JP6831008B2 - Uniform amorphous high heat epoxy blends, articles, and their use - Google Patents

Description

Cross-reference to related applications This application claims priority to US Provisional Application No. 62 / 399,879 filed on September 26, 2016, the contents of which are incorporated herein by reference.

Epoxy polymers are used in a wide variety of applications including protective coatings, adhesives, electronic laminates, floor and pavement applications, fiberglass reinforced pipes, and automotive parts. Epoxy polymers, in cured form, provide desirable properties including good adhesion to other materials, excellent resistance to corrosion and chemicals, high tensile strength, and good electrical resistance. However, the cured epoxy polymer may be brittle and lack toughness.

WO2016 / 014536A1 Published in the United States 2015/0413 38 U.S. Pat. No. 3,334,110

Angew. Makromol. Chem., Vol. 44, (1975), pp. 151-163

Epoxy-based materials with improved properties are needed.

formula:

(In the formula, R ¹ and R ² for each appearance are independently epoxide-containing functional groups; R ^a and R ^b for each appearance are independently halogen, C _{1 to} C ₁₂ alkyl, and C _{2 respectively.} ~ C ₁₂ alkenyl, C ₃ ~ C ₈ cycloalkyl, or C ₁ ~ C ₁₂ alkoxy; p and q per appearance are 0-4 independently, respectively; R ¹³ per appearance is independent Halogen, or C _{1 to} C ₆ alkyl group; c per appearance is 0 to 4 independently; R ¹⁴ per appearance is independently C _{1 to} C ₆ alkyl, phenyl, or max. Phenyl substituted with 5 halogens or C _{1 to} C ₆ alkyl groups; each appearance R ^g is independently C _{1 to} C ₁₂ alkyl or halogen, or 2 R ^g groups are Together with the carbon atoms they are attached to, they form a 4, 5- or 6-membered cycloalkyl group; t is 0 to 10).
A hot epoxy composition comprising a hot epoxy compound having a hot epoxy compound and an auxiliary epoxy compound different from the hot epoxy compound; between -10 ° C and 62 ° C, preferably 15 ° C to 62 ° C, measured according to ASTM D3418. Has a glass transition temperature between, preferably between 30 ° C and 62 ° C, preferably between 40 ° C and 62 ° C, at 80 ° C below 2,100,000 cP, preferably at 80 ° C below 1,700,000 cP, preferably at 80 ° C. A composition having a parallel plate viscosity of 400,000 cP or less, or preferably 140,000 cP or less at 80 ° C. is provided.

The above and other features are illustrated by the detailed description below.

We have discovered a composition that provides the desired properties. The composition comprises a hot epoxy compound and an auxiliary epoxy compound different from the hot epoxy compound. The composition has desirable properties, including a glass transition temperature between -10 ° C and 62 ° C as measured according to ASTM D3418. In one embodiment, the glass transition temperature of the composition is between 15 ° C and 62 ° C as measured according to ASTM D3418. In one embodiment, the glass transition temperature of the composition is between 30 ° C and 62 ° C as measured according to ASTM D3418. In one embodiment, the glass transition temperature of the composition is between 40 ° C and 62 ° C as measured according to ASTM D3418. In one embodiment, the parallel plate viscosity of the composition is no more than 2,100,000 cP at 80 ° C. In one embodiment, the parallel plate viscosity of the composition is less than 1,700,000 cP at 80 ° C. In one embodiment, the parallel plate viscosity of the composition is not less than 400,000 cP at 80 ° C. In one embodiment, the parallel plate viscosity of the composition is 140,000 cP or less at 80 ° C.

In embodiments, the hot epoxy compounds are of formulas (I)-(IX) :.

(In the formula, R ¹ and R ² for each appearance are independently epoxide-containing functional groups; R ^a and R ^b for each appearance are independently halogen, C _{1 to} C ₁₂ alkyl, and C _{2 respectively.} ~ C ₁₂ alkenyl, C ₃ ~ C ₈ cycloalkyl, or C ₁ ~ C ₁₂ alkoxy; p and q per appearance are 0-4 independently, respectively; R ¹³ per appearance is independent Halogen, or C _{1 to} C ₆ alkyl group; c per appearance is 0 to 4 independently; R ¹⁴ per appearance is independently C _{1 to} C ₆ alkyl, phenyl, or max. Phenyl substituted with 5 halogens or C _{1 to} C ₆ alkyl groups; each appearance R ^g is independently C _{1 to} C ₁₂ alkyl or halogen, or 2 R ^g groups are Together with the carbon atoms they are attached to, they form a 4, 5- or 6-membered cycloalkyl group; t is 0 to 10).
Have.

In the embodiment, R ¹ and R ² for each appearance are independent of each other:

(In the formula, R ^3a and R ^3b are independently hydrogen or C _{1 to} C ₁₂ alkyl, respectively)
Can be. In certain embodiments, R ¹ and R ² are independent of each other.

Is.

In an embodiment, the hot epoxy compound is of formula

(In the formula, R ^a and R ^b for each appearance are independently halogen, C _{1 to} C ₁₂ alkyl, C _{2 to} C ₁₂ alkenyl, C _{3 to} C ₈ cycloalkyl, or C _{1 to} C ₁₂ alkoxy. Yes; p and q per appearance are independently 0-4; R ¹³ per appearance is independently halogen or C _1- C ₆ alkyl group; c per appearance is independent And 0-4; R ¹⁴ per appearance is independently C _1- C ₆ alkyl, phenyl, or phenyl substituted with up to 5 halogens or C _1- C ₆ alkyl groups; Each R ^g is independently C _{1 to} C ₁₂ alkyl or halogen, or two R ^g groups, together with the carbon atom to which they are attached, are 4, 5 or 6-membered cycloalkyl. Form a group; t is 0 to 10)
Have.

In some embodiments, R ^a and R ^b per appearance are independently halogen, C _{1 to} C ₁₂ alkyl, or C _{1 to} C ₁₂ alkoxy, respectively; p and q per appearance are independent, respectively. And 0 to 2; R ¹³ per appearance is an independent halogen, or C _{1 to} C ₃ alkyl group; c per appearance is 0 to 2 independently; R per appearance. ¹⁴ is independently C _{1 to} C ₆ alkyl, or phenyl; each appearance R ^g is independently C _{1 to} C ₁₂ alkyl, or two R ^g groups are attached to them. Together with the carbon atoms present, it forms a 4, 5- or 6-membered cycloalkyl group; t is 1-5.

In some embodiments, R ^a and R ^b per appearance are independently C _{1 to} C ₆ alkyl, or C _{1 to} C ₆ alkoxy, respectively; p and q per appearance are independent, respectively. 0 to 2; R ¹³ per appearance is an independent C _{1 to} C ₃ alkyl group; c per appearance is 0 to 2 independently; R ¹⁴ per appearance is independent C _{1 to} C ₃ alkyl, or phenyl; R ^g for each appearance is independently C _{1 to} C ₆ alkyl; t is 1 to 5.

In embodiments, the hot epoxy compounds are of formula (1-a), (2-a), or (4-b).

Have.

In one embodiment, the hot epoxy compound is of formula (1-a).

Have. The hot epoxy compound can be prepared, for example, by the method described in WO 2016/014536. The hyperthermal epoxy compound can be derived from the corresponding bisphenol compound [eg, bisphenol of formulas (1')-(9')].

Bisphenols can be provided as a mixture with an epoxide source such as epichlorohydrin. The resulting mixture can be treated with a catalytic amount of base at selected temperatures. Suitable bases include carbonates (eg, sodium bicarbonate, ammonium carbonate, or dissolved carbon dioxide), and hydroxide bases (eg, sodium hydroxide, potassium hydroxide, or ammonium hydroxide). Not limited to. The base can be added as a powder (eg, powdered sodium hydroxide). The base can be added slowly (eg, over a period of 60-90 minutes). The temperature of the reaction mixture can be maintained, for example, between 20 ° C and 24 ° C. The reaction can be stirred for a selected period of time (eg, 5 to 24 hours, or 8 to 12 hours). The reaction can be quenched by the addition of an aqueous solvent, optionally with one or more organic solvents (eg, ethyl acetate). The aqueous layer can be extracted (eg with ethyl acetate) and the organic extract can be dried and concentrated. Crude organisms can be purified (eg, by silica gel chromatography) and isolated. The isolated product can be obtained in yields of 80% or higher, 85% or higher, or 90% or higher.

In certain embodiments, the composition can comprise a high thermal epoxy compound having a purity of 95% or higher, preferably 97% or higher, preferably 99% or higher, as determined by high performance liquid chromatography (HPLC). WO 2016/014536A1 and US Publication No. 2015/041338 disclose that high-purity epoxies with low oligomer content exhibit lower viscosities, which can promote infiltration of fibers during processing to produce prepregs and laminates. ..

The hot 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 compound can have an unknown impurity content of 0.1% by mass or less. Compounds 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 when measured using the test method ASTM D1209. be able to.

The hot epoxy compound can be substantially free of epoxide oligomer impurities. Epoxides have an oligomeric impurity content of 3% or less, 2% or less, 1% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less, as determined by high-performance liquid chromatography. Can have. The epoxide has an epoxy equivalent corresponding to a purity of 95% or higher, a purity of 96% or higher, a purity of 97% or higher, a purity of 98% or higher, a purity of 99% or higher, or a purity of 100% pure bisepoxide. be able to. Epoxy equivalent (EEW) is the mass of material in grams containing 1 mole of epoxy group. It is also the molecular weight of the compound divided by the number of epoxy groups in one molecule of the compound.

The hot epoxy composition contains an auxiliary epoxy compound that is different from the hot epoxy compound. In one embodiment, the hot epoxy composition comprises 5-50% by weight of an auxiliary epoxy compound. In one embodiment, the hot epoxy composition comprises 5-25% by weight of an auxiliary epoxy compound. In one embodiment, the hot epoxy composition comprises 5-10% by weight of an auxiliary epoxy compound.

In embodiments, the auxiliary epoxy compounds are aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, phenol novolac epoxy polymers, cresol-novolac epoxy polymers, biphenyl epoxy compounds, Triglycidyl p-aminophenol, tetraglycidyldiaminodiphenylmethane, polyfunctional epoxy compound, naphthalene epoxy compound, divinylbenzenedioxide compound, 2-glycidylphenylglycidyl ether, dicyclopentadiene type epoxy compound, polyaromatic epoxy polymer, bisphenol S A type epoxy compound, an isocyanurate type epoxy compound, a hidden toin type epoxy compound, or a combination containing at least one of the above. In embodiments, the auxiliary epoxy compounds are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, neopentyl glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-diglycidyl. -4-Glysidyloxyaniline, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, or a combination containing at least one of the above.

The auxiliary epoxy compound has the formula:

(In the formula, A is an organic or inorganic group with a valence of n, X is oxygen or nitrogen, m is 1 or 2, which matches the valence of X, and R is hydrogen or methyl. And n is 1 to 1000, specifically 1 to 8, more specifically 2 or 3 or 4)
Can have.

Examples of other auxiliary epoxy compounds include halogenated hydantin epoxy compounds, triphenylmethane epoxy compounds, tetraphenyl-glycidyl-ether of tetraphenylethane (tetrafunctional epoxy compounds), and novolak type epoxy compounds.

As an auxiliary epoxy compound, the following structure:

(In the formula, each appearance of R is independently hydrogen or methyl; each appearance of M independently optionally further comprises an oxylane, carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, or nitrile. C1-C18 hydrocarbylene; each appearance of X independently contains hydrogen, chloro, fluoro, bromo, or optionally carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, or nitrile, C1-C18 hydrocarbyl. Each appearance of B is independently a carbon-carbon single bond, C1-C18 hydrocarbyl, C1-C12 hydrocarbyloxy, C1-C12 hydrocarbylthio, carbonyl, sulfide, sulfonyl, sulfinyl, phosphoryl, silane, or carboxyalkyl. , Carboxamides, ketones, aldehydes, alcohols, halogens, or nitriles, these groups; n is 1-20; each occurrence of p and q is 0-20 independently).
Those having

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-dihydroxynaphthalene, 2- (diphenylphosphoryl) hydroquinone, bis (2,6-dimethylphenol) 2,2'- Biphenols, 4,4-biphenols, 2,2', 6,6'-tetramethylbiphenols, 2,2', 3,3', 6,6'-hexamethylbiphenols, 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'-isopropyridene diphenol (bisphenol A), 4,4'-isopropyridenebis (2,6-dibromophenol) (tetrabromobisphenol A), 4,4' -Isopropyridenebis (2,6-dimethylphenol) (teramethylbisphenol A), 4,4'-isopropyridenbis (2-methylphenol), 4,4'-isopropyridenbis (2-allylphenol), 4 , 4'-(1,3-phenylenediisopropylidene) bisphenol (bisphenol M), 4,4'-isopropylidenebis (3-phenylphenol), 4,4'-(1,4-phenylenediisoproprylidene) ) Bisphenol (Bisphenol P), 4,4'-Echilidendiphenol (Bisphenol E), 4,4'-Oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis (2,6-dimethyl) Phenolase), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis (2,6-dimethylphenol) 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisoproylidene) bisphenol (bisphenol) AF), 4,4'-(1-phenylethylidene) bisphenol (bisphenol AP), bis (4-hydroxyphenyl) -2,2-dichloroethylene (bisphenol C), bis (4-hydroxyphenyl) methane (bisphenol-F) ), Bis (2,6-dimethyl-4-hydroxyphenyl) methane, 4,4'-(cyclopentylidene) diphenol, 4,4'-(cyclohexylidene) diphenol (bisphenol Z), 4,4 '-(Cyclododecylidene) diphenol 4,4'-(bicyclo [2.2.1] heptylidene ) Diphenol, 4,4'-(9H-fluoren-9,9-diyl) diphenol, 3,3-bis (4-hydroxyphenyl) isobenzofuran-1 (3H) -one, 1- (4-hydroxy) Phenol) -3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1- (4-hydroxy-3,5-dimethylphenyl) -1,3,3,4,6-pentamethyl- 2,3-Dihydro-1H-Inden-5-ol, 3,3,3', 3'-tetramethyl-2,2', 3,3'-tetrahydro-1,1'-spirobi [inden] -5 , 6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) propane, tris (4-hydroxyphenyl) Butane, tris (3-methyl-4-hydroxyphenyl) methane, tris (3,5-dimethyl-4-hydroxyphenyl) methane, tetrakis (4-hydroxyphenyl) ethane, tetrakis (3,5-dimethyl-4-hydroxy) Phenyl) ethane, bis (4-hydroxyphenyl) phenylphosphine oxide, dicyclopentadienylbis (2,6-dimethylphenol), dicyclopentadienylbis (2-methylphenol), dicyclopentadienylbisphenol, etc. , And mixtures thereof. In some examples, the epoxy compound comprises a bisphenol A diglycidyl ether epoxy compound.

Other suitable auxiliary epoxy compounds include N-glycidyl phthalimide, N-glycidyl tetrahydrophthalimide, phenyl glycidyl ether, p-butyl phenyl glycidyl ether, styrene oxide, neohexene oxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol type epoxy compound, phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, adipate diglycidyl ester , Sebasic acid diglycidyl ester, and phthalic acid diglycidyl ester.

Other auxiliary epoxy compounds include glycidyl ethers of phenolic compounds such as glycidyl ethers of phenol-formaldehyde novolac, cresol-formaldehyde novolac, t-butylphenol-formaldehyde novolak, sec-butylphenol-formaldehyde novolak, tert-octylphenol-formaldehyde novolak, ku Examples thereof include alkyl-substituted phenol-formaldehyde compounds including milphenol-formaldehyde novolak and decylphenol-formaldehyde novolac. Other useful auxiliary epoxy compounds are bromophenol-formaldehyde novolac, chlorophenol formaldehyde novolak, phenol-bis (hydroxymethyl) benzene novolac, phenol-bis (hydroxymethylbiphenyl) novolak, phenol-hydroxybenzaldehyde novolac, phenol-dicyclo. Glycidyl ethers such as pentadiene novolac, naphthol-formaldehyde novolac, naphthol-bis (hydroxymethyl) benzene novolac, naphthol-bis (hydroxymethylbiphenyl) novolak, naphthol-hydroxybenzaldehyde novolac, and naphthol-dicyclopentadiene novolac, and mixtures thereof. Is.

Other suitable auxiliary epoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols. Examples of such polyhydric alcohols include 1,4-butanediol, 1,6-hexanediol, polyalkylene glycol, glycerol, trimethylolpropane, 2,2-bis (4-hydroxycyclohexyl) propane, and pentaerythritol. Can be mentioned.

Further suitable auxiliary epoxy compounds include epichlorohydrin or similar epoxy compounds, oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid, 2,6- A polyglycidyl ester obtained by reacting with an aliphatic, alicyclic, or aromatic polycarboxylic acid such as a naphthalenedicarboxylic acid and a dimerized fatty acid. Examples are diglycidyl terephthalate and diglycidyl hexahydrophthalate. Further, a polyepoxide compound which contains epoxide groups randomly distributed on the molecular chain and can be prepared by emulsion copolymerization using an olefinically unsaturated compound containing such an epoxide group, for example, a glycidyl ester of acrylic acid or methacrylic acid. Can be used.

Examples of additional auxiliary epoxy compounds that can be used are those based on a heterocyclic ring system, such as hydantin epoxy compounds, triglycidyl isocyanurate and its oligomers, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether, Tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenyl ether, tetrakis (4-glycidyloxyphenyl) ethane, urasol epoxide, uracil epoxide, and oxazolidinone-modified epoxy compounds.

Other examples of co-epoxy compounds are polyepoxy based on aromatic amines such as aniline, eg N, N-diglycidyl aniline, diaminodiphenylmethane, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4 , 4'-(1,2-epoxyethyl) biphenyl, 4,4'-di (1,2-epoxyethyl) diphenyl ether, bis (2,3-epoxycyclopentyl) ether and other alicyclic epoxy compounds. ..

Another example of a co-epoxy compound is a mixed polyfunctional epoxy compound obtained from a compound containing the combination of functional groups described above, such as 4-aminophenol.

Examples of monofunctional auxiliary epoxy compounds include 2-ethylhexyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, t-butyl glycidyl ether, o-cresyl glycidyl ether, and nonylphenol glycidyl ether.

Oxazolidinone-modified auxiliary epoxy compounds, such as those disclosed in Angew. Makromol. Chem., Vol. 44, (1975), pp. 151-163, and US Pat. No. 3,334,110 to Schramm can also be used. One example is the reaction product of bisphenol A diglycidyl ether and diphenylmethane diisocyanate in the presence of a suitable accelerator.

The auxiliary epoxy compound can be prepared by condensing the epoxy compound with a phenol such as bisphenol. A typical example is the condensation of bisphenol A with bisphenol A diglycidyl ether to produce an oligomeric diglycidyl ether. In another example, phenols that are not similar to those used to induce epoxy compounds can be used. For example, tetrabromobisphenol A can be condensed with bisphenol A diglycidyl ether to produce a halogen-containing oligomeric diglycidyl ether.

The auxiliary epoxy compound can be solid at room temperature. Therefore, in some embodiments, 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. Therefore, in some embodiments, the auxiliary epoxy compound has a softening point of less than 25 ° C.

The hot epoxy composition can include a curing promoter. The term "curing promoter", as used herein, has a role in the curing of epoxy compounds, among other things: hardening accelerators, hardening catalysts, and curing catalysts. It includes compounds that are variously described as co-catalyst roles. The curing promoter can be an aromatic diamine compound.

In one embodiment, the hot epoxy composition comprises a curing agent. In one embodiment, the curing agent is an amine compound. In embodiments, the amine compounds are 4-aminophenylsulfone (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, It can be a combination containing p-xylylenediamine, diethyltoluenediamine, or at least one of the above. In embodiments, the amine compound is a combination comprising 4-aminophenyl sulfone (DDS), 4,4'-methylenebis- (2,6-diethylaniline) (MDEA), or at least one of the above. Can be done. In one embodiment, the curing agent is methyl-5-norbornene-2,3-dicarboxylic acid anhydride (NMA). The amount of curing promoter depends on the type of curing promoter and the properties and amounts of other components of the hot epoxy composition. For example, if the curing promoter is an aromatic diamineamine compound, it can be used in an amount of 10-30% by weight of the hot epoxy composition.

The curing promoter can be an aromatic dianhydride. In embodiments, the aromatic dianhydride compound has a general structure.

(In the formula, R is a single bond,

, Other bisphenols, -C (CF ₃ ) _2- , -O-, or -C (= O)-)
Have.

Examples of curing promoters are 4,4'-(4,4'-isopropyridenediphenoxy) bis- (phthalic anhydride) (CAS registration number 38103-06-9), 4,4'-(hexafluoro). Isopropyridene) Diphthalic anhydride (CAS registration number 1107-00-2), 4,4'-oxydiphthalic anhydride (CAS registration number 1823-59-2), benzophenone-3,3', 4,4'- Tetracarboxylic dianhydride (CAS registration number 2421-28-5), and 3,3', 4,4'-biphenyltetracarboxylic dianhydride (CAS registration number 2420-87-3), and specifically Examples of compounds having the following formula.

The curing promoter can be a bicyclic anhydride. In embodiments, the bicyclic anhydride compounds are methyl-5-norbornene-2,3-dicarboxylic acid anhydride (CAS registration number 25134-21-8), and cis-5-norbornen-endo-2,3-. It can be a dicarboxylic acid anhydride (CAS registration number 129-64-6), and specifically a compound having the following formula.

In one embodiment, the cured sample of the high thermal epoxy composition has a glass transition temperature of less than 270 ° C. as measured by differential scanning calorimetry. In one embodiment, the cured sample of the hot epoxy has a glass transition temperature between 150 ° C and 270 ° C as measured by differential scanning calorimetry. In one embodiment, the cured sample of the hot epoxy has a glass transition temperature between 170 ° C and 270 ° C as measured by differential scanning calorimetry. In one embodiment, the cured sample of hot epoxy has a glass transition temperature between 175 ° C and 275 ° C as measured by a dynamic mechanical thermal analyzer. In one embodiment, the cured sample of hot epoxy has a glass transition temperature between 190 ° C and 275 ° C as measured by a dynamic mechanical thermal analyzer.

In one embodiment, the composition is solvent-free. The hot epoxy composition can contain a solvent to prepare a uniform epoxy blend, and then the solvent can be removed.

Applications of high thermal epoxy compositions include, for example, acid bath vessels; neutralization tanks; aircraft components; bridge girders; bridge floors; electrolytic tanks; exhaust stacks; cleaners; sports equipment; stairs; pedestrian paths; bonnets and trunk lids. Automotive skins such as; floor pans; air intakes; pipes and ducts including heater ducts; industrial fans, fan housings, and blowers; industrial mixers; hulls and decks; wharf barriers; tiles and coatings; building materials panels Office equipment housings; trays containing cable trays; concrete modifiers; dishwashers and refrigerator parts; electrical encapsulants; electrical panels; electrical refining tanks, hard water softener tanks, fuel tanks, and various filament winding tanks and Tanks including tank linings; Furniture; Garage doors; Grating; Protective body gear; Bags; Outdoor vehicles; Pressure tanks; Printed wiring boards; Optical waveguides; Radomes; Handrails; Railway parts such as tank cars; Hopper car covers; Trackbed liners; Satellite antennas; Signs; Solar energy panels; Telephone switch housings; Tractor parts; Transformer covers; Track parts such as fenders, bonnets, bodies, cabs, and beds; Ground insulation, turn insulation, and phases. Insulation for rotating machinery including separation insulation; rectifiers; core wire insulation and cords and racing tapes; drive shaft joints; propeller blades; missile components; rocket motor cases; wings; soccer rods; fuselage; wing skins and flares Rings; engine nacelles; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; sideways leaf springs; pumps such as automobile smog pumps; electrical components such as electric cable joints, embedding Materials and tools; Windings and high density mounting multi-element assemblies; Sealing materials for electromechanical devices; Battery cases; Resistors; Fuse and overheat blocking devices; Coatings for printed wiring boards; Condenses, transformers, crankcase heaters, etc. Molded products; Small molded electronic components including coils, capacitors, resistors, and semiconductors; Steel alternatives in chemical processing, pulp and paper, power generation, and wastewater treatment; Cleaning towers; Structural components, glazing, and safety rails Draw-out parts for structural applications including; swimming pools, swimming pool sliders, hot tubs, and saunas; drive shafts for under-bonnet applications; dry toner for copying machines; marine tools and composites; thermal sea Ludo; Submarine hull; Prototype generation; Experimental model development; Laminate trim; Drill fittings; Joining jigs; Inspection tools; Industrial metal molding dies; Aircraft stretch blocks and hammer foams; Vacuum molding tools; Manufacturing and assembly areas, Flooring materials including clean rooms, metal workshops, control rooms, laboratories, parking garages, freezers, coolers, and flooring for outdoor loading and unloading; conductive compositions for antistatic; decorative flooring; telescopic joints for bridges Injectable mortar for repairing and repairing cracks in structural concrete; grouting for tiles; mechanical rails; metal dowels; bolts and stanchions; repairing oil and fuel storage tanks, and many other applications.

The compositions and methods described herein will be further described by the following non-limiting examples.

The materials listed in Table 1 were used. Unless otherwise specified, the amount of each component in the following examples is a mass percentage based on the total mass of the composition.

The composition was tested using the test methods listed in Table 2. Unless otherwise instructed, all test methods are valid as of the filing date of the present application.

(Example 1)
Comparative Examples Comparative Examples A, B, and C show the effect on the viscosity of the PPPBP-epoxy / DDS sample with increasing temperature. 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.

Over the temperature range investigated, the viscosity increases rapidly over time. Higher viscosities can lead to, for example, reduced fluidity, improper wetting of fiber reinforced materials in composites, reduced pot life, and premature gelation.

Crystallization begins below 120 ° C, so processing must be performed above 120 ° C. However, as shown in Table 3, at temperatures above 120 ° C, the viscosity increases significantly over time.

(Example 2)
High heat epoxy composition
To avoid the need for high temperatures when preparing the composition with PPPBP-epoxy, a hyperthermal epoxy composition using an auxiliary epoxy compound was prepared. In one embodiment, the auxiliary epoxy compound is a liquid at room temperature. These amorphous blends can exhibit a glass transition temperature near room temperature or below. The hot epoxy compositions described do not require a solvent. In one embodiment, the solvent can be used to prepare a uniform epoxy blend, then the solvent can be removed.

Procedure for preparing an amorphous composition Step 1: The auxiliary epoxy compound was warmed to 100-140 ° C. and PPPBP-epoxy was added with stirring. After the PPPBP-epoxy was dissolved, the mixture was cooled.

Step 2: PPPBP-epoxy and auxiliary epoxy compounds were weighed and placed together in a container and heated with stirring. After the PPPBP-epoxy was dissolved, the mixture was allowed to cool to room temperature.

In the following examples, procedure 1 was used.

The absence of a crystalline melting point suggests that the mixture was amorphous. The high crystal melting point (Tm) of PPPBP-epoxy is shown in Comparative Example D. In the table below, ND indicates that no endothermic transition (melting) was detected.

Table 4 shows the results of the glass transition temperature measurement for the composition of PPPBP-epoxy and BPA DGE-1. There were no signs of any crystal melting point over the composition range investigated. BPA DGE-1 was effective in producing a uniform amorphous blend. In addition, the glass transition temperature of the composition decreases as the amount of BPA DGE-1 used increases.

Table 5 shows the results of glass transition temperature measurements for the composition of PPPBP-epoxy and NPG DGE. There were no signs of any crystal melting point over the composition range investigated. NPG DGE was effective in producing a uniform amorphous blend. In addition, the glass transition temperature of the composition decreases as the amount of NPG DGE used increases.

Table 6 shows the results of the glass transition temperature measurement for the composition of PPPBP-epoxy and ECHM. There were no signs of any crystal melting point over the composition range investigated. ECHM was effective in producing a uniform amorphous blend. In addition, the glass transition temperature of the composition decreases as the amount of ECHM used increases.

In the following examples, procedure 2 was used.

The results of the glass transition temperature measurement for the composition of PPPBP-epoxy and BPA-DGE-2 are shown in Table 7. There were no signs of any crystal melting point over the composition range investigated. BPA DGE-2 was effective in producing a uniform amorphous blend. In addition, the glass transition temperature and viscosity of the composition decrease as the amount of BPA DGE-2 used increases.

Table 8 shows the results of the glass transition temperature measurement for the composition of PPPBP-epoxy and BISF-DGE. There were no signs of any crystal melting point over the composition range investigated. BISF-DGE was effective in producing a uniform amorphous blend. In addition, the glass transition temperature and viscosity of the composition decrease as the amount of BISF-DGE used increases.

Table 9 shows the results of the glass transition temperature measurement for the composition of PPPBP-epoxy and TGAP. There were no signs of any crystal melting point over the composition range investigated. TGAP was effective in producing a uniform amorphous blend. In addition, the glass transition temperature and viscosity of the composition decrease as the amount of TGAP used increases.

Table 10 shows the results of the glass transition temperature measurement for the composition of PPPBP-epoxy and TGDDM. There were no signs of any crystal melting point over the composition range investigated. TGDDM was effective in producing a uniform amorphous blend. In addition, the glass transition temperature and viscosity of the composition decrease as the amount of TGDDM used increases.

Experiments have shown that the addition of an auxiliary epoxy compound to a hot epoxy results in a uniform amorphous blend. In addition, the addition of an auxiliary epoxy compound results in a reduction in glass transition temperature and viscosity in the composition. Lowering the glass transition temperature and viscosity of a uniform amorphous epoxy blend facilitates blending with curing agents and processing to form prepregs, laminates, and composites.

(Example 3)
Molded articles The use of a uniform amorphous epoxy blend of hot epoxy and auxiliary epoxy compounds in the preparation of articles is shown below.

Preparation of the part involved mixing an epoxy polymer at 90-140 ° C. In some cases, the temperature was reduced to 80-110 ° C. after the blend was uniform. The solid curing agent was melted before being added to the uniform epoxy blend. The liquid curing agent was added with stirring. The blended polymer was degassed in a vacuum furnace at 100 ° C., then poured into a mold and cured according to a curing schedule A or B.

In some cases, the temperature was maintained at 140 ° C. even after the blend was uniform to reduce the time required to produce the part. The solid curing agent was melted before being added to the uniform epoxy blend. The liquid curing agent was added with stirring. The blended polymer was degassed at 140 ° C. under vacuum, then poured into a mold and cured according to a curing schedule A or B.

Optionally, after the blend was uniform, the temperature was lowered to room temperature and stored overnight. The next day, the blend was warmed to 80-110 ° C. The solid curing agent was melted before being added to the uniform epoxy blend. The liquid curing agent was added with stirring. The blended polymer was degassed in a vacuum furnace at 100 ° C., then poured into a mold and cured according to a curing schedule A or B.

Optionally, degassed polymer samples were used for small-amplitude vibration rheology tests at 80 and 90 ° C.

Curing schedule A
After pouring the polymer into a mold, it was placed in a furnace at 120 ° C. After 30 minutes, the temperature was raised to 130 ° C. After 30 minutes, the temperature was raised to 140 ° C. After 30 minutes, the temperature was raised to 150 ° C. After 30 minutes, the temperature was raised to 175 ° C. After 30 minutes, the temperature was raised to 220 ° C. After 60 minutes, the furnace was shut down and allowed to cool overnight. The part was removed from the mold for testing.

Curing schedule B
The polymer was poured into a mold preheated to 140 ° C and then placed in a 140 ° C furnace. After 60 minutes, the temperature was raised to 160 ° C. After 60 minutes, the temperature was raised to 180 ° C. After 60 minutes, the temperature was raised to 200 ° C. After 30 minutes, the temperature was raised to 220 ° C. After 30 minutes, the furnace was shut down. After cooling to room temperature, the molded product was taken out of the mold and tested.

Molds were prepared from a blend of PPPBP-epoxy containing a DDS hardener and BPA-DGE-2 using Curing Schedule B. Prior to curing, degassed polymer samples were taken and viscosity was determined using a small-amplitude vibration rheology test at 80 and 90 ° C. Table 11 shows the results of the glass transition temperature and viscosity. The use of BPA-DGE-2 resulted in a significant reduction in viscosity in the blended polymer. The part showed a very high glass transition temperature.

Molds were prepared from a blend of PPPBP-epoxy and BISF-DGE using Curing Schedule B. In Example 33, MDEA was used as the curing agent. In Examples 34 to 37 and Comparative Example K, DDS was used as a curing agent. Prior to curing, degassed polymer samples were taken and their viscosities were determined using a small-amplitude vibration rheology test at 90 ° C. Table 12 shows the results of the glass transition temperature and viscosity. The use of BISF-DGE resulted in a significant reduction in viscosity in the formulated polymers. The part showed a very high glass transition temperature.

Molds were prepared from a blend of PPPBP-epoxy and TGAP using Curing Schedule B. In Example 38, MDEA was used as the curing agent. In Examples 39 to 41 and Comparative Example L, DDS was used as a curing agent. Prior to curing, degassed polymer samples were taken and their viscosities were determined using a small-amplitude vibration rheology test at 90 ° C. Table 13 shows the results of the glass transition temperature and viscosity. The use of TGAP resulted in a significant reduction in viscosity in the blended polymer. The part showed a very high glass transition temperature.

Molds were prepared from a blend of PPPBP-epoxy with TGDDM containing a DDS curing agent using Curing Schedule B. Prior to curing, degassed polymer samples were taken and their viscosities were determined using a small-amplitude vibration rheology test at 90 ° C. Table 14 shows the results of the glass transition temperature and viscosity. The use of TGDDM resulted in a significant reduction in viscosity in the formulated polymers. The part showed a very high glass transition temperature.

Molds were prepared from a blend of PPPBP-epoxy containing a DDS curing agent and two auxiliary epoxy compounds: ECHM and either NPGDGE or DGEBPA-1 using curing schedule A. Table 15 shows the results of the glass transition temperature. The part showed a very high glass transition temperature.

Example 16 shows the use of an anhydride curing agent with an epoxy blend of PPPBP-epoxy. Molds were prepared from a blend of PPPBP-epoxy and BPADGE-2 containing an NMA curing agent and a 1-MeI catalyst using curing schedule A. The amount of catalyst is expressed in ppm (number of parts per 100 parts by mass of polymer). Table 16 shows the results of the glass transition temperature for the molded sample. The part showed a very high glass transition temperature.

The compositions, methods, articles, and other embodiments will be further described by embodiments below.

Embodiment 1: Equation:

(In the formula, R ¹ and R ² for each appearance are independently epoxide-containing functional groups; R ^a and R ^b for each appearance are independently halogen, C _{1 to} C ₁₂ alkyl, and C _{2 respectively.} ~ C ₁₂ alkenyl, C ₃ ~ C ₈ cycloalkyl, or C ₁ ~ C ₁₂ alkoxy; p and q per appearance are 0-4 independently, respectively; R ¹³ per appearance is independent Halogen, or C _{1 to} C ₆ alkyl group; c per appearance is 0 to 4 independently; R ¹⁴ per appearance is independently C _{1 to} C ₆ alkyl, phenyl, or max. Phenyl substituted with 5 halogens or C _{1 to} C ₆ alkyl groups; each appearance R ^g is independently C _{1 to} C ₁₂ alkyl or halogen, or 2 R ^g groups are Together with the carbon atoms they are attached to, they form a 4, 5- or 6-membered cycloalkyl group; t is 0 to 10).
A high-heat epoxy composition comprising a high-heat epoxy compound having an auxiliary epoxy compound different from the high-heat epoxy compound, measured according to ASTM D3418, between -10 ° C and 62 ° C, preferably 15 ° C to 62 ° C. Has a glass transition temperature between, preferably between 30 ° C and 62 ° C, preferably between 40 ° C and 62 ° C, at 80 ° C below 2,100,000 cP, preferably at 80 ° C below 1,700,000 cP, preferably at 80 ° C. A composition having a parallel plate viscosity of 400,000 cP or less, or preferably 140,000 cP or less at 80 ° C.

Embodiment 2: The composition according to embodiment 1, comprising an auxiliary epoxy compound of 5 to 50% by weight, preferably 5 to 25% by weight, preferably 5 to 10% by weight.

Embodiment 3: The composition of Embodiment 1 or 2, further comprising a curing agent.

Embodiment 4: The cured sample of the composition has a glass transition temperature of less than 270 ° C., preferably between 150 ° C. and 270 ° C., preferably between 170 ° C. and 270 ° C. as measured by differential scanning calorimetry. The composition according to the third embodiment.

Embodiment 5: In Embodiment 3, the cured sample of the composition has a glass transition temperature between 175 ° C. and 275 ° C., preferably 190 ° C. and 275 ° C. as measured by a dynamic mechanical thermal analyzer. The composition described.

Embodiment 6: The composition according to embodiment 3, wherein the curing agent is an amine compound.

Embodiment 7: The curing agent is 4-aminophenylsulfone (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, diethyltoluenediamine, preferably 4-aminophenylsulfone (DDS), 4,4'-methylenebis- ( 2,6-Diethylaniline) (MDEA), or a combination comprising at least one of the above, according to embodiment 3.

Embodiment 8: The composition according to embodiment 3, wherein the curing agent is an aromatic dianhydride or a bicyclic dianhydride.

Embodiment 9: The composition according to embodiment 3, wherein the curing agent is methyl-5-norbornene-2,3-dicarboxylic acid anhydride (NMA).

Embodiment 10: Auxiliary epoxy compounds include aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, phenol novolac epoxy polymers, cresol-novolac epoxy polymers, biphenyl epoxy compounds, Triglycidyl p-aminophenol, tetraglycidyldiaminodiphenylmethane, polyfunctional epoxy compound, naphthalene epoxy compound, divinylbenzenedioxide compound, 2-glycidylphenylglycidyl ether, dicyclopentadiene type epoxy compound, polyaromatic epoxy polymer, or the above The composition according to any one of embodiments 1 to 9, which is a combination containing at least one of.

Embodiment 11: Auxiliary epoxy compounds are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, neopentyl glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-diglycidyl. -4-Glysidyloxyaniline, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, or a combination comprising at least one of the above, any of embodiments 1-10. The composition according to paragraph 1.

Embodiment 12: R1 and R2 for each appearance are independent of each other:

(In the formula, R ^3a and R ^3b are independently hydrogen or C _{1 to} C ₁₂ alkyl, respectively)
The composition according to any one of embodiments 1 to 11.

Embodiment 13: The hot epoxy compound is of formula (1-a), (2-a), or (4-b).

The composition according to any one of embodiments 1 to 12, wherein the composition comprises.

Embodiment 14: The composition according to any one of embodiments 1 to 13, which does not contain a solvent.

The compositions, methods, and articles can, as an alternative, consist of, or essentially consist of, any suitable ingredient or step disclosed herein. The composition, method, and article may, in addition or as an alternative, any step, ingredient, material, raw material, adjuvant, or seed that is not otherwise necessary to achieve the function or purpose of the composition, method, and article. It can be formulated so that it is lacking or substantially free.

The singular forms "one (a)", "one (an)" and "the" include multiple referents unless the context clearly indicates otherwise. "Or" means "and / or" unless the context clearly dictates otherwise.

The endpoints of all ranges for the same component or property are inclusive and can be combined independently (eg, "25% by weight or less, or 5% to 20% by weight" range is "5% by weight". Includes end points in the range of ~ 25% by mass and all intermediate values, etc.). Disclosure of a narrower or more specific group in addition to a wider range does not abandon the wider or larger group. Unless defined elsewhere, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. "Combination" includes blends, mixtures, alloys, reaction products and the like.

As used herein, the terms "hydrocarbyl" and "hydroxyl" include carbon and hydrogen, optionally 1-3 heteroatoms, such as oxygen, nitrogen, halogen, silicon, sulfur, or. Broadly refers to substituents containing a combination thereof; "alkyl" refers to a linear or branched saturated monovalent hydrocarbon group; "alkylene" refers to a straight or branched saturated divalent hydrocarbon group. "Alkylidene" refers to a linear or branched saturated divalent hydrocarbon group having both valences on a single common carbon atom; "alkenyl" is attached by a carbon-carbon double bond. Refers to a linear or branched monovalent hydrocarbon group having at least 2 carbons; "cycloalkyl" is a non-aromatic monovalent monocyclic or polycyclic hydrocarbon group having at least 3 carbon atoms. "Cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least 3 carbon atoms with at least 1 unsaturated degree; "aryl" refers to in one or more aromatic rings. Refers to an aromatic monovalent group containing only carbon; "arylene" refers to an aromatic divalent group containing only carbon in one or more aromatic rings; "alkylaryl" as defined above. Aryl groups substituted with such alkyl groups, 4-methylphenyl is an exemplary alkylaryl group; "arylalkyl" refers to alkyl groups substituted with aryl groups as defined above, benzyl. Is an exemplary arylalkyl group; "acyl" refers to an alkyl group as defined above that contains the indicated number of carbon atoms bonded via a carbonyl carbon bridge (-C (= O)-); "Aryloxy" refers to an alkyl group as defined above that contains a indicated number of carbon atoms bonded via an oxygen bridge (-O-); "aryloxy" refers to an alkyl group via an oxygen bridge (-O-). Refers to an aryl group as defined above that contains the indicated number of bonded carbon atoms.

Unless otherwise indicated, each of the above groups can be unsubstituted or substituted provided that it does not significantly adversely affect the synthesis, stability, or use of the compound. As used herein, the term "substitution" means that at least one hydrogen on a specified atom or group is on another group, provided that it does not exceed the normal valence of the specified atom. Means to be replaced. If the substituent is oxo (ie = O), the two hydrogens on the atom are replaced. Substituents or combinations of variables are acceptable provided that the substitution does not significantly adversely affect the synthesis or use of the compound. Exemplary groups which may be present in the "substituted" position, cyano; hydroxyl; nitro; azido; alkanoyl (e.g. C ₂ ~ ₆ alkanoyl group acyl, etc.); carboxamide; C ₁ ~ ₆ or C ₁ ~ ₃ alkyl, cyclo alkyl, alkenyl, and alkynyl (at least one unsaturated bond, 2-8 or containing 2-6 groups having a carbon atom); C ₁ ~ ₆ or C ₁ ~ ₃ alkoxy; C _{6 to 10} aryl Oxy, such as phenoxy; C ₁ to ₆ alkylthios; C ₁ to ₆ or C ₁ to ₃ alkylsulfinyl; C ₁ to ₆ or C ₁ to ₃ alkylsulfonyls; aminodi (C ₁ to ₆ or C ₁ to ₃ ) acrylics; at least C _6-12 aryls with one aromatic ring (eg, phenyl, biphenyl, naphthyl, etc., each ring is either a substituted or unsubstituted aromatic); with 1-3 separate or fused rings, C _7-19 arylalkyls with 6-18 ring-carbon atoms; or arylalkoxys with _{1- to} 3 separate or fused rings and 6-18 ring-carbon atoms (benzyloxy is an exemplary aryl) Aryl), but is not limited to this. As is typical in the art, the line extending from the structure means the terminal methyl group-CH ₃ .

All cited patents, patent applications and other references are incorporated herein by reference in their entirety. However, if the term in the present application conflicts with or contradicts the term in the incorporated reference, the term in the present application takes precedence over the contradictory term from the incorporated reference.

Although typical embodiments have been described for purposes of illustration, the above description should not be considered as limiting the scope of this specification. Thus, without departing from the spirit and scope of this specification, one of ordinary skill in the art may come up with various modifications, adaptations, and alternatives.

Claims (15)

formula:

(During the ceremony,
R ¹ and R ^{2 at} each appearance are independently epoxide-containing functional groups;
R ^a and R ^b for each appearance are independently halogen, C _{1 to} C ₁₂ alkyl, C _{2 to} C ₁₂ alkenyl, C _{3 to} C ₈ cycloalkyl, or C _{1 to} C ₁₂ alkoxy;
P and q for each occurrence are 0-4 independently, respectively;
R ^{13 on} each appearance is independently a halogen, or a C _{1 to} C ₆ alkyl group;
The c for each occurrence is 0-4 independently;
R ¹⁴ per appearance is independently C _{1 to} C ₆ alkyl, phenyl, or phenyl substituted with up to 5 halogens or C _{1 to} C ₆ alkyl groups;
The R ^g for each appearance is C _{1 to} C ₁₂ alkyl or halogen independently, or two R ^g groups are combined with the carbon atom to which they are attached to a 4, 5- or 6-membered cyclo. Form an alkyl group;
t is 0 to 10)
With high heat epoxy compounds with;
A high-heat epoxy composition containing an auxiliary epoxy compound different from the high-heat epoxy compound;
The hot epoxy composition comprises an amorphous blend of the hot epoxy compound and the auxiliary epoxy compound.
The high heat epoxy composition does not contain a solvent and
The auxiliary epoxy compound is the high heat epoxy composition.
− Measured according to ASTM D3418 with a glass transition temperature between -10 ° C and 62 ° C, preferably between 15 ° C and 62 ° C, preferably between 30 ° C and 62 ° C, preferably between 40 ° C and 62 ° C. ,
- 2,100,000CP at 80 ° C. or less, preferably 1,700,000cP at 80 ° C. or less, preferably 400,000cP at 80 ° C. or less, or preferably selected to have a <br/> less parallel plate viscosity 140,000cP at 80 ° C. that, high fever epoxy compositions. The high thermal epoxy composition according to claim 1, which comprises 5 to 50% by mass, preferably 5 to 25% by mass, preferably 5 to 10% by mass of an auxiliary epoxy compound. The high thermal epoxy composition according to claim 1 or 2, further comprising a curing agent. Claim that the cured sample of the high thermal epoxy composition has a glass transition temperature of less than 270 ° C., preferably between 150 ° C. and 270 ° C., preferably between 170 ° C. and 270 ° C. as measured by differential scanning calorimetry. The high thermal epoxy composition according to 3. 30. High heat epoxy composition. The high thermal epoxy composition according to claim 3, wherein the curing agent is an amine compound. Hardeners are 4-aminophenylsulfone (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, diethyltoluenediamine, preferably 4-aminophenylsulfone (DDS), 4,4'-methylenebis- (2,6-) The high thermal epoxy composition according to claim 3, which is a combination containing diethylaniline) (MDEA), or at least one of those described above. The high thermal epoxy composition according to claim 3, wherein the curing agent is an aromatic dianhydride or a bicyclic anhydride. The high thermal epoxy composition according to claim 3, wherein the curing agent is methyl-5-norbornene-2,3-dicarboxylic acid anhydride (NMA). Auxiliary epoxy compounds are aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, phenol novolac epoxy polymers, cresol-novolac epoxy polymers, biphenyl epoxy compounds, triglycidyl p- Aminophenol, tetraglycidyldiaminodiphenylmethane, polyfunctional epoxy compound, naphthalene epoxy compound, divinylbenzenedioxide compound, 2-glycidylphenylglycidyl ether, dicyclopentadiene type epoxy compound, polyaromatic epoxy polymer, or at least one of the above. The high thermal epoxy composition according to any one of claims 1 to 9, which is a combination containing seeds. Auxiliary epoxy compounds are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, neopentyl glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-diglycidyl-4-glycidyl. The expression according to any one of claims 1 to 10, which is a combination containing at least one of oxyaniline, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, or the above-mentioned ones. High heat epoxy composition. R ¹ and R ² for each spawn are independent:

(In the formula, R ^3a and R ^3b are independently hydrogen or C _{1 to} C ₁₂ alkyl, respectively)
The high thermal epoxy composition according to any one of claims 1 to 11. The hot epoxy compound is of formula (1-a), (2-a), or (4-b).

The high thermal epoxy composition according to any one of claims 1 to 12. The hot epoxy composition according to any one of claims 1 to 13 , wherein the hot epoxy compound has the formula (1-a). The high-temperature epoxy compound has the formula (1-a), and the auxiliary epoxy compounds are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, neopentyl glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-. Epoxycyclohexanecarboxylate, N, N-diglycidyl-4-glycidyloxyaniline, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, or a combination containing at least one of the above. , The high thermal epoxy composition according to any one of claims 1 to 14 .