Classifications

• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/26—Di-epoxy compounds heterocyclic
• • 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
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • 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
  • C08G59/68—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 catalysts used
  • C08G59/686—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 catalysts used containing nitrogen

Definitions

• Epoxy polymers are used in a wide variety of applications including protective coatings, adhesives, electronic laminates, flooring and paving applications, glass fiber-reinforced pipes, and automotive parts. In their cured form, epoxy polymers offer desirable properties including good adhesion to other materials, excellent resistance to corrosion and chemicals, high tensile strength, and good electrical resistance. However, cured epoxy polymers can be brittle and lack toughness.
• a high heat epoxy composition comprising: a high heat epoxy compound having formula:
• R 1 and R 2 at each occurrence are each independently an epoxide-containing functional group;
• R a and R b at each occurrence are each independently halogen, C1-C12 alkyl, C2-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy;
• p and q at each occurrence are each independently 0 to 4;
• R 13 at each occurrence is independently a halogen or a Ci-Ce alkyl group;
• c at each occurrence is independently 0 to 4;
• R 14 at each occurrence is independently a Ci-Ce alkyl, phenyl, or phenyl substituted with up to five halogens or Ci-Ce alkyl groups;
• R g at each occurrence is independently C1-C12 alkyl or halogen, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six- membered cycloal
• compositions that provide desirable properties.
• the compositions include a high heat epoxy compound and an auxiliary epoxy compound different from the high heat epoxy compound.
• the compositions have desirable properties, including a glass transition temperature between -10°C and 62°C measured as per ASTM D3418.
• the glass transition temperature of the composition is between 15°C and 62°C measured as per ASTM D3418.
• the glass transition temperature of the composition is between 30°C and 62°C measured as per ASTM D3418.
• the glass transition temperature of the composition is between 40°C and 62°C measured as per ASTM D3418.
• the parallel-plate viscosity of the composition is 2,100,000 cP or less at 80°C. In an embodiment, the parallel-plate viscosity of the composition is 1,700,000 cP or less at 80°C. In an embodiment, the parallel-plate viscosity of the composition is 400,000 cP or less at 80°C. In an embodiment, the parallel-plate viscosity of the composition is 140,000 cP or less at 80°C.
• the high heat epoxy compound has formula (I) to (IX):
• R 1 and R 2 at each occurrence are each independently an epoxide-containing functional group;
• R a and R b at each occurrence are each independently halogen, C1-C12 alkyl, C2-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy;
• p and q at each occurrence are each independently 0 to 4;
• R 13 at each occurrence is independently a halogen or a Ci-C 6 alkyl group;
• c at each occurrence is independently 0 to 4;
• R 14 at each occurrence is independently a Ci-C 6 alkyl, phenyl, or phenyl substituted with up to five halogens or Ci-C 6 alkyl groups;
• R g at each occurrence is independently C1-C12 alkyl or halogen, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloal
• R 1 and R 2 at each occurrence can each be independently: wherein R a and R , i 3 b b are each independently hydrogen or C1-O2 alkyl. In certain embodiments, R 1 and R 2 are each independently ⁇
• the high heat epoxy compound has the formula
• R a and R b at each occurrence are each independently halogen, C1-C12 alkyl, C2-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy; p and q at each occurrence are each independently 0 to 4; R 13 at each occurrence is independently a halogen or a Ci-C 6 alkyl group; c at each occurrence is independently 0 to 4; R 14 at each occurrence is independently a Ci-C 6 alkyl, phenyl, or phenyl substituted with up to five halogens or Ci-C 6 alkyl groups; R g at each occurrence is independently C1-C12 alkyl or halogen, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloalkyl group; and t is 0 to 10.
• R a and R b at each occurrence are each independently halogen, C1-C12 alkyl, or C1-C12 alkoxy; p and q at each occurrence are each independently 0 to 2; R 13 at each occurrence is independently a halogen or a C1-C3 alkyl group; c at each occurrence is independently 0 to 2; R 14 at each occurrence is independently a Ci-C 6 alkyl or phenyl; R g at each occurrence is independently C1-C12 alkyl, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloalkyl group; and t is 1 to 5.
• R a and R b at each occurrence are each independently Ci- Ce alkyl, or Ci-C 6 alkoxy; p and q at each occurrence are each independently 0 to 2; R 13 at each occurrence is independently a C1-C3 alkyl group; c at each occurrence is independently 0 to 2; R 14 at each occurrence is independently a C1-C3 alkyl or phenyl; R g at each occurrence is independently Ci-C 6 alkyl; and t is 1 to 5.
• the high heat epoxy compound has the formula (1-a), (2- a), or
• the high heat epoxy compound can be prepared by methods described in, for example, WO2016/014536.
• the high heat epoxy compound can be from a corresponding bisphenol compound [e.g., a bisphenol of formula ( ) to (9')] ⁇
• the bisphenol can be provided in a mixture with an epoxide source, such as epichlorohydrin.
• the resultant mixture can be treated with a catalytic amount of base at a selected temperature.
• bases include, but are not limited to, carbonates (e.g., sodium bicarbonate, ammonium carbonate, or dissolved carbon dioxide), and hydroxide bases (e.g., sodium hydroxide, potassium hydroxide, or ammonium hydroxide).
• the base can be added as a powder (e.g., powdered sodium hydroxide).
• the base can be added slowly (e.g., over a time period of 60 to 90 minutes).
• the temperature of the reaction mixture can be maintained at 20 °C to 24 °C, for example.
• the reaction can be stirred for a selected time period (e.g., 5 hours to 24 hours, or 8 hours to 12 hours).
• the reaction can be quenched by addition of an aqueous solvent, optionally along with one or more organic solvents (e.g., ethyl acetate).
• the aqueous layer can be extracted (e.g., with ethyl acetate), and the organic extract can be dried and concentrated.
• the crude product can be purified (e.g., by silica gel chromatography) and isolated.
• the isolated product can be obtained in a yield of 80% or greater, 85% or greater, or 90% or greater.
• the composition can comprise a high heat epoxy compound wherein the purity is 95% or greater, preferably 97% or greater, preferably 99% or greater, as determined by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• the high heat epoxy compound can have a metal impurity content of 3 ppm or less, 2 ppm or less, 1 ppm or less, 500 ppb or less, 400 ppb or less, 300 ppb or less, 200 ppb or less, or 100 ppb or less.
• the metal impurities may be iron, calcium, zinc, aluminum, or a combination thereof.
• the compounds can have an unknown impurities content of 0.1 wt% or less.
• the compounds can have a color APHA value of 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less, as measured using test method ASTM D1209.
• the high heat epoxy compounds can be substantially free of epoxide oligomer impurities.
• the epoxides can have an oligomer impurity content of less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.4%, less than or equal to 0.3%, less than or equal to 0.2%, or less than or equal to 0.1%, as determined by high performance liquid chromatography.
• the epoxides can have an epoxy equivalent weight corresponding to purity of the bisepoxide of 95% purity or greater, 96% purity or greater, 97% purity or greater, 98% purity or greater, 99% purity or greater, or 100% purity.
• Epoxy equivalent weight (EEW) is the weight of material in grams that contains one mole of epoxy groups. It is also the molecular weight of the compound divided by the number of epoxy groups in one molecule of the compound.
• the high heat epoxy composition includes an auxiliary epoxy compound different from the high heat epoxy compound.
• the high heat epoxy composition includes 5 to 50 wt% of the auxiliary epoxy compound.
• the high heat epoxy composition includes 5 to 25 wt% of the auxiliary epoxy compound.
• the high heat epoxy composition includes 5 to 10 wt% of the auxiliary epoxy compound.
• the auxiliary epoxy compound is an aliphatic epoxy compound, cycloaliphatic epoxy compound, aromatic epoxy compound, bisphenol A epoxy compound, bisphenol-F epoxy compound, phenol novolac epoxy polymer, cresol-novolac epoxy polymer, biphenyl epoxy compound, triglycidyl p-aminophenol, tetraglycidyl diamino diphenyl methane, polyfunctional epoxy compound, naphthalene epoxy compound, divinylbenzene dioxide compound, 2-glycidylphenylglycidyl ether, dicyclopentadiene-type epoxy compound, multi aromatic type epoxy polymer, bisphenol-S type epoxy compound, isocyanurate type epoxy compound, hydantoin type epoxy compound or a combination comprising at least one of the foregoing.
• the auxiliary epoxy compound is a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether, a neopentylglycol diglycidyl ether, a 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexane carboxylate, a N,N-diglycidyl-4-glycidyloxyaniline, a ⁇ , ⁇ , ⁇ ', ⁇ '- tetraglycidyl-4,4'-diaminodiphenylmethane, or a combination comprising at least one of the foregoing.
• the auxiliary epoxy compound can have formula: wherein A is an organic or inorganic radical of valence n, X is oxygen or nitrogen, m is 1 or 2 and consistent with the valence of X, R is hydrogen or methyl, n is 1 to 1000, specifically 1 to 8, more specifically 2 or 3 or 4.
• auxiliary epoxy compounds include, for example, halogenated hydantoin epoxy compounds, triphenylmethane epoxy compounds, tetra phenyl-glycidyl-ether of tetraphenyl ethane (4 functionality epoxy compound), and novolac type epoxy compounds.
• Auxiliary epoxy compounds include those having the following structures:
• Auxiliary epoxy compounds for many applications include those produced by the reaction of epichlorohydrin or epibromohydrin with a phenolic compound.
• Suitable phenolic compounds include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7- dihydroxynapthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol)2,2'- biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2'6,6'-tetramethylbiphenol, 3, 3 '-dibromo-2,2', 6,6' -tetramethylbiphenol, 2,2' ,6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidened
• auxiliary epoxy compounds include N-glycidyl phthalimide, N- glycidyltetrahydrophthalimide, phenyl glycidyl ether, p-butylphenyl glycidyl ether, styrene oxide, neohexene oxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethyleneglycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol-type epoxy compounds, phenol novolac-type epoxy compounds, ortho-cresol novolac-type epoxy compounds, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, and phthalic acid diglycidyl ester.
• auxiliary epoxy compounds include the glycidyl ethers of phenolic compounds such as the glycidyl ethers of phenol-formaldehyde novolac, alkyl substituted phenol-formaldehyde compounds including cresol-formaldehyde novolac, i-butylphenol- formaldehyde novolac, sec-butylphenol-formaldehyde novolac, ie/t-octylphenol-formaldehyde novolac, cumylphenol-formaldehyde novolac, decylphenol-formaldehyde novolac.
• phenolic compounds such as the glycidyl ethers of phenol-formaldehyde novolac, alkyl substituted phenol-formaldehyde compounds including cresol-formaldehyde novolac, i-butylphenol- formaldehyde novolac, sec-butylphenol-formaldehyde
• auxiliary epoxy compounds are the glycidyl ethers of bromophenol-formaldehyde novolac, chlorophenolformaldehyde novolac, phenol-bis(hydroxymethyl)benzene novolac, phenol- bis(hydroxymethylbiphenyl) novolac, phenol-hydroxybenzaldehyde novolac, phenol- dicylcopentadiene novolac, naphthol-formaldehyde novolac, naphthol- bis(hydroxymethyl)benzene novolac, naphthol-bis(hydroxymethylbiphenyl) novolac, naphthol- hydroxybenzaldehyde novolac, and naphthol-dicylcopentadiene novolacs, and the like, and mixtures thereof.
• auxiliary epoxy compounds include the polyglycidyl ethers of polyhydric aliphatic alcohols.
• polyhydric alcohols include 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols, glycerol, trimethylolpropane, 2,2-bis(4- hydroxycyclohexyl)propane, and pentaerythritol.
• auxiliary epoxy compounds are polyglycidyl esters which are obtained by reacting epichlorohydrin or similar epoxy compounds with an aliphatic,
• cycloaliphatic, or aromatic polycarboxylic acid such as oxalic acid, adipic acid, glutaric acid, phthalic, isophthalic, terephthalic, tetrahydrophthalic or hexahydrophthalic acid, 2,6- naphthalenedicarboxylic acid, and dimerized fatty acids.
• aromatic polycarboxylic acid such as oxalic acid, adipic acid, glutaric acid, phthalic, isophthalic, terephthalic, tetrahydrophthalic or hexahydrophthalic acid, 2,6- naphthalenedicarboxylic acid, and dimerized fatty acids.
• Examples are diglycidyl terephthalate and diglycidyl hexahydrophthalate.
• polyepoxide compounds which contain the epoxide groups in random distribution over the molecule chain and which can be prepared by emulsion copolymerization using olefinically unsaturated compounds that contain these epoxide groups, such as, for example, glycidyl esters of acrylic or methacrylic acid, can be used.
• auxiliary epoxy compounds that can be used are those based on heterocyclic ring systems, for example hydantoin epoxy compounds, triglycidyl isocyanurate and its oligomers, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether,
• tetraglycidyldiaminodiphenylmethane tetraglycidyldiaminodiphenyl ether
• tetrakis(4- glycidyloxyphenyl)ethane urazole epoxides, uracil epoxides, and oxazolidinone-modified epoxy compounds .
• auxiliary epoxy compounds are polyepoxides based on aromatic amines, such as aniline, for example ⁇ , ⁇ -diglycidylaniline, diaminodiphenylmethane and cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate, 4,4'-(l,2-epoxyethyl)biphenyl, 4,4'-di(l,2-epoxyethyl)diphenyl ether, and bis(2,3-epoxycyclopentyl)ether.
• auxiliary epoxy compounds are mixed multifunctional epoxy compounds obtained from compounds that contain a combination of functional groups mentioned above, for example 4-aminophenol.
• Examples of mono-functional auxiliary epoxy compounds include 2-ethylhexyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, t-butyl glycidyl ether, o-cresyl glycidyl ether, and nonyl phenol glycidyl ether.
• Oxazolidinone-modified auxiliary epoxy compounds can also be used, such as those disclosed in Angew. Makromol. Chem., vol. 44, (1975), pages 151-163, and U.S. Patent No. 3,334,110 to Schramm.
• An example is the reaction product of bisphenol A diglycidyl ether with diphenylmethane diisocyanate in the presence of an appropriate accelerator.
• Auxiliary epoxy compounds can be prepared by condensation of an epoxy compound with a phenol such as a bisphenol.
• a phenol such as a bisphenol.
• a typical example is the condensation of bisphenol A with a bisphenol A diglycidyl ether to produce an oligomeric diglycidyl ether.
• a phenol dissimilar to the one used to derive the epoxy compound can be used.
• tetrabromobisphenol A can be condensed with bisphenol A diglycidyl ether to produce an oligomeric diglycidyl ether containing halogens.
• the auxiliary epoxy compound can be a solid at room temperature.
• the epoxy compound has a softening point of 25°C to 150°C.
• the auxiliary epoxy compound can be a liquid or a softened solid at room temperature.
• the auxiliary epoxy compound has a softening point less than 25°C.
• the high heat epoxy composition can include a curing promoter.
• curing promoter encompasses compounds whose roles in curing epoxy compounds are variously described as those of a hardener, a hardening accelerator, a curing catalyst, and a curing co-catalyst, among others.
• the curing promoter can be an aromatic diamine compound.
• the high heat epoxy composition includes a hardener.
• the hardener is an amine compound.
• the amine compound can be 4-aminophenyl sulfone (DDS), 4,4'- methylenedianiline, diethyltoluenediamine, 4,4'- methylenebis(2,6-diethylaniline), m-phenylenediamine, p-phenylenediamine, 2,4-bis(p- aminobenzyl)aniline, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, m- xylylenediamine, p-xylylenediamine, a diethyl toluene diamine, or a combination comprising at least one of the foregoing.
• DDS 4-aminophenyl sulfone
• the amine compound can be 4-aminophenyl sulfone (DDS), 4,4'-methylenebis-(2,6-diethylaniline) (MDEA), or a combination comprising at least one of the foregoing.
• the hardener is methyl-5-norbornene-2,3-dicarboxylic anhydride (NMA). The amount of curing promoter will depend on the type of curing promoter, as well as the identities and amounts of the other components of the high heat epoxy
• the curing promoter is an aromatic diamine amine compound
• it can be used in an amount of 10 to 30 weight percent of the high heat epoxy composition.
• the curing promoter can be an aromatic dianhydride.
• the curing promoter can be an aromatic dianhydride.
• aromatic dianhydride compound has the general structure , where R
• curing promotors examples include 4,4'-(4,4'-isopropylidenediphenoxy)bis- (phthalic anhydride) (CAS Reg. No. 38103-06-9), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (CAS Reg. No. 1107-00-2), 4,4'-oxydiphthalic anhydride (CAS Reg. No. 1823-59-2), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (CAS Reg. No. 2421-28-5), and 3,3 ',4,4'- biphenyltetracarboxylic dianhydride (CAS Reg. No. 2420-87-3), and specifically compounds having the formulas below.
• the curing promoter can be a bicyclic anhydride.
• the bicyclic anhydride compound can be methyl-5-norbornene-2,3-dicarboxylic anhydride (CAS Reg. No. 25134-21-8) and cis-5-norbornene-endo-2,3-dicarboxylic anhydride (CAS Reg. No. 129-64-6) and specificall compounds having the formulas below.
• a cured sample of the high heat epoxy composition has a glass transition temperature of less than 270°C as measured by differential scanning calorimetry. In an embodiment, a cured sample of the high heat epoxy has a glass transition temperature between 150°C to 270°C as measured by differential scanning calorimetry. In an embodiment, a cured sample of the high heat epoxy has a glass transition temperature between 170°C to 270°C as measured by differential scanning calorimetry. In an embodiment, a cured sample of the high heat epoxy has a glass transition temperature between 175°C to 275°C, as measured by dynamic mechanical thermal analyzer. In an embodiment, a cured sample of the high heat epoxy has a glass transition temperature between 190°C to 275°C, as measured by dynamic mechanical thermal analyzer.
• the composition does not contain a solvent.
• the high heat epoxy compositions can include a solvent to prepare homogeneous epoxy blends and then the solvent can be removed.
• Applications for the high heat epoxy compositions include, for example, acid bath containers; neutralization tanks; aircraft components; bridge beams; bridge deckings; electrolytic cells; exhaust stacks; scrubbers; sporting equipment; stair cases; walkways;
• automobile exterior panels such as hoods and trunk lids; floor pans; air scoops; pipes and ducts, including heater ducts; industrial fans, fan housings, and blowers; industrial mixers; boat hulls and decks; marine terminal fenders; tiles and coatings; building panels; business machine housings; trays, including cable trays; concrete modifiers; dishwasher and refrigerator parts; electrical encapsulants; electrical panels; tanks, including electrorefining tanks, water softener tanks, fuel tanks, and various filament-wound tanks and tank linings; furniture; garage doors; gratings; protective body gear; luggage; outdoor motor vehicles; pressure tanks; printed circuit boards; optical waveguides; radomes; railings; railroad parts such as tank cars; hopper car covers; car doors; truck bed liners; satellite dishes; signs; solar energy panels; telephone switchgear housings; tractor parts; transformer covers; truck parts such as fenders, hoods, bodies, cabs, and beds; insulation for rotating machines including ground insulation, turn insulation, and phase separation insulation; commut
• compositions and methods described herein are further illustrated by the following non-limiting examples.
• compositions were tested using the test methods listed in Table 2. Unless indicated otherwise, all test methods are the test methods in effect as of the filing date of this application.
• Comparative Examples A, B, and C show the effect on viscosity of a PPPBP- epoxy/DDS sample as the temperature increases.
• PPPBP-epoxy 81.7 grams was heated to 160°C and DDS (18.3 grams) was added and dissolved. The temperature was lowered to 120°C (Comparative Example A), 140°C (Comparative Example B), or 160°C (Comparative Example C) and the spindle viscosity was measured over time.
• high heat epoxy compositions using auxiliary epoxy compounds were prepared.
• the auxiliary epoxy compound is liquid at room temperature. These amorphous blends can exhibit glass transition temperatures around room temperature or below.
• the high heat epoxy compositions described do not require a solvent.
• a solvent can be used to prepare homogenous epoxy blends and then the solvent can be removed.
• Procedure 1 The auxiliary epoxy compound was warmed to 100 to 140°C and the PPPBP-epoxy was added with stirring. After the PPPBP-epoxy dissolved, the mixture was cooled.
• Procedure 2 The PPPBP-epoxy and the auxiliary epoxy compound were weighed and placed together in a vessel and heated while stirring. After the PPPBP-epoxy dissolved, the mixture was allowed to cool to room temperature.
• results of glass transition temperature measurements for compositions of PPPBP-epoxy and NPG DGE are provided in Table 5. Over the compositional range studied, there was no indication of any crystalline melting point. NPG DGE was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperature of the composition decreases as an increasing amount of NPG DGE was used.
• results of glass transition temperature measurements for compositions of PPPBP-epoxy and ECHM are provided in Table 6. Over the compositional range studied, there was no indication of any crystalline melting point. ECHM was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperatures of the compositions decreased when increasing amounts of ECHM were used.
• Results of glass transition temperature measurements for compositions of PPPBP-epoxy and BPA-DGE-2 are provided in Table 7. Over the compositional range studied, there was no indication of any crystalline melting point. BPA DGE-2 was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperature and the viscosity of the compositions decrease as an increasing amounts of BPA DGE-2 was used.
• results of glass transition temperature measurements for compositions of PPPBP-epoxy and BISF-DGE are provided in Table 8. Over the compositional range studied, there was no indication of any crystalline melting point. BISF-DGE was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperature and the viscosity of the compositions decrease as an increasing amounts of BISF-DGE was used.
• Results of glass transition temperature measurements for compositions of PPPBP-epoxy and TGAP are provided in Table 9. Over the compositional range studied, there was no indication of any crystalline melting point. TGAP was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperature and the viscosity of the compositions decrease as an increasing amounts of TGAP was used.
• results of glass transition temperature measurements for compositions of PPPBP-epoxy and TGDDM are provided in Table 10. Over the compositional range studied, there was no indication of any crystalline melting point. TGDDM was effective in producing homogeneous, amorphous blends. In addition, the glass transition temperature and the viscosity of the compositions decrease as an increasing amounts of TGDDM was used
• Preparing castings involved mixing the epoxy polymers from 90 to 140°C. In some cases, after the blend was homogeneous, the temperature was decreased to 80 to 110°C. Solid curatives were melted before adding to the homogeneous epoxy blends. Liquid curatives were added with stirring. After degassing the formulated polymer in a vacuum oven at 100°C, it was poured into a mold and cured according to Cure Schedule A or B.
• the temperature was maintained at 140°C even after the blend was homogeneous.
• Solid curatives were melted before adding to the homogeneous epoxy blends. Liquid curatives were added with stirring. After degassing the formulated polymer under vacuum at 140°C, it was poured into a mold and cured according to Cure Schedule A or B.
• the temperature was decreased to ambient temperature and stored overnight. The following day, the blend was warmed to 80 to 110°C. Solid curatives were melted before adding to the homogeneous epoxy blends. Liquid curatives were added with stirring. After degassing the formulated polymer in a vacuum oven at 100°C, it was poured into a mold and cured according to Cure Schedule A or B.
• Castings were prepared from a blend of PPPBP-epoxy and BPA-DGE-2 with DDS hardener using Cure Schedule B. Before curing, samples of the degassed polymers were taken and viscosity determined using Small Amplitude Oscillatory Rheological testing at 80 and 90 °C. Table 11 provides glass transition temperature and viscosity results. The use of BPA- DGE-2 resulted in significant decreases in viscosity in the formulated polymers. The castings exhibited very high glass transition temperatures.
• Castings were prepared from a blend of PPPBP-epoxy BISF-DGE using Cure Schedule B.
• Example 33 used MDEA as a hardener.
• Examples 34-37 and Comparative Example K used DDS as a hardener.
• samples of the degassed polymers were taken and viscosity determined using Small Amplitude Oscillatory Rheological testing at 90°C.
• Table 12 provides glass transition temperature and viscosity results.
• the use of BISF-DGE resulted in significant decreases in viscosity in the formulated polymers.
• the castings exhibited very high glass transition temperatures.
• Castings were prepared from a blend of PPPBP-epoxy and TGAP using Cure Schedule B.
• Example 38 used MDEA as a hardener.
• Examples 39-41 and Comparative Example L used DDS as a hardener.
• samples of the degassed polymers were taken and viscosity determined using Small Amplitude Oscillatory Rheological testing at 90°C.
• Table 13 provides glass transition temperature and viscosity results.
• the use of TGAP resulted in significant decreases in viscosity in the formulated polymers.
• the castings exhibited very high glass transition temperatures.
• Castings were prepared from a blend of PPPBP-epoxy and TGDDM with DDS hardener using Cure Schedule B. Before curing, samples of the degassed polymers were taken and viscosity determined using Small Amplitude Oscillatory Rheological testing at 90°C. Table 14 provides glass transition temperature and viscosity results. The use of TGDDM resulted in significant decreases in viscosity in the formulated polymers. The castings exhibited very high glass transition temperatures.
• Castings were prepared from a blend of PPPBP-epoxy with two auxiliary epoxy compounds: ECHM and either NPG DGE or DGE BPA-1 with DDS hardener using Cure Schedule A. Table 15 provides glass transition temperature results. The castings exhibited very high glass transition temperatures.
• Example 16 shows the use of an anhydride hardener with epoxy blends of PPPBP-Epoxy. Castings were prepared from a blend of PPPBP-epoxy and BPA DGE-2 with NMA hardener and 1-MeI catalyst using Cure Schedule A. The catalyst amount is expressed in ppm (parts per hundred polymer by weight). Table 16 provides glass transition temperature results for a cast sample. The castings exhibited very high glass transition temperatures.
• compositions, methods, articles and other aspects are further described by the Embodiments below.
• Embodiment 1 A high heat epoxy composition comprising: a high heat epoxy compound having formula:
• R 1 and R 2 at each occurrence are each independently an epoxide-containing functional group;
• R a and R b at each occurrence are each independently halogen, C1-C12 alkyl, C2-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy;
• p and q at each occurrence are each independently 0 to 4;
• R 13 at each occurrence is independently a halogen or a Ci-C 6 alkyl group;
• c at each occurrence is independently 0 to 4;
• R 14 at each occurrence is independently a Ci-C 6 alkyl, phenyl, or phenyl substituted with up to five halogens or Ci-C 6 alkyl groups;
• R g at each occurrence is independently C1-C12 alkyl or halogen, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloal
• Embodiment 2 The composition of Embodiment 1, comprising 5 to 50 wt%, preferably 5 to 25 wt%, preferably 5 to 10 wt% of the auxiliary epoxy compound.
• Embodiment 3 The composition of Embodiment 1 or 2, further comprising a hardener.
• Embodiment 4 The composition of Embodiment 3, wherein a cured sample of the composition has a glass transition temperature of less than 270°C, preferably between 150°C to 270°C, preferably between 170°C to 270°C as measured by differential scanning calorimetry.
• Embodiment 5 The composition of Embodiment 3, wherein a cured sample of the composition has a glass transition temperature between 175°C to 275°C , preferably between 190°C to 275°C, as measured by dynamic mechanical thermal analyzer.
• Embodiment 6 The composition of Embodiment 3, wherein the hardener is an amine compound.
• Embodiment 7 The composition of Embodiment 3, wherein the hardener is 4- aminophenyl sulfone (DDS), 4,4'-methylenebis-(2,6-diethylaniline) (MDEA), 4,4'- methylenedianiline, diethyltoluenediamine, 4,4'-methylenebis-(2,6-dimethylaniline), m- phenylenediamine, p-phenylenediamine, 2,4-bis(p-aminobenzyl)aniline, 3,5-diethyltoluene-2,4- diamine, 3,5-diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylenediamine, diethyl toluene diamines, preferably 4-aminophenyl sulfone (DDS), 4,4'-methylenebis-(2,6- diethylaniline) (MDEA), or
• Embodiment 8 The composition of Embodiment 3, wherein the hardener is an aromatic dianhydride or a bicyclic anhydride.
• Embodiment 9 The composition of Embodiment 3, wherein the hardener is methyl-5-norbornene-2,3-dicarboxylic anhydride (NMA).
• NMA methyl-5-norbornene-2,3-dicarboxylic anhydride
• Embodiment 10 The composition of any one or more of Embodiments 1 to 9, wherein the auxiliary epoxy compound is an aliphatic epoxy compound, cycloaliphatic epoxy compound, aromatic epoxy compound, bisphenol A epoxy compound, bisphenol-F epoxy compound, phenol novolac epoxy polymer, cresol-novolac epoxy polymer, biphenyl epoxy compound, triglycidyl p-aminophenol, tetraglycidyl diamino diphenyl methane, polyfunctional epoxy compound, naphthalene epoxy compound, divinylbenzene dioxide compound, 2-glycidylphenylglycidyl ether, dicyclopentadiene-type epoxy compound, multi aromatic type epoxy polymer, or a combination comprising at least one of the foregoing.
• the auxiliary epoxy compound is an aliphatic epoxy compound, cycloaliphatic epoxy compound, aromatic epoxy compound, bisphenol A epoxy compound, bisphenol-F epoxy compound, phenol novolac epoxy polymer, cresol-novolac
• Embodiment 11 The composition of any one or more of the Embodiments 1 to 10, wherein the auxiliary epoxy compound is a bisphenol A diglycidylether, a bisphenol F diglycidylether, a neopentylglycol diglycidyl ether, a 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate, a N,N-diglycidyl-4-glycidyloxyaniline, a ⁇ , ⁇ , ⁇ ', ⁇ '- tetraglycidyl-4,4'-diaminodiphenylmethane, or a combination comprising at least one of the foregoing.
• the auxiliary epoxy compound is a bisphenol A diglycidylether, a bisphenol F diglycidylether, a neopentylglycol diglycidyl ether, a 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohe
• Embodiment 12 The composition of any one or more of Embodiments 1 to 11, wherein Rl and R2 at each occurrence are each independently:
• R ia and R b are each independently hydrogen or CVC12 alkyl.
• Embodiment 13 The composition of any one or more of Embodiments 1 to 12, wherein the high heat epoxy compound has the formula (1-a), (2-a), or 4(b)
• Embodiment 14 The composition of any one or more of Embodiments 1 to 13, wherein the composition does not contain a solvent.
• compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
• the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
• hydrocarbyl and “hydrocarbon” refers broadly to a substituent comprising carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof;
• alkyl refers to a straight or branched chain, saturated monovalent hydrocarbon group;
• alkylene refers to a straight or branched chain, saturated, divalent hydrocarbon group;
• alkylidene refers to a straight or branched chain, saturated divalent hydrocarbon group, with both valences on a single common carbon atom;
• alkenyl refers to a straight or branched chain monovalent hydrocarbon group having at least two carbons joined by a carbon-carbon double bond;
• cycloalkyl refers to a non- aromatic monovalent monocyclic or multicyclic hydrocarbon group having at least three carbon atoms, "cycloalkenyl” refers to a non-aromatic cyclic di
• each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.
• substituted means that at least one hydrogen on the designated atom or group is replaced with another group, provided that the designated atom's normal valence is not exceeded.
• two hydrogens on the atom are replaced.
• Combinations of substituents or variables are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the compound.
• Exemplary groups that can be present on a "substituted" position include, but are not limited to, cyano; hydroxyl; nitro; azido; alkanoyl (such as a C2-6 alkanoyl group such as acyl); carboxamido; C 1-6 or C1-3 alkyl, cycloalkyl, alkenyl, and alkynyl (including groups having at least one unsaturated linkages and from 2 to 8, or 2 to 6 carbon atoms); C 1-6 or C1-3 alkoxys; C6-10 aryloxy such as phenoxy; C 1-6 alkylthio; C 1-6 or C1-3 alkylsulfinyl; C 1-6 or C1-3
• alkylsulfonyl aminodi(Ci-6 or Ci-3)alkyl; C 6 -i2 aryl having at least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic); C7-19 arylalkyl having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms; or arylalkoxy having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms, with benzyloxy being an exemplary arylalkoxy.
• a line extending from a structure signifies a terminating methyl group -CH3.

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