids and their salts and any combinations thereof. The ethylenediamine, 2,4,4-trimethylhexamethylenediamine, groups may be present in a terminal, pendant or backbone and octamethylenediamine, and an N-substituted aliphatic configuration or any combinations thereof. 5o diamine thereof; and ether diamines, such as poly(alkylene There are no particular restrictions on the hardener or ether)diamines including poly(ethylene ether)diamine, poly curing agent. Specific examples of hardeners include 4,4'- (propylene ether)diamine, poly(tetramethylene ether)di- methylenedianiline (MDA), various isomers of diaminodi- amine; random or block copolymers of ethylene oxide and phenylsulfone (DDS), various isomers of diaminodipheny- propylene oxide including propylene oxide and poly(pro- lether (DDE), imidazole, hexamethylenediamine, 55 pylene oxide) terminated poly(ethylene ether)diamine, 4,4'- polyamidoamine, dicyan diamide, phenol novolak, and any oxydianaline; and aminated random or block copolymers of combinations thereof. In particular, from the standpoint of tetrahydrofuran with minor amounts of a second monomer reaction stability, amine-based hardeners and phenol-based such as ethylene oxide, propylene oxide, methyl tetrahydro- hardeners are preferred, with amine-based hardeners being furan, bis[4-(3-aminophenoxyl)phenyl]methane, bis[4-(4- particularly preferred. In some cases, it is preferable to use 6o aminophenoxyl)phenyl]methane, 1,1-bis[4-(3-aminophe- an imidazole that will serve as the epoxy resin polymeriza- noxyl)phenyl]e thane, 1,1-bis[4-(4-aminophenoxyl)phenyl] tion catalyst in conjunction with a hardener. A curing accel- ethane, 1,2- his[ 4-(3-aminophenoxyl)phenyl]ethane, 1,2-bis erator or catalyst may be used in conjunction as necessary [4-(4-aminophenoxyl)phenyl]ethane, 2,2-bis[4-(3- with these hardeners. The catalyst may be latent. aminophenoxyl)phenyl]propane, 2,2-bis[4-(4- A diamine curing agent may be aliphatic or aromatic and 65 aminophenoxyl)phenyl]propane, 2,2-bis[4-(3- includes diamines containing other hetero atoms. One or aminophenoxyl)phenyl]butane, 2,2-bis[ 4-(4- more other diamines may be used. Examples of diamines aminophenoxyl)phenyl]butane, 2,2-bis[4-(3- US 9,550,911 B2 13 14 aminophenoxyl)phenyl]- 1,1,1,3,3,3- hexafluoropropane, fiber, and in other embodiments, they may include from 2,2-bis[ 4-(4-aminophenoxyl)phenyl]- 1,1,1,3,3,3-hexafluo- about 5 vol. % to about 70 vol. %, about 10 vol. % to about ropropane, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4- 60 vol. %, or about 20 vol. % to about 50 vol.% glass fiber, aminophenoxy)biphenyl, bis[4-(3-aminophenoxyl)phenyl] carbon fiber, organic fiber and/or ceramic fiber. ketone, bis[4-(4-aminophenoxyl)phenyl]ketone, bis[4-(3- 5 Process of Making aminophenoxy)phenyl]s ulfide, bis[4-(4-aminophenoxyl) The epoxy copolymeric composition may be generated by phenyl]sulfide, bis[4-(3-aminophenoxyl)phenyl]sulfone, his mixing together the one or more epoxy resins with the one [4-(4-aminophenoxyl)phenyl]sulfone, and any or more amino terminated fluoro alkyl ether compounds and combinations thereof. other optional components. For example, the epoxy com- The amount of curing agent may be selected based upon io positions may be prepared by simply admixing the ingredi- the type and amount of epoxy resin selected. For example, ents in any desired order with sufficient mixing. The result- the curing agent may be present in ratios ranging from about ing mixture may be admixed until all the composition 1:1 to about 1:0.1, about 1:1 to about 1:0.2, about 1:1 to ingredients are substantially homogeneously blended. Mix- about 1:0.5, or about 1:1 to about 1:0.8 of epoxy to curing ing equipment can be operated in batch, semi-batch, or agent. 15 continuous mode. Examples of mixers include rotor-stator, Additional Component(s) microfluidizer, high pressure homogenizer, ultrasonic, In some embodiments, the epoxy compositions may fur- impinging jet, CowlesTM blade, planetary mixers, and melt ther optionally include additional components such as, but kneading devices such as extruders. not limited to, fillers (e.g., silica, molybdenum disulfide, iron The epoxy compositions may be prepared by reacting the oxide, inorganic oxides), chopped or continuous fibers, 20 amino terminated fluoro alkyl ether oligomers or polymers metal fibers, aramid fibers, carbon fibers, ceramic fibers, with any epoxy compound, oligomer, and/or polymer con- surfactants, organic binders, polymeric binders, crosslinking taining at least one glycidyl group, alicyclic epoxy group, agents, diluents, coupling agents, flame retardant agents oxirane group, or ethoxyline group. The epoxy composition such as phosphates, phosphinates, phosphonates, and oli- may comprise the reaction product of the epoxy resin with gomers or polymers thereof, anti-dripping agents such as 25 the amino terminated fluorinated alkyl ether oligomer or fluorinated polyolefins, silicones, and, lubricants, mold polymer where the amine reacts with the epoxy resin and the release agents such as pentaerythritol tetrastearate, nucleat- fluorinated pendant group migrates to the surface of the ing agents, anti-static agents such as conductive blacks, epoxy composition to provide for low surface energies (e.g., carbon nanotubes, graphite, graphene, oxidized graphene, about 25 mN/m or less). The epoxy resin and amino termi- and organic antistatics, such as polyalkylene ethers, alkyl- 3o nated fluoro alkyl ether may be reacted under any suitable sulfonates, perfluorosulfonic acid, perfluorobutane sulfinic conditions known in the art. acid potassium salt, and polyamide-containing polymers, If prepared for use as a coating, the epoxy compositions catalysts, colorants, inks, dyes, antioxidants, UV stabilizers, may be prepared and applied as a solvent-free powder and the like and any combinations of the foregoing addi- coating, as a substantially solvent-free hot melt coating, as tional components. 35 a substantially solvent-free liquid admixture, or the resins In the instance when fillers are present, the fillers may may be reduced in viscosity by dilution with one or more range in size from nanometers (nm) to micrometers (mm), solvents and applied as a liquid admixture. By way of for example, about 1 nm to about 10 mm. In particular, the example, the at least one epoxy resin, the at least one amino filler particles may range from about 1 to about 500 mu, terminated fluorinated alkyl ether oligomer or polymer, about 5 to about 100 nm, or about 7 to about 40 nm in size. 40 optionally, at least one curing agent; and optionally, addi- The fillers may also be of any suitable shape, e.g., spherical, tional components (e.g., fillers) may be dissolved in a cylindrical, platelet, and/or amorphous. solvent under agitation. Suitable solvents may include These additional components may be present to improve ketone containing solvents, such acetone, MEK (methyl the processability or manufacturability of the composition, ethyl ketone), cyclohexanone, DEK (diethyl ketone), MPK enhance composition aesthetics, and/or improve a particular 45 (methyl propyl ketone), MIBK (methyl iso-butyl ketone), functional property or characteristic of the coating compo- MAK (methyl amyl ketone), and the like. Preferably, the sition or the resultant cured compositions, such as adhesion solvent includes at least methyl ethyl ketone. In some to a substrate or adjacent composition. Each optional ingre- embodiments, the solvent is methyl ethyl ketone. If present, dient can be included in a sufficient amount to serve its the filler content of the solids component of the solution intended purpose, but preferably not in such an amount to 50 (e.g., for spraying) may range from about 5 to about 66 wt. adversely affect a coating composition or a cured coating % based on the total weight of the solution. resulting therefrom. The dissolved composition may be coated on a substrate. In some embodiments, the one or more additional com- The substrate may include any suitable substrate, such as ponents or additives may make up from about 0.01 wt.% to glass, ceramic, metal and alloys, polymers, carbon allo- about 50 wt.% based on the total composition. In particular, 55 tropes, inorganic oxides, and adhesive-backed materials. In when fillers, such as silica, molybdenum disulfide, iron some embodiments, the substrate is aluminum. In some oxide, inorganic oxides, and mixtures thereof, are used, the embodiments, the substrate is an adhesive-backed material. filler may be present in an amount of about 1 to about 40 wt. The coating can be applied to the substrate using any %, about 5 to about 40 wt. %, about 5 to about 30 wt. %, suitable procedure such as spray coating, roll coating, coil about 5 to about 20 wt. %,o r about 5 to about 10 wt.% based 60 coating, curtain coating, immersion coating, meniscus coat- on the total weight of the composition. In other embodi- ing, kiss coating, blade coating, knife coating, dip coating, ments, additional components such as glass fiber, carbon slot coating, slide coating, brushing, casting, spin coating, fiber, organic fiber, ceramic fiber and/or other fillers may be injection molding, and the like, as well as other types of provided at much higher concentrations up to about 70 pre-metered coating. Preferably, the coating is applied via volume (vol.) %. For example, in some embodiments the 65 spray coating. novel epoxy compositions may include up to about 70 vol. After applying the coating composition onto the substrate, % glass fiber, carbon fiber, organic fiber and/or ceramic the composition can be cured using a variety of processes, US 9,550,911 B2 15 16 including, for example, oven baking by either conventional epoxy compositions oft he invention can be used to fabricate or unconventional methods. In preferred embodiments, the coatings, free-standing films, fibers, foams, molded articles, epoxy composition is a thermal-cure coating composition. adhesive formulations, and fiber reinforced composites. The curing process may be performed in either discrete or Since the materials described herein are hydrophobic, they combined steps. The curing process may be performed 5 can also provide corrosion protection to a variety of surfaces thermally, as a result of UV-light exposure, may occur under that undergo electrochemical corrosion upon the ingress of ambient conditions, or may be any combination of these water. conditions. For example, the coated substrate can be dried at Due to the properties that the materials of the instant ambient temperature or under forced air to evaporate the invention possess, they can be used in the various forms residual solvent and/or leave the coating composition in a io mentioned above for applications, such as, but not limited largely un-crosslinked or partially crosslinked state. The to; aircraft and aerospace vehicle (launch vehicles, helicop- coated substrate can then be heated to fully cure the coating ters, unmanned aerial vehicles, etc.) surfaces to prevent composition. In certain instances, the coating composition adhesion of a variety of materials such as insect reside, ice, can be dried and cured in one step. In preferred embodi- dirt and dust and other deposits, ship hulls, ship surfaces, ments, the epoxy composition is a heat-curable coating 15 barge surfaces, oil rig surfaces, pipes, valves and pumps composition. For example, the coated substrate may be (interior and exterior), electrical transmission wires and allowed to air dry, and subsequently, the coated substrate cables, filters, filtration components, electronic components, may be thermally curing under heating (e.g., about 100 to printed circuit boards (PCB)s, controlled fluid flow devices, 175° C. for about 2 to about 6 hours). medical implants, automobile, truck, motorcycle and boat Properties and Applications 20 surfaces, racing vehicle surfaces, infrastructural surfaces The epoxy-based systems were modified with the amine- such as roads, bridges, building exteriors and interiors, terminated moieties to act as surface modifying agents, stairs, railings, firefighting clothing and equipment, tactical, which migrate to the surface. When used as coatings, these rescue and emergency response clothing, protective gear and coatings exhibit extreme water contact angles enabling equipment, windpower (windmill) blades and wind turbine super-hydrophobic surfaces. Water droplets placed on the 25 systems, and exposed surfaces. surface readily slide off with tilt angles as low as a few Construction material applications such as coatings on degrees relative to horizontal. Several reasons for this wood, cement, concrete and other masonry forms to prevent include the fact that the fluorinated alky ether moieties will or minimize water penetration, paper and fabric moisture migrate to the surface resulting in a polymer matrix that is barrier coatings for paper and cardboard products such as chemically anisotropic relative to the thickness direction of 30 insulation, "tar" paper (usually placed underneath roofing the coating. The coatings may also be transparent (i.e., not shingles), cardboard molds for concrete, coatings on glass or opaque), clear, or having no color. The particular fillers, ceramics for self-cleaning applications, structural and func- when present, also provide topographical modifications to tional composites such as carbon ceramic or glass fiber the surface resulting in increased roughness that enable reinforced composites used in the construction of automo- entrapment of air generating a Cassie-Baxter wetting state 35 biles, aircraft, boats, space vehicles, launch vehicles, con- which may be requisite for generation of a super-hydropho- struction products (such as shingles)i n which the composite bic surface. can, for example, provide structural mechanical properties The surface energy may be quantified by measuring the and at the same time have a low adhesion surface or hydrophobic characteristic of the surface by analyzing the moisture resistant surface. contact angle of a drop of water, ethylene glycol, or 40 The materials of the instant invention may be applied to diiodomethane, for example, on the surface. The shape of a variety of substrates such as but not limited to various the water drop and the angle between the surface and the types of glasses, ceramics, metals, metal alloys, polymers, tangent of the water drop is called the contact angle and is carbon allotropes, and inorganic oxides. Composites con- related to the surface energy. In general, the greater the sisting of various combinations of chopped or continuous contact angle the lower the surface energy. The epoxy resin 45 carbon, glass, inorganic, or organic fibers with an organic, compositions of the present invention may exhibit a water metallic, metal oxide, organometallic, carbon or ceramic contact angle greater than about 100, for example, ranging matrix. These substrates can be in a variety of forms, such from about 100 to about 150, about 120 to about 150, or as, but not limited to, flat, curved, concave, convex, or a about 140 to about 150. The epoxy resin compositions may variety of contours or combinations thereof. The substrates exhibit low surface energies of about 25 mN/m or less, for 50 may be monolithic or combined in a multitude of ways example, ranging from about 0.1 to about 25 mN/m, about including stacked, layered, or randomly intermixed. The 0.1 to about 20 mN/m,a bout 0.5 to about 15 mN/m, or about substrates may be in the form of solid pieces, chopped or 0.5 to about 5 mN/m. continuous fibers, woven mats or products, nonwoven mats Due to the improved properties of the epoxy resin com- or products, particulates of various dimensions, molded position, coated substrates, for example, may be readily 55 articles of complex shapes or architectures. cleaned of any and all residual contaminations. For example, The various substrates may be pretreated to change the coated surfaces impacted with fruit flies may have enhanced surface properties (surface energy), for example using, but cleanability such that the adhered insect residue may be not limited to, abrasive, mechanical, energetic radiation readily removed with water and a dampened cloth (e.g., a (laser, plasma electron beam, ultraviolet), chemical or elec- cheesecloth) with minimal effort. 60 trochemical processes. Specific pretreatment oft he substrate In some embodiments, the epoxy compositions of the is substrate dependent. For example, with metals and metal invention may be used, for example, as coatings on plastics, alloys it may be desirable to pretreat the metal to remove any metals, glass, carbon, ceramic, adhesive formulations or in oils or grease remaining from a machining process or to fiber reinforced composites or wood products which can be create specific surface chemistries. For example with tita- in a variety of forms, such as a fiber, woven mat, nonwoven 65 nium 6A14V alloy, this often involves an acid etch to create mat, cloth, broadgood, fabric, molding, laminate, foam, a fresh oxide surface followed by a priming agent to extruded shape and the like. In other embodiments, the preserve that surface. The surface pretreatment may include

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