WO2011041625A1 - Benzoxazine based curable composition for coatings applications - Google Patents

Benzoxazine based curable composition for coatings applications Download PDF

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Publication number
WO2011041625A1
WO2011041625A1 PCT/US2010/051034 US2010051034W WO2011041625A1 WO 2011041625 A1 WO2011041625 A1 WO 2011041625A1 US 2010051034 W US2010051034 W US 2010051034W WO 2011041625 A1 WO2011041625 A1 WO 2011041625A1
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Prior art keywords
powder composition
heat curable
curable powder
unsubstituted
substituted
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PCT/US2010/051034
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French (fr)
Inventor
Derek Kincaid
Lorenzo Petway
Dong LE
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Huntsman Advanced Materials Americas Llc
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Publication of WO2011041625A1 publication Critical patent/WO2011041625A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • FIELD OF INVENTION This invention relates to a benzoxazine based powder composition which may be cured to form a film coating exhibiting enlianced thermal, chemical and mechanical properties.
  • the benzoxazine based powder composition may be used in a variety of applications including industrial, electronic and automotive applications.
  • Powder coatings are film-forming coatings which are first applied to an object and then heat-melted to provide protection for the object. Advantages in using such powder coatings are that they are typically solvent-free, they can form a thick coating film with just one coating, and they can include high molecular weight resins. Accordingly, use and demand for powder coatings are increasing in the fields of construction materials, automobile parts, pipes, mechanical parts, electronic products, iron furniture and the like.
  • fusion bonded epoxy coatings are popular coatings used to protect metal pipe, rebar and piping valves and connections from corrosion. These coatings typically contain a base resin derived from bisphenol A and epichlorohydrin and a hardener such as a tertiary amine, a polyphenols compound or a strong acid.
  • a base resin derived from bisphenol A and epichlorohydrin
  • a hardener such as a tertiary amine, a polyphenols compound or a strong acid.
  • One drawback to the use of such fusion bonded epoxy coatings is the maximum glass transition temperature which can be achieved by the cured product is less than 140° C. In many instances however, the coated pipe will be exposed to much higher temperatures than this causing the coating to soften and deform under stress and become permeable thus diminishing its effectiveness.
  • an epoxy-based coating is a coating material used to provide protection for electronic devices. These coating materials are often applied to and cured on the surface of the device by heat. However, too much heat can damage and affect the performance of the device. In addition, the coating material can expand or shrink significantly during heating, causing the device to warp.
  • the present invention provides a heat curable powder composition comprising a benzoxazine monomer and a catalyst.
  • the heat curable powder composition comprises
  • each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted Ci-C 8 alky I or unsubstituted or substituted C 3 - C 8 cycloalkyl;
  • the heat curable powder composition may be used in a variety of applications including those which require the composition to exhibit, upon rapid curing, a glass transition temperature of greater than 150° C and near zero volumetric change.
  • the heat curable powder composition is especially suitable for use as a coating in piping and construction applications and in electronic devices.
  • the present invention provides a heat curable powder composition including: (a) a benzoxazine monomer; (b) a catalyst; and optionally (c) a toughening agent; and/or (d) one or more additives.
  • a heat curable powder composition refers to a particulate composition that is solid and free flowing at ambient conditions. It has been surprisingly found that the powder composition of the present invention, upon relatively moderate heating, cures in an unexpectedly short time period with a near-zero percent volume change so as to minimize any possibilities of stress induced damage to the coating.
  • the term “cures” refers to partial crosslinking of the crosslinkable components of the composition.
  • the degree of crosslinking may range from 5% to 100% of complete crosslinking. In other embodiments, the degree of crosslinking may range 50% to 85% of full crosslinking.
  • the degree of crosslinking may be determined by known means, for example, DMTA or DSC.
  • DMTA dimethyl methacrylate
  • DSC dimethyl methacrylate
  • the cured product exhibits an excellent balance of thermal, mechanical and chemical properties including, for example, a high glass transition temperature (T g ), high tensile strength, good flexibility and low flammability.
  • the heat curable powder composition of the present invention includes from about 1-99 parts by weight, preferably from about 5-95 parts by weight, and more preferably from about 10-90 parts by weight, per 100 parts by weight of the powder composition, of a benzoxazine monomer.
  • a benzoxazine monomer refers to a monomer having at least one substituted or unsubstituted benzoxazine group.
  • the benzoxazine monomer may be a mono-functional, di-functional, or tri-functional benzoxazine compound.
  • the term "benzoxazine monomer” it is to be understood that one benzoxazine monomers may be used together.
  • the benzoxazine monomer may be represented by the general formula
  • R is a substituted or unsiibstituted C 1 - C 20 alkyl group, a substituted or unsubstituted C 2 - C 20 alkenyl group, a substituted or unsubstituted C 6 - C 20 aryl group, a substituted or unsubstituted C 2 - C 20 heteroaryl group, a substituted or unsubstituted C 4 - C 20 carbocyclic group, a substituted or unsubstituted C 2 - C 20 heterocyclic group, or a C 3 ⁇ Cg cycloalkyl group;
  • the benzoxazine monomer is a compound of the general formula (I)
  • each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C 1 -C 8 alkyl or unsubstituted or substituted C 3- C 8 cycloalkyl.
  • Suitable substituents on the R-groups include amino, C 1 -C 4 alkyl and allyl.
  • One to four substituents may be present on the R-group.
  • the R-groups are the same and more preferably are phenyl.
  • the benzoxazine monomers are available commercially from several sources including Huntsman Advanced Materials Americas Inc., Georgia Pacific Resins Inc. and Shikoku Chemicals Corporation.
  • the benzoxazine monomers may also be obtained by reacting a phenol compound, for example, bisphenol A or phenolphthalein, with an aldehyde, for example, formaldehyde, and a primary amine, under conditions in which water is removed.
  • a phenol compound for example, bisphenol A or phenolphthalein
  • an aldehyde for example, formaldehyde
  • the molar ratio of phenol compound to aldehyde may be from about 1 :3 to 1:10, preferably from about 1 :4: to 1 :7, and more preferably from about 1:4.5 to 1 :5.
  • the molar ratio of phenol compound to primary amine reactant may be from about 1 :1 to 1 :3, preferably from about 1 : 1.4 to 1:2.5, and more preferably from about 1:2.1 to 1 :2.2.
  • primary amines include: aromatic mono- or di-amines, aliphatic amines, cycloaliphatic amines and heterocyclic monoamines; for example, aniline, o-, m- and p-plienylene diamine, benzidine, 4,4'-diaminodiphenyl methane, cyclohexylamine, butylamine, methylamine, hexylamine, allylamine, furfurylamine ethylenediamine, and propylenediamine.
  • the amines may, in their respective carbon part, be substituted by C 1- C 8 alkyl or allyl.
  • Preferred primary amines are according to the general formula R a NH2, wherein R a is allyl, unsubstituted or substituted phenyl, unsubstituted or substituted Q-Cs alkyl or unsubstituted or substituted C 3 -C 3 cycloalkyl.
  • Suitable substituents on the R a group include amino, C 1 -C 4 alkyl and allyl. Typically, one to four substituents may be present on the R a group.
  • R a is phenyl.
  • the heat curable powder composition also contains from about 0.1-30 parts by weight, preferably from about 1-25 parts by weight, more preferably from about at 2-20 parts by weight, and most preferably from about 5-15 parts by weight, per 100 parts by weight of the powder composition, of a catalyst to accelerate the curing of the powder composition.
  • the catalyst is a phenolic compound.
  • phenolic compounds include phenol, o-cresol, o- ⁇ m- or p-dihydroxybenzene, 2,4,6-trinitrophenol, 2,6-di-t- butyl-p-cresolo-hydroxybenzene, 2,2'-dihydiOxybiphenol, bisphenol-A, bisphenol-F, bisphenol- S, and 4,4-thiodiphenol.
  • the phenolic compound has a functionality of two or more. More preferably, the phenolic compound is 2,2'-dihydroxybiphenol or 4,4-thiodiphenol.
  • the catalyst is an acid compound.
  • acid compounds include acetic, propionic, oxalic, adipic, sebacic, benzoic, sulfuric, p-toluene sulfonic, phosphoric and thiodipropionic acid.
  • Preferred acid compounds include adipic acid and thiodipropionic acid.
  • the heat curable powder composition of the present invention may optionally include from about 0.1-40 parts by weight, preferably from about 0.5-20 parts by weight, per 100 parts by weight of the powder composition, of a toughening agent.
  • the toughening agent is a compound of the formula
  • R o is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin
  • X and Y independently of one another are -O- or -NR 3 -, at least one X or Y being -NR 3 -
  • R 2 is an m+1-valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group(s) and optionally of the amino group
  • R 3 is hydrogen, C 1 - C 6 alkyl or phenol.
  • the toughening agent of fonnula is given in U.S. Pat. No. 5,278,257, column 4, line 20 to column 16, line 20, the disclosure of which is incorporated herein by reference.
  • the toughening agent is a phenol-terminated polyurethane.
  • An example of such a toughening agent is Flexibilizer DY 965 (available from Huntsman Advanced Materials Americas Inc., prepared similarly to Examples 16-20 of U.S. Pat. No. 5,278,257).
  • the toughening agent is a polyurethane polyol.
  • polyurethane polyol is a compound having two or more hydroxyl groups and one or more urethane bonds per molecule.
  • examples of the polyurethane polyol include the reaction product of a 2- to 5-functional polyisocyanate and a polyalcohol having at least 2 hydroxyl groups, or the reaction product of a polyamine and a cyclic carbonate.
  • the reactants and the molar ratios of the reactants are chosen in such a way that they provide a reaction product having a number of residual hydroxyl groups.
  • the cyclic moieties in the polyurethane polyol can be aromatic, cycloaliphatic, heterocyclic or mixtures thereof.
  • the cyclic moieties may be present in the polyalcohol reactant(s) and/or the isocyanate reactant(s) of the polyurethane.
  • the 2- to 5-functional polyisocyanate may be isophorone diisocyanate, tetramethylxylene diisocyanate, methylene bis(4 ⁇ cyclohexyl isocyanate), norbornane diisocyanate, isocyanurate trimer of isophorone diisocyanate, the reaction product of 3 moles of m-tetramethylxylene diisocyanate with 1 mole of trimethylol propane, the reaction product of 3 moles of toluene diisocyanate with 1 mole of trimethylol propane, toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate, the uretdione of isophorone diisocyanate, the uretdione of hexamethylene diisocyanate, the allophanate of hexamethylene diisocyanate, and mixtures thereof.
  • the polyalcohol may be selected from the group of diols and triols.
  • the diol preferably is selected from the group of ethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,3-butane diol, 2-methyl- 1,3 -propane diol, 2-ethyl-2-butyl- 1,3 -propane diol, 2,2,4,-tnmethyl-l,3-pentane diol, 2-ethyl-l,3-hexane diol, neopentyl glycol, cyclohexane dimethanol, hydrogenated Bisphenol A and mixtures thereof.
  • diols are low- molecular weight (Mw ⁇ 500) condensates of dicarboxylic acids and monomelic diols, for example, as prepared from 1 mole of hexahydrophthalic anhydride and 2 moles of 2-butyl-2- ethyl- 1,3 -propane diol. Up to about 70 parts by weight of diol is used, preferably from about 20 parts by weight to about 65 parts by weight
  • Triols preferred for use as the polyalcohol are glycerol, trimethylol propane, trimethylol ethane or mixtures thereof. Up to about 25 parts by weight of triol may be used, preferably from about 1 part by weight to about 20 parts by weight
  • reactant(s) for preparation of the polyurethane polyol may be used, such as C 1 -C 18 monoalcohols, the molar ratio of monoalcohol to diol and/or triol component being less than 2, C 2 -C 25 primary or secondary monoamine compounds, optionally substituted with a hydroxyl group, the molar ratio of the monoamine to diol and/or triol being lower than 2, and C 2 -C 25 diamine compounds comprising primary and/or secondary amine groups, the molar ratio of the diamine to diol and/or triol being lower than 2.
  • C 1 -C 18 monoalcohols the molar ratio of monoalcohol to diol and/or triol component being less than 2
  • C 2 -C 25 primary or secondary monoamine compounds optionally substituted with a hydroxyl group
  • C 2 -C 25 diamine compounds comprising primary and/or secondary amine groups
  • the molar ratio of the diamine to diol and/or triol being lower than
  • Suitable monoalcohols are for example methanol, ethanol, butanol, 2-ethyl hexanol, cyclohexanol, benzyl alcohol, stearyl alcohol, and mixtures thereof.
  • Suitable monoamines are for example butyl amine, dibutyl amine, isopropanol amine, N-methyl ethanol amine, benzyl amine, and mixtures thereof.
  • Suitable diamines are for example isophorone diamine, cyclohexane diamine, propylene diamine, piperazine, aminoethyl piperazine, and mixtures thereof.
  • the ratio of hydroxyl groups and, optionally, amine groups to isocyanate groups ranges from about 1.2 to about 3.
  • the number average molecular weight (Mn) of the polyurethane polyol is less than 5,000, most preferred are polyurethane polyols having a Mn of less than 3,000, as determined by gel permeation chromatography using polystyrene or polypropylene glycol as a standard.
  • the degree of molecular dispersion, i.e. the ratio of Mw to Mn preferably is in the range of 1.1 to 5, ranges from 1.1 to 3 being preferred particularly.
  • the polyurethane polyols have a hydroxyl number below 350 mg KOH/g solid resin, more preferably in the range from 50 to 350 mg KOH/g solid resin, even more preferably in the range of 50 to 250 mg KOH/g solid resin.
  • the synthesis of the polyurethane polyols of the invention preferably is carried out at a temperature of 125°C or less, most preferably in the range from 15°C to 100°C.
  • the components may optionally be reacted in the presence of a polyurethane catalyst, for example organic tin compounds such as dibutyl tin dilaurate or tertiary amine such as triethylene diamine.
  • the heat curable powder composition may also include, if necessary, additives for enhancing strength, release properties, hydrolysis resistance, electrical conductivity and other characteristics.
  • the additives may be added to the heat curable powder composition in an amount of less than about 50 parts by weight, preferably less than about 30 parts by weight and most preferably less than about 20 parts by weight, per 100 parts by weight of the heat curable powder composition.
  • Such optional additives may include epoxy resins; reinforcement fibers, such as: metal fibers (e.g. iron, copper, brass, bronze, aluminum) ceramic fibers, glass fibers, carbon fibers, gypsum fibers, rock wool, wollastonite, sepiolite, attapulgites, synthetic mineral fibers, aramid fibers, polyimide fibers, polyamide fibers, phenolic fibers, cellulose fibers and acrylic fibers; fillers (e.g. silica, fumed silica, calcium silicate and aluminum oxide); micro or hollow spheres; nanosilica particles; plasticizers; antioxidants; UV absorbers; colorants (e.g.
  • the heat curable powder composition is substantially free of epoxy resins. In other embodiment, the heat curable powder composition is substantially free of solvents.
  • the heat curable powder compositions of the present invention can be prepared in known manner, for example, by premixing individual components and then mixing these premixes or by mixing all of the components together, using customary devices.
  • all of the components may be blended together in a mixing container and mixed together to form a blended mixture.
  • the blended mixture may then be melt blended, for example, in a melt extruder.
  • the extruded composition may then be cooled and broken into chips and ground to a powder, The ground powder may then be subsequently screened to achieve the desired particle size.
  • the heat curable powder composition is produced by a process including: [00054] (a) providing a benzoxazine monomer of the formula (I)
  • each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C 1 -C 8 alkyl or unsubstituted or substituted C 3 -C 8 cycloalkyl;
  • the heat curable powder composition of the present invention is prepared by providing from about 5-95 parts by weight of the benzoxazine monomer, from about 2-20 parts by weight of the catalyst, and optionally from about 0.1-40 parts by weight of the toughening agent, per 100 parts by weight of the heat curable powder composition and mixing the benzoxazine monomer, catalyst and optionally toughening agent under conditions suitable to produce the heat curable powder composition.
  • the heat curable powder composition of the present invention is prepared by providing from about 10-90 parts by weight of the benzoxazine monomer, from about 5-15 parts by weight of the catalyst, and optionally from about 0.5-20 parts by weight of the toughening agent, per 100 parts by weight of the heat curable powder composition and mixing the benzoxazine monomer, catalyst and optionally toughening agent under conditions suitable to produce the heat curable powder composition.
  • the heat curable powder composition of the present invention can be packaged in a variety of containers such as steel, tin, aluminium, plastic, glass or cardboard containers.
  • the heat curable powder composition may be applied to a substrate and cured by heating at a temperature greater than about 100°C to form a coated substrate.
  • the powder composition may be applied by any known means, for example, spraying, dipping, fluidized bed, etc.
  • the heat curable powder composition may be cured by heating at a temperature ranging from about 120°C to about 250°C, preferably from about 180°C to about 220°C. Heating can be effected by any means known in the art, such as by placing the coated substrate in an oven. IR radiation can also be used to heat cure the coated substrate.
  • the powder coated surface should be exposed to curing temperatures for a period of time sufficient to cure the powder particles into a substantially continuous uniform coating.
  • a curing time of from about 1 minute to about 10 minutes or more will convert the powdered particles into a substantially continuous uniform coating.
  • the curing may be conducted in two or more stages, for example, by partially curing at a lower temperature, then fully curing at an elevated temperature.
  • the heat curable powder composition may achieve 85% full state cure within 5 minutes, preferably within 2 minutes, more preferably within 1 minute and most preferably within 45 seconds when cured at a temperature ranging between about 180° C to about 220° C.
  • the heat curable powder composition upon mixing and curing, provides a film having a glass transition temperature greater than 150°C, preferably greater than 170°C, most preferably greater than 180°C, and especially preferably greater than 190°C.
  • the present invention further provides a heat curable powder composition comprising:
  • each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C ⁇ Cs alkyl or unsubstituted or substituted C 3 -C 8 cyeloalkyl;
  • the heat curable powder composition wherein the heat curable powder composition, upon curing, has a glass transition temperature greater than 150°C, preferably greater than 170°C, and more preferably greater than 190°C,
  • the heat curable powder composition of the present invention may be used in a variety of applications, such as, casting, laminating, impregnating, coating, adhering, sealing, painting, binding, insulating, or in embedding, pressing, injection molding, extruding, sand mold binding, foam and ablative materials.
  • the heat curable powder composition may be used in the preparation of and/or as a sealant, adhesive or coating.
  • the sealant, adhesive or coating comprising the heat curable powder composition may be applied to the surface of one or more substrates and subjected to heat to form a hardened film.
  • the substrate may be metallic or non-metallic. Examples of the substrate include a metal, silicate, metal oxide, concrete, wood, plastic, cardboard, particleboard, ceramics, glass, graphite, cellulosic materials, electronic chip materials, and semiconductor materials.
  • Further substrates are pipelines including the internal and/or external surfaces of steel pipes, structural steel used in concrete or in marine environments, storage tanks, valves and oil production tubing and casings.
  • the surface of the substrate may be subjected to a mechanical treatment, such as blasting followed by, in case of metal substrates, acid rinsing, or cleaning followed by chemical treatment.
  • the substrate to be coated may be pre-heated before the application of the powder composition.
  • the heat curable powder composition is used as a coating, it may be used in a one-coating system or as a coating layer in a multi-layer film build.
  • the powder composition according to the invention can be applied directly on the substrate surface or on a layer of a primer which can be a liquid or a powder based primer.
  • the powder composition according to the invention can also be applied as a coating layer of a multilayer coating system based on liquid or powder coats, for example, based on a powder or liquid clear coat layer applied onto a color-imparting and/or special effect-imparting base coat layer or a pigmented one-layer powder or liquid top coat applied onto a prior coating.
  • the powder composition may be applied by spraying, electrostatic spraying thermal or flame spraying, coil coating techniques, triboelectric guns or by the use of a fluidized bed.
  • the powder coating may be applied in a single sweep or in several passes. After application, the powder coating coated substrate is then heated at a temperature sufficient to cure the powder composition and form a film-coated substrate.
  • the film coating will generally have a thickness after cure of about 1 to 10 mils, preferably about 2-4 mils
  • the heat curable powder composition may be used as an adhesive for gluing or adhering parts made of the same or different substrates to form an article.
  • the heat curable powder composition is first placed in contact with at least one of two or more of the same or different substrates to be bonded.
  • the heat curable powder composition is sandwiched between a first and second substrate.
  • the heat curable powder composition and substrates are then heated at a temperature greater than 100°C, preferably greater than 190° C. By applying heat, an adhesive bond is formed so as to adhere the substrates together and form the article.

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Abstract

The present invention provides a heat curable powder composition including a benzoxazine monomer, a catalyst, and optionally a toughening agent. The heat curable powder composition is especially suited for use in industrial, automotive and electronic applications as the powder composition, upon curing, produces a film having a high glass transition temperature and near zero percent volume change.

Description

BΕΝΖΟΧΑΖΙΝΕ-BASED CURABLE COMPOSITION
FOR COATINGS APPLICATIONS
[0001] CROSS-REFERENCE TO RELATED APPLICATION
[0002] This application claims priority to U.S. Pat. App. Ser No. 61/ 248,111, filed October 2,
2009, which is incorporated herein by reference.
[0003] STATEMENT REGARDING FEDERALLY
SPONSORED RESEARCH OR DEVELOPMENT
[0004] Not Applicable.
[0005] FIELD OF INVENTION [0006] This invention relates to a benzoxazine based powder composition which may be cured to form a film coating exhibiting enlianced thermal, chemical and mechanical properties. The benzoxazine based powder composition may be used in a variety of applications including industrial, electronic and automotive applications.
[0007] BACKGROUND OF THE INVENTION [0008] Powder coatings are film-forming coatings which are first applied to an object and then heat-melted to provide protection for the object. Advantages in using such powder coatings are that they are typically solvent-free, they can form a thick coating film with just one coating, and they can include high molecular weight resins. Accordingly, use and demand for powder coatings are increasing in the fields of construction materials, automobile parts, pipes, mechanical parts, electronic products, iron furniture and the like.
[0009] Most powder coatings are based at least in part on an epoxy resin. For example, fusion bonded epoxy coatings are popular coatings used to protect metal pipe, rebar and piping valves and connections from corrosion. These coatings typically contain a base resin derived from bisphenol A and epichlorohydrin and a hardener such as a tertiary amine, a polyphenols compound or a strong acid. One drawback to the use of such fusion bonded epoxy coatings is the maximum glass transition temperature which can be achieved by the cured product is less than 140° C. In many instances however, the coated pipe will be exposed to much higher temperatures than this causing the coating to soften and deform under stress and become permeable thus diminishing its effectiveness.
[00010] Another example of an epoxy-based coating is a coating material used to provide protection for electronic devices. These coating materials are often applied to and cured on the surface of the device by heat. However, too much heat can damage and affect the performance of the device. In addition, the coating material can expand or shrink significantly during heating, causing the device to warp.
[00011] Notwithstanding the state of the technology, it would be desirable to provide alternative heat curable powder coatings which rapidly cure and exhibit improved thermal resistance and mechanical properties.
[00012]
SUMMARY OF THE INVENTION
[00013] The present invention provides a heat curable powder composition comprising a benzoxazine monomer and a catalyst.
[00014] In one embodiment, the heat curable powder composition comprises
[00015] a benzoxazine monomer of the formula (I)
Figure imgf000004_0001
[00016] wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted Ci-C8 alky I or unsubstituted or substituted C3- C8 cycloalkyl;
[00017] (b) a catalyst comprising a phenolic compound or acidic compound; and optionally
[00018] (c) a toughening agent.
[00019] The heat curable powder composition may be used in a variety of applications including those which require the composition to exhibit, upon rapid curing, a glass transition temperature of greater than 150° C and near zero volumetric change. Thus, the heat curable powder composition is especially suitable for use as a coating in piping and construction applications and in electronic devices.
[00020] DETAILED DESCRIPTION OF THE INVENTION
[00021] In general, the present invention provides a heat curable powder composition including: (a) a benzoxazine monomer; (b) a catalyst; and optionally (c) a toughening agent; and/or (d) one or more additives. As used herein, the term "powder composition" refers to a particulate composition that is solid and free flowing at ambient conditions. It has been surprisingly found that the powder composition of the present invention, upon relatively moderate heating, cures in an unexpectedly short time period with a near-zero percent volume change so as to minimize any possibilities of stress induced damage to the coating. As used herein, the term "cures" refers to partial crosslinking of the crosslinkable components of the composition. In some embodiments, the degree of crosslinking may range from 5% to 100% of complete crosslinking. In other embodiments, the degree of crosslinking may range 50% to 85% of full crosslinking. The degree of crosslinking may be determined by known means, for example, DMTA or DSC. In addition, it has also been surprisingly found that the cured product exhibits an excellent balance of thermal, mechanical and chemical properties including, for example, a high glass transition temperature (Tg), high tensile strength, good flexibility and low flammability.
[00022] Benzoxazine Monomer
[00023] The heat curable powder composition of the present invention includes from about 1-99 parts by weight, preferably from about 5-95 parts by weight, and more preferably from about 10-90 parts by weight, per 100 parts by weight of the powder composition, of a benzoxazine monomer. As used herein, the term "benzoxazine monomer" refers to a monomer having at least one substituted or unsubstituted benzoxazine group. The benzoxazine monomer may be a mono-functional, di-functional, or tri-functional benzoxazine compound. Moreover, where the term "benzoxazine monomer" is used, it is to be understood that one benzoxazine monomers may be used together.
[00024] The benzoxazine monomer may be represented by the general formula
Figure imgf000006_0001
[00025] wherein b is an integer from 0 to 3; R is a substituted or unsiibstituted C1 - C20 alkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C6 - C20 aryl group, a substituted or unsubstituted C2 - C20 heteroaryl group, a substituted or unsubstituted C4 - C20 carbocyclic group, a substituted or unsubstituted C2 - C20 heterocyclic group, or a C3~Cg cycloalkyl group; Rj is hydrogen, an alkyl group or an alkenyl group; and Z is a direct bond (when b=2), a substituted or unsubstituted C1 - C20 alkyiene group, a substituted or unsubstituted C6 - C20 arylene group, a substituted or unsubstituted C2 - C20 heteroarylene group or C=0.
[00026] In one embodiment, the benzoxazine monomer is a compound of the general formula (I)
Figure imgf000007_0001
[00027] wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl or unsubstituted or substituted C3-C8 cycloalkyl. Suitable substituents on the R-groups include amino, C1-C4 alkyl and allyl. One to four substituents may be present on the R-group. Preferably, the R-groups are the same and more preferably are phenyl.
[00028] The benzoxazine monomers are available commercially from several sources including Huntsman Advanced Materials Americas Inc., Georgia Pacific Resins Inc. and Shikoku Chemicals Corporation. The benzoxazine monomers may also be obtained by reacting a phenol compound, for example, bisphenol A or phenolphthalein, with an aldehyde, for example, formaldehyde, and a primary amine, under conditions in which water is removed. The molar ratio of phenol compound to aldehyde may be from about 1 :3 to 1:10, preferably from about 1 :4: to 1 :7, and more preferably from about 1:4.5 to 1 :5. The molar ratio of phenol compound to primary amine reactant may be from about 1 :1 to 1 :3, preferably from about 1 : 1.4 to 1:2.5, and more preferably from about 1:2.1 to 1 :2.2. Examples of primary amines include: aromatic mono- or di-amines, aliphatic amines, cycloaliphatic amines and heterocyclic monoamines; for example, aniline, o-, m- and p-plienylene diamine, benzidine, 4,4'-diaminodiphenyl methane, cyclohexylamine, butylamine, methylamine, hexylamine, allylamine, furfurylamine ethylenediamine, and propylenediamine. The amines may, in their respective carbon part, be substituted by C1-C8 alkyl or allyl. Preferred primary amines are according to the general formula RaNH2, wherein Ra is allyl, unsubstituted or substituted phenyl, unsubstituted or substituted Q-Cs alkyl or unsubstituted or substituted C3-C3 cycloalkyl. Suitable substituents on the Ra group include amino, C1-C4 alkyl and allyl. Typically, one to four substituents may be present on the Ra group. Preferably Ra is phenyl.
[00029] Catalyst
[00030] The heat curable powder composition also contains from about 0.1-30 parts by weight, preferably from about 1-25 parts by weight, more preferably from about at 2-20 parts by weight, and most preferably from about 5-15 parts by weight, per 100 parts by weight of the powder composition, of a catalyst to accelerate the curing of the powder composition.
[00031] In one embodiment, the catalyst is a phenolic compound. Examples of phenolic compounds include phenol, o-cresol, o-} m- or p-dihydroxybenzene, 2,4,6-trinitrophenol, 2,6-di-t- butyl-p-cresolo-hydroxybenzene, 2,2'-dihydiOxybiphenol, bisphenol-A, bisphenol-F, bisphenol- S, and 4,4-thiodiphenol. Preferably, the phenolic compound has a functionality of two or more. More preferably, the phenolic compound is 2,2'-dihydroxybiphenol or 4,4-thiodiphenol.
[00032] In another embodiment, the catalyst is an acid compound. Examples of acid compounds include acetic, propionic, oxalic, adipic, sebacic, benzoic, sulfuric, p-toluene sulfonic, phosphoric and thiodipropionic acid. Preferred acid compounds include adipic acid and thiodipropionic acid.
[00033] Toughening Agent
[00034] The heat curable powder composition of the present invention may optionally include from about 0.1-40 parts by weight, preferably from about 0.5-20 parts by weight, per 100 parts by weight of the powder composition, of a toughening agent.
[00035] In one embodiment, the toughening agent is a compound of the formula
Figure imgf000009_0001
[00036] where m is 1 or 2, n is 2 to 6, Rº is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin, X and Y independently of one another are -O- or -NR3-, at least one X or Y being -NR3-, R2 is an m+1-valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group(s) and optionally of the amino group, and R3 is hydrogen, C1 - C6 alkyl or phenol. A detailed description of the toughening agent of fonnula (II) is given in U.S. Pat. No. 5,278,257, column 4, line 20 to column 16, line 20, the disclosure of which is incorporated herein by reference. Preferably, the toughening agent is a phenol-terminated polyurethane. An example of such a toughening agent is Flexibilizer DY 965 (available from Huntsman Advanced Materials Americas Inc., prepared similarly to Examples 16-20 of U.S. Pat. No. 5,278,257).
[00037] In another embodiment, the toughening agent is a polyurethane polyol. As used herein, "polyurethane polyol" is a compound having two or more hydroxyl groups and one or more urethane bonds per molecule. Examples of the polyurethane polyol include the reaction product of a 2- to 5-functional polyisocyanate and a polyalcohol having at least 2 hydroxyl groups, or the reaction product of a polyamine and a cyclic carbonate. The reactants and the molar ratios of the reactants are chosen in such a way that they provide a reaction product having a number of residual hydroxyl groups. The cyclic moieties in the polyurethane polyol can be aromatic, cycloaliphatic, heterocyclic or mixtures thereof. The cyclic moieties may be present in the polyalcohol reactant(s) and/or the isocyanate reactant(s) of the polyurethane.
[00038] The 2- to 5-functional polyisocyanate may be isophorone diisocyanate, tetramethylxylene diisocyanate, methylene bis(4~cyclohexyl isocyanate), norbornane diisocyanate, isocyanurate trimer of isophorone diisocyanate, the reaction product of 3 moles of m-tetramethylxylene diisocyanate with 1 mole of trimethylol propane, the reaction product of 3 moles of toluene diisocyanate with 1 mole of trimethylol propane, toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate, the uretdione of isophorone diisocyanate, the uretdione of hexamethylene diisocyanate, the allophanate of hexamethylene diisocyanate, and mixtures thereof. Preferably, from about 20 parts by weight to about 80 parts by weight of polyisocyanate is used in the preparation of the polyurethane polyol, more preferably from about 30 parts by weight to about 70 parts by weight.
[00039] The polyalcohol may be selected from the group of diols and triols. [00040] The diol preferably is selected from the group of ethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,3-butane diol, 2-methyl- 1,3 -propane diol, 2-ethyl-2-butyl- 1,3 -propane diol, 2,2,4,-tnmethyl-l,3-pentane diol, 2-ethyl-l,3-hexane diol, neopentyl glycol, cyclohexane dimethanol, hydrogenated Bisphenol A and mixtures thereof. Also preferred diols are low- molecular weight (Mw<500) condensates of dicarboxylic acids and monomelic diols, for example, as prepared from 1 mole of hexahydrophthalic anhydride and 2 moles of 2-butyl-2- ethyl- 1,3 -propane diol. Up to about 70 parts by weight of diol is used, preferably from about 20 parts by weight to about 65 parts by weight
[00041] Triols preferred for use as the polyalcohol are glycerol, trimethylol propane, trimethylol ethane or mixtures thereof. Up to about 25 parts by weight of triol may be used, preferably from about 1 part by weight to about 20 parts by weight
[00042] Optionally, up to 30 parts by weight of further reactant(s) for preparation of the polyurethane polyol may be used, such as C1-C18 monoalcohols, the molar ratio of monoalcohol to diol and/or triol component being less than 2, C2-C25 primary or secondary monoamine compounds, optionally substituted with a hydroxyl group, the molar ratio of the monoamine to diol and/or triol being lower than 2, and C2-C25 diamine compounds comprising primary and/or secondary amine groups, the molar ratio of the diamine to diol and/or triol being lower than 2.
[00043] Suitable monoalcohols are for example methanol, ethanol, butanol, 2-ethyl hexanol, cyclohexanol, benzyl alcohol, stearyl alcohol, and mixtures thereof.
[00044] Suitable monoamines are for example butyl amine, dibutyl amine, isopropanol amine, N-methyl ethanol amine, benzyl amine, and mixtures thereof. [00045] Suitable diamines are for example isophorone diamine, cyclohexane diamine, propylene diamine, piperazine, aminoethyl piperazine, and mixtures thereof.
[00046] For the preparation of the polyurethane polyol the ratio of hydroxyl groups and, optionally, amine groups to isocyanate groups ranges from about 1.2 to about 3.
[00047] It is preferred that the number average molecular weight (Mn) of the polyurethane polyol is less than 5,000, most preferred are polyurethane polyols having a Mn of less than 3,000, as determined by gel permeation chromatography using polystyrene or polypropylene glycol as a standard. The degree of molecular dispersion, i.e. the ratio of Mw to Mn, preferably is in the range of 1.1 to 5, ranges from 1.1 to 3 being preferred particularly. Preferably, the polyurethane polyols have a hydroxyl number below 350 mg KOH/g solid resin, more preferably in the range from 50 to 350 mg KOH/g solid resin, even more preferably in the range of 50 to 250 mg KOH/g solid resin.
[00048] The synthesis of the polyurethane polyols of the invention preferably is carried out at a temperature of 125°C or less, most preferably in the range from 15°C to 100°C. The components may optionally be reacted in the presence of a polyurethane catalyst, for example organic tin compounds such as dibutyl tin dilaurate or tertiary amine such as triethylene diamine.
[00049] Additives
[00050] In addition to the components identified above, the heat curable powder composition may also include, if necessary, additives for enhancing strength, release properties, hydrolysis resistance, electrical conductivity and other characteristics. The additives may be added to the heat curable powder composition in an amount of less than about 50 parts by weight, preferably less than about 30 parts by weight and most preferably less than about 20 parts by weight, per 100 parts by weight of the heat curable powder composition.
[00051] Such optional additives may include epoxy resins; reinforcement fibers, such as: metal fibers (e.g. iron, copper, brass, bronze, aluminum) ceramic fibers, glass fibers, carbon fibers, gypsum fibers, rock wool, wollastonite, sepiolite, attapulgites, synthetic mineral fibers, aramid fibers, polyimide fibers, polyamide fibers, phenolic fibers, cellulose fibers and acrylic fibers; fillers (e.g. silica, fumed silica, calcium silicate and aluminum oxide); micro or hollow spheres; nanosilica particles; plasticizers; antioxidants; UV absorbers; colorants (e.g. carbon black or graphite); flame retardants, dyestuffs; waxes (e.g. carnauba wax or paraffin wax); coupling agents (e.g. silane type coupling agent); solvents; and, metal powders. In some embodiments, the heat curable powder composition is substantially free of epoxy resins. In other embodiment, the heat curable powder composition is substantially free of solvents.
[00052] The heat curable powder compositions of the present invention can be prepared in known manner, for example, by premixing individual components and then mixing these premixes or by mixing all of the components together, using customary devices. In one embodiment, all of the components may be blended together in a mixing container and mixed together to form a blended mixture. The blended mixture may then be melt blended, for example, in a melt extruder. The extruded composition may then be cooled and broken into chips and ground to a powder, The ground powder may then be subsequently screened to achieve the desired particle size.
[00053] Thus, according to another embodiment, the heat curable powder composition is produced by a process including: [00054] (a) providing a benzoxazine monomer of the formula (I)
Figure imgf000014_0001
[00055] wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl or unsubstituted or substituted C3-C8 cycloalkyl;
[00056] (b) providing with mixing a catalyst; and optionally a toughening agent and/or additives; and
[00057] (c) mixing the benzoxazine monomer, catalyst and optionally toughening agent and/or additives under conditions suitable to produce the heat curable powder composition.
[00058] In one embodiment, the heat curable powder composition of the present invention is prepared by providing from about 5-95 parts by weight of the benzoxazine monomer, from about 2-20 parts by weight of the catalyst, and optionally from about 0.1-40 parts by weight of the toughening agent, per 100 parts by weight of the heat curable powder composition and mixing the benzoxazine monomer, catalyst and optionally toughening agent under conditions suitable to produce the heat curable powder composition. In another embodiment, the heat curable powder composition of the present invention is prepared by providing from about 10-90 parts by weight of the benzoxazine monomer, from about 5-15 parts by weight of the catalyst, and optionally from about 0.5-20 parts by weight of the toughening agent, per 100 parts by weight of the heat curable powder composition and mixing the benzoxazine monomer, catalyst and optionally toughening agent under conditions suitable to produce the heat curable powder composition.
[00059] Once formulated, the heat curable powder composition of the present invention can be packaged in a variety of containers such as steel, tin, aluminium, plastic, glass or cardboard containers.
[00060] According to another embodiment, the heat curable powder composition may be applied to a substrate and cured by heating at a temperature greater than about 100°C to form a coated substrate. The powder composition may be applied by any known means, for example, spraying, dipping, fluidized bed, etc. In another embodiment, after application, the heat curable powder composition may be cured by heating at a temperature ranging from about 120°C to about 250°C, preferably from about 180°C to about 220°C. Heating can be effected by any means known in the art, such as by placing the coated substrate in an oven. IR radiation can also be used to heat cure the coated substrate. The powder coated surface should be exposed to curing temperatures for a period of time sufficient to cure the powder particles into a substantially continuous uniform coating. Typically, a curing time of from about 1 minute to about 10 minutes or more will convert the powdered particles into a substantially continuous uniform coating. If desired, the curing may be conducted in two or more stages, for example, by partially curing at a lower temperature, then fully curing at an elevated temperature. In yet a further embodiment, the heat curable powder composition may achieve 85% full state cure within 5 minutes, preferably within 2 minutes, more preferably within 1 minute and most preferably within 45 seconds when cured at a temperature ranging between about 180° C to about 220° C.
[00061] In another embodiment, the heat curable powder composition, upon mixing and curing, provides a film having a glass transition temperature greater than 150°C, preferably greater than 170°C, most preferably greater than 180°C, and especially preferably greater than 190°C.
[00062] Thus, the present invention further provides a heat curable powder composition comprising:
[00063] (a) 10-90 parts by weight of a benzoxazine monomer of the formula (I)
Figure imgf000016_0001
[00064] wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C^Cs alkyl or unsubstituted or substituted C3-C8 cyeloalkyl;
[00065] (b) 0.1-20 parts by a catalyst comprising a phenolic compound or acidic compound;
[00066] (c) optionally 0.1 -40 parts by weight of a toughening agent; and optionally [00067] (d) 1-50 parts by weight of one or more additives,
[00068] per 100 parts by weight of the heat curable powder composition wherein the heat curable powder composition, upon curing, has a glass transition temperature greater than 150°C, preferably greater than 170°C, and more preferably greater than 190°C,
[00069] The heat curable powder composition of the present invention may be used in a variety of applications, such as, casting, laminating, impregnating, coating, adhering, sealing, painting, binding, insulating, or in embedding, pressing, injection molding, extruding, sand mold binding, foam and ablative materials.
[00070] According to some embodiments, the heat curable powder composition may be used in the preparation of and/or as a sealant, adhesive or coating. The sealant, adhesive or coating comprising the heat curable powder composition may be applied to the surface of one or more substrates and subjected to heat to form a hardened film. The substrate may be metallic or non-metallic. Examples of the substrate include a metal, silicate, metal oxide, concrete, wood, plastic, cardboard, particleboard, ceramics, glass, graphite, cellulosic materials, electronic chip materials, and semiconductor materials. Further substrates are pipelines including the internal and/or external surfaces of steel pipes, structural steel used in concrete or in marine environments, storage tanks, valves and oil production tubing and casings. If desired, prior to or subsequent of application of the powder composition, the surface of the substrate may be subjected to a mechanical treatment, such as blasting followed by, in case of metal substrates, acid rinsing, or cleaning followed by chemical treatment. In addition, the substrate to be coated may be pre-heated before the application of the powder composition. [00071] In embodiments where the heat curable powder composition is used as a coating, it may be used in a one-coating system or as a coating layer in a multi-layer film build. The powder composition according to the invention can be applied directly on the substrate surface or on a layer of a primer which can be a liquid or a powder based primer. The powder composition according to the invention can also be applied as a coating layer of a multilayer coating system based on liquid or powder coats, for example, based on a powder or liquid clear coat layer applied onto a color-imparting and/or special effect-imparting base coat layer or a pigmented one-layer powder or liquid top coat applied onto a prior coating. The powder composition may be applied by spraying, electrostatic spraying thermal or flame spraying, coil coating techniques, triboelectric guns or by the use of a fluidized bed. In addition, the powder coating may be applied in a single sweep or in several passes. After application, the powder coating coated substrate is then heated at a temperature sufficient to cure the powder composition and form a film-coated substrate. In some embodiments, the film coating will generally have a thickness after cure of about 1 to 10 mils, preferably about 2-4 mils
[00072] In another embodiment of the invention, the heat curable powder composition may be used as an adhesive for gluing or adhering parts made of the same or different substrates to form an article. The heat curable powder composition is first placed in contact with at least one of two or more of the same or different substrates to be bonded. In one embodiment, the heat curable powder composition is sandwiched between a first and second substrate. The heat curable powder composition and substrates are then heated at a temperature greater than 100°C, preferably greater than 190° C. By applying heat, an adhesive bond is formed so as to adhere the substrates together and form the article. [00073] EXAMPLES
[00074] A) The components in Tables 1 and 2 were added on a weight basis to a container and sufficiently mixed to homogeneity, cured, then analytically tested and provided the follovving properties:
Figure imgf000019_0001
Figure imgf000020_0001
[00077] Although making and using various embodiments of the present invention have been described in detail above, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention, and do not delimit the scope of the invention.

Claims

WHAT IS CLAIMED IS:
1. A heat curable powder composition comprising:
(a) a benzoxazine monomer of the formula (I)
Figure imgf000021_0001
wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted Cj-Cg alkyl or unsubstituted or substituted C3-C8 cycloalkyl;
(b) a catalyst comprising a phenolic compound or acidic compound; and optionally
(c) a toughening agent of the formula (II)
Figure imgf000021_0002
wherein m is 1 or 2} n is 2 to 6, R is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin, X and Y independently of one another are -O- or -NR3-, at least one X or Y being -NR3-, R2 is an m+l-valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group (s) and optionally of the amino group, and R3 is hydrogen, C1 - C6 alkyl or phenol.
2. The heat curable powder composition according to claim 1 wherein R is phenyl.
3. The heat curable powder composition according to claim 1 wherein the phenolic compound has a functionality of two or more.
4. The heat curable powder composition according to claim 3 wherein the phenolic compound is 2,2'-dihydroxybiphenol or 4,4-thiodiphenol.
5. The heat curable powder composition according to claim 1 wherein the toughening agent is present.
6. The heat curable powder composition according to claim 5, wherein the toughening agent is a phenol-terminated polyurethane.
7. The heat curable powder composition according to claim 1, wherein the composition is substantially free of epoxy resins.
8. A heat curable powder composition comprising:
(a) 10-90 parts by weight of a benzoxazine monomer of the formula (I)
Figure imgf000023_0001
wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8-alkyl or unsubstituted or substituted C3-C8 cycloalkyl;
(b) 0.1-20 parts by a catalyst comprising a phenolic compound or an acidic compound; and optionally
(c) 0.1-40 parts by weight of a toughening agent
per 100 parts by weight of the heat curable powder composition wherein the heat curable powder composition, upon curing, has a glass transition temperature greater than 150°C.
9. The heat curable powder composition according to claim 8, wherein the glass transition temperature is greater than 170°C. 10, The heat curable powder composition according to claim 8, wherein the glass transition temperature is greater than 190°C,
11. A method for producing a heat curable powder composition comprising:
(a) providing a benzoxazine monomer of the formula (I)
Figure imgf000024_0001
wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8-alkyl or unsubstituted or substituted C3-C8 cycloalkyl;
(b) providing with mixing a catalyst; and optionally a toughening agent; and
(c) mixing the benzoxazine monomer, catalyst and optionally toughening agent under conditions suitable to produce the heat curable powder composition. heat curable powder composition produced according to the method of claim 11.
13. A substrate comprising a layer of a heat curable powder composition wherein the heat curable powder composition comprises a benzoxazine monomer of the formula (I)
Figure imgf000025_0001
wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl or unsubstituted or substituted C3-C8 cycloalkyl; a catalyst comprising a phenolic compound; and optionally a toughening agent of the formula (II)
Figure imgf000025_0002
wherein m is 1 or 2, n is 2 to 6, R is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin, X and Y independently of one another are -O- or -NR at least one X or Y being -NR3-, R2 is an m+l-valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group(s) and optionally of the amino group, and R3 is hydrogen, C1-C6 alkyl or phenol.
14. A process for forming a coated substrate comprising the steps of:
(a) applying a heat curable powder composition to a surface of a substrate; and
(b) heating the powder composition at a temperature greater than 100° C to cure the powder composition, wherein the heat curable powder composition comprises a benzoxazine monomer of the formula (I)
Figure imgf000026_0001
wherein each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl or unsubstituted or substituted C3-C8 cycloalkyl; a catalyst comprising a phenolic compound; and optionally a toughening agent of the formula (II)
Figure imgf000026_0002
wherein m is 1 or 2, n is 2 to 6, R is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin, X and Y independently of one another are -O- or -NR at least one X or Y being -NR3-, R2 is an m+l -valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group (s) and optionally of the amino group, and R is hydrogen, C1 - C6 alkyl or phenol.
15. The process according to claim 14, wherein the heat curable powder composition is heated a temperature ranging from about 180° C to about 220° C.
16. A process for producing a film-coated substrate comprising the steps of:
(a) providing a heat curable powder composition comprising
(i) a benzoxazine monomer of the formula (I)
Figure imgf000027_0001
wherem each R is, independently from one another, allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl or unsubstituted or substituted C3-C8 cycloalkyl;
(ii) a catalyst comprising a phenolic compound; and optionally (iii) a toughening agent of the formula (II)
Figure imgf000028_0001
wherein m is 1 or 2, n is 2 to 6, R is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxy! groups, the elastomeric prepolymer being soluble or dispersible in epoxy resin, X and Y independently of one another are -O- or ~NR at least one X or Y being -NR R is an m+l-valent radical of polyphenol or aminophenol after the removal of the phenolic hydroxyl group(s) and optionally of the amino group, and R is hydrogen, Ci - C6 alkyl or phenol.
(b) applying the heat curable powder composition to the surface of a substrate;
(c) subjecting the heat curable powder composition to heat to form a film coating on the substrate,
17. The process of claim 16 wherein the substrate is metallic.
18. The process of claim 17, wherein the heat curable powder composition is applied by spraying or a fluidized bed.
19. The process of claim 16 wherein the substrate is non-metallic.
20. The process of claim 16, wherein the film coating has a glass transition temperature greater than 150° C.
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WO2013122800A1 (en) * 2012-02-17 2013-08-22 Huntsman Advanced Materials Americas Llc Mixture of benzoxazine, epoxy and anhydride
CN113355043A (en) * 2021-06-24 2021-09-07 浙江华峰合成树脂有限公司 Heat-activated polyurethane hot melt adhesive and preparation method thereof
CN113355043B (en) * 2021-06-24 2022-09-30 浙江华峰合成树脂有限公司 Heat-activated polyurethane hot melt adhesive and preparation method thereof

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