WO1980001804A1 - Liquefaction of acid anhydride - Google Patents

Abstract

Diels-Alder reaction products of maleic anhydride which is in a solid state in a room temperature and a dimethyloctatriene are liquefied by heat-treatment in the presence of an isomerization catalyst of compounds selected from the group consisting of a) alkali metal salts, b) amines and quaternary ammonium salts, c) phosphine compounds and quaternary phosphonium salts, d) thiocyanates, and e) solid basic compounds. The liquefied acid anhydrides thus obtained are useful as a curing agent for epoxy resins.

Description

 Liquefaction method of acid anhydride

 The present invention relates to a method for liquefying a Diels-Alder reaction product of maleic anhydride and dextrin which shows a solid state at ordinary temperature.

 The resulting liquid acid anhydride is useful as a curing agent for epoxy resins and as a raw material for unsaturated alkyds. Background technology

Diels-Chemical Reaction Product of Decatriene and Maleic Anhydride (In the present specification, this is called "maleic anhydride-decatriene".) For example, a reaction product of maleic anhydride and acetaminophen (hereinafter, referred to as "anhydrous malediary dentist"), and a mixture of maleic anhydride and milsenic The reactant (hereinafter referred to as “anhydrous maleinhymilsen”) is used as a curing agent for epoxy resin and an acid component for producing non-aerated aluminum resin. However, these anhydrous maleinated decatrienes are often solid at room temperature, and are liquid from the viewpoint of reactivity and workability for use in the above applications. It is desirable to make it. In this way, solid anhydrous maleidic anhydride is liquid. It is necessary to shape.

 Conventionally, as a method of liquefying an anhydrous maleated arosimine, for example, in British Patent No. To

It is described that heat treatment is carried out at a temperature of C for a long time to liquefy by thermal isomerization. However, such long-term heating is not possible.] The method of isomerization is carried out in a stream of nitrogen. There was a shortcoming in the yield of indigenous simone. In addition, even if the liquefied product after the distillation purification is temporarily liquid, the crystal often precipitates after 2 to 2 days.

 Crystallizes at a low temperature of about / C. In the example of the same specification, anhydrous maleated arosimene is referred to as << 2/0 to I20.

 If the product after the heat treatment is left for a period of time, it crystallizes if left to stand, but if this product is further heated for << 2 / ~ 2. However, it is stated that a liquid material was obtained.However, such a long-time heat treatment is a method that can be first liquefied, which is extremely disadvantageous industrially.

 Also, US Patent No.

Epoxy resin cured by blending maleinated slime, blended maleic anhydride and hexahydrophthalic anhydride Agents have been proposed, such as this

' A melt-mixing step is required to liquefy solid materials by blending them at room temperature. However, there is a disadvantage that the cost is high.

 The present invention provides a treatment method for easily and advantageously liquefying anhydrous maleinated decatriene at room temperature. Disclosure of the invention

 That is, the present invention provides a method for liquefying an anhydrous maleinated decatylene that is solid at room temperature by heating in the presence of a compound selected from the following groups a) to β): It is provided.

 a) Alkali metal salt

 ¾) Organic compounds containing nitrogen element

 C) Organic compounds containing elemental elements selected from phosphine compounds and first-class phosphine salts

 d) Chi cyanide cyanate

 θ) Solid basic compounds (excluding Al-metal salts belonging to group a) above).

Further, the present invention provides a method for preparing an anhydrous maleinated decatriene which is solid at room temperature in the presence of a compound selected from the above-mentioned groups e) to 3). A method for liquefaction treatment of solid anhydrous maleinated triton, characterized by heat treatment in the presence of an acidic catalyst or a noble metal medium. It provides

 Thus, anhydrous maleinated decatriene that is solid at room temperature can be easily liquefied by simply heat-treating it in the presence of a compound selected from the above &) to e) groups. .

 It is presumed that this liquefaction causes the anhydrous maleinated decatriene to undergo an isomerization reaction to generate several isomers, and to lower the freezing point due to the coexistence of these several isomers. The details are unknown.

 For example, in the case of heat treatment in the presence of sodium iodide using anhydrous maleinated alosimene as an anhydrous maleinated decatrain, It is estimated as follows.

 There are two types of trans-isomer, trans-trans-isomer and trans-trans-isomer. J "k ~ 7, trans-transformation is contained ^ 0 ~ 0.

 If maleic anhydride is added to the aroosimine by a Diels-Alder reaction, it can be easily converted to a maleic anhydride. Anhydrous maleated aromatics obtained by such a method are generally as follows:

(I) and (Π) << a mixture of two isomers whose melting point is higher than C, for example, ^ to C] ?, and of course, they are solid at room temperature (to C).

 CH, 0

(I) (I) When the solid anhydrous maleinated osmum at room temperature is heat-treated in the presence of sodium iodide,

 (I) and some of the (E) isomers form the following (additional isomers and αν) isomers, and the double bond isomerization reaction occurs. It is considered that a very large number of isomers coexist in the processed product, the freezing point is reduced, and the product is liquefied.

(ID)

3U ', ひ>--\ i f> ^ The thus obtained anhydrous maleinated maleated decatriene which is liquid at room temperature is liquid and can be easily mixed with epoxy resin. It is most suitable as a curing agent for epoxy resin. BEST MODE FOR CARRYING OUT THE INVENTION

 The present invention will be described in more detail.

(1) Anhydrous maleated decatriene

 As the maleic anhydride maleated decatrin at room temperature used in the method of the present invention, the following decatylene is used in combination with maleic anhydride and Diels-Als An ordinary maleic anhydride-dried solid at room temperature, which is obtained by a dipping reaction.

 (ί)

OH _s 0H _S

0H _S — C = CH— CH = CH— C = GH— CH.

Osimen

 OH, OH,

CH, = 0— OH, CH ₂ — OH = C— CH = CH,

• 2, -dimethyl / ,, 7-year-old

 0H.GH.

CH ₂ = C— 0H = CH— CH ₂ — 0H ₂ — C = CHj • 2, -Dimethyl-1-/, «?, ^

CH ₃

 1

 CE, = 0— CH CH— 0H-— C = OH CH,

Particularly preferred in the present invention is anhydrous malein

 Trien is a dilute criminal or a dimer of 1,2-octatriene and a maleic anhydride deal.

 Alder reaction product, that is, maleic anhydride

 才 シ お よ ァ ァ ァ ァ ァ ァ ァ ァ

 Deal with a mixture of vinyl acetate and maleic anhydride

 The product is a reaction product.

(2) Isomerization catalyst

 In the process of the present invention, the solid maleic anhydride

 A compound that exists when liquefying a tree, (hereinafter referred to as “isomerization medium”).

 The compounds in the group e) will be described in detail below. a) Alkali metal salt

 Alkali metal salts include, for example, lithium chloride, sodium odor, sodium chloride, sodium chloride,

 Salt, potassium bromide, salt hill,

 Cesium chloride, lithium iodide, sodium iodide

 , Potassium iodide, sodium chloride, and sodium chloride

 Such as sodium chloride, rubidium bromide, bromide

 Halogenated metal salts: Lithium sulfate, nitric acid Au'P!

".yipo / Lithium, Lithium Nitrite, Lithium Oxalate, Lithium Cyanide, Lithium Carbonate, Sodium Sulfate, Sodium Nitrate, Pelic Acid Sodium, sodium cyanide, sodium carbonate, calcium sulfate, nitric acid potassium, luminous acid potassium, cyanate sodium Inorganic salts of metals such as potassium carbonate and lithium carbonate; lithium acetate, lithium benzoate, lithium octylate, lithium stearate; Lithium salicylate, lithium oxalate, sodium acetate, sodium oleate

Organic salts of alkali metals, such as aluminum, sodium benzoate, potassium acetate, potassium sulfate, potassium lactate; lithium pheno Rate, lithium resorcinolate, lithium salt of bisphenol A, sodium phenolate, potassium phenolate, etc. Salts of alkali metals with phenols; sodium methylate, lithium methylate, sodium methylate, and potassium Salts of alcohol metals such as mucilat and alcohols; and the like.

 Of these, lycium, lycium, lycium, lycium, oxidized sodium are easily available and inexpensive. So preferred o

 Organic compounds containing nitrogen element

 Used as an isomerization catalyst in the method of the present invention

,-If

' one

Nitrogen element-containing organic compounds contain-primary, secondary, tertiary, and Z or quaternary nitrogen elements in the molecule. Organic compounds, and various nitrogen-containing organic compounds, including derivatives such as salts of these compounds.

 The following are typical examples of the primary amine-containing nitrogen-containing organic compounds.

 Alkylamins

 For example, there is a railroad arm, a stealing lamin-· 2-technol- ogy.

 Amines represented by the following general formula

Η ₂ Ν (0Η ₂ ) _η ΝΗ,

(Where: = / ~: i 0 0 For example, there are ethylamine, propylamine, hexamethylamine, etc.).

 Polyalkylene amines represented by the following general formula

E ₂ N (CH ₂ ) _n NH (0H ₂ ) _n NH ₂

(In the formula, 11 = ^ ^ ^) For example, propylentrimin, butylentrimin, diethylentrimin, etc. To

 (IV) Polyethylene boramines represented by the following general formula

H ₂ N [(0H ₂ ), NH _n (0H ₂ ) ₂ NE ₂

(Where:-to f0 ヽ For example, triethylentetramine, tetraethylenepentamine-pentaethylenehexamin, etc. There o

 (V) Alkanol amines

 For example, there is an amine ethanol amine.

 (VI) Alicyclic amines

 For example, there are menthol diamide, diamino shrinkage, and isoholodiamine.

 (vii) Aromatic amines

 For example, Kisekijinmin, Tetrakuroru P—Kishirenjimin, Metafujirenjimin, Methylenjinrin , Diamino sulphone, aniline, trizine, etc.

Representative examples of the organic compound containing a secondary ammine nitrogen element include, for example, N-methylbibedine, hydroxylethylbiradine-biazine.ぺ There are ligins, virgins, morpholins, and ethanol amines.

 The following are typical examples of the tertiary amino nitrogen-containing organic compounds.

^ O

 (j) Aliphatic tertiary diamines

 Tertiary amines represented by the following general formula.

_{(CH 3) 2 N (CH} 2) n N (CH 3) 2

(Where, 11 = 2 to 0) For example, Ν, Ν, Ν ', ΙΓ — Tetramethyl /, S Butanemine

 Tetramethyldangin.

 Tertiary fans represented by the following general formula

NC (0H ₂ ) _n 0H _{3 3}

(Where η = ί? 〜 << 2k) For example, tree η-butylamine, tri-one • 2-ethylethylamine, trilauryla There are mines, etc.

 Trietanolamin ο

 • 2—Dimethyl Amino 《2—Hydroxiv Mouth Pan ο

 The following formula represents the following formula:

0 so-called Knolls

_{[0H 3 (CJH 2) n 2} N (CH 2) 2 OH

(Where::!-~ ク) For example, dimethylaminoethanol, dibutylaminoethanol, and the like are hexamethylphosphoramides.

 Alicyclic tertiary amines

Examples include Ν, Ν'-dimethyl biperazine, Ν, Ν'-bis [(<< 2—hydroxy) brovir], Piberazine, U—Rukirumo Ruholin, /,, 1-jazabi-sik mouth [... 2,2] year old tan (triethylenamine), hexamethylene Ν, Ν, Ν — dimethylcyclohexylamine, Ν — alkyl pyridine, U — methyl hexylamine-K-alkyl pyridine Oh ₀

 Unsealed Japanese tertiary amines

 The following are examples.

/ Idyloxy Shechilloo 2 ^ Butadecyl Glogaridine.

 Viridin and its derivatives, for example pyridin, α-vicolin — —picolin-r-vicolin,

O. PI — —, J "

 Piperazine and its derivatives.

 Quinolin and its derivatives.

 Alkaline alkaloids represented by the following general formula.

(Where, ii = ~ //, m-«2 ~) For example, /, ^ one dither bicyclo [· ·] ゥ デ デ, /, one dither bicyclo [, <<? There are non-metals.

 Imidazoline derivatives, for example, << 2—methylimidazole, · 2—furimidazole, etc. o Imidazoline derivatives, for example, << 2—methylimidazoline, 2—f D-louis midazoline and the like. In addition, heterocycles such as oxazole, flazan, thiazol, inter * zol, brin, xanthin, naphthyridine, quinoxaline, etc. Formula compounds and their derivatives.

(IV) Aromatic tertiary amines

 For example, benzyl dimethylamine, you

0.V.PI u (Dimethylaminomethyl) phenol, << 2,, tris (dimethylaminomethyl) phenol, Ν, Ν—dimethylamine , Ν Ν, Ν ', tetramethyldiamine aminomethane, Ν, Ν-dimethyltilidine and the like. In addition, the above primary, secondary or tertiary amino nitrogen

 1

Derivatives such as RRNII salts of element-containing compounds can also be used. For example, hydrochloric acid of these nitrogen-containing organic compounds

 S

Mineral salts such as salts and sulfates; and organic acid salts such as «2-ethylhexylate and sulphate. In addition, phenols such as hydroquinone, carboxylate, bisphenol II, and salts of these nitrogen-containing organic compounds can be mentioned. Specific examples thereof include triethylamine hydrochloride, << 2,, 1-tris (dimethylaminoaminomethyl) phenol << 2—ethylhexylate , La © Li Rua Mi emissions of acetic acid salt, /, there is one Jiaza velvetleaf Shi-click opening [^ - - <?] © Ndese down one ⁷ carbolic acid salt of, La c Li Rua Mi emissions of acetic acid salts, and the like.

 In addition, the class of ammonium-based salt-containing organic compounds having the general formula

X

o .Pi- ^v il-° (In the formula, R ¹ , ^, R * and are monovalent hydrocarbon groups, which may be the same or different. ∑ represents a halogen such as chlorine, bromine or iodine. Atom.)

The compound represented by these is mentioned. In this general formula, the monovalent hydrocarbon groups of R ² , R »and R * are usually« alkyl groups having 2 ^ lower carbon atoms (eg, methyl group, ethyl group, butyl group). Group, hexadecyl group, octyl group, rauryl group, etc.), cycloalkyl group (eg, cyclohexyl, cyclobutyl, etc.), aryl (For example, phenyl), alkyl (for example, methyl or dodecyl phenyl), or arylalkyl (for example, benzene) And the French Building). Specific examples of the quaternary ammonium salt represented by this general formula include, for example, tetraethylammonium iodide, laurel trimethylamine Monitor Chloride, Disaster Relief Methyl Chloride-Alkyl Benzyl Dimethyl Chloride Mo-Chloride And others.

Other quaternary ammonium salts include those known as cation activators, for example, alkyl amide methyl vinyl chloride, lauric. Known as amphoteric agents, such as rupidium chloride For example, there may be mentioned rawyl betaine, stearyl betaine and the like, and anion exchange resin derived from polystyrene resin and the like.

 Preferred as these various nitrogen element-containing organic compounds are a primary amine nitrogen element, a secondary amine nitrogen element, a tertiary amine nitrogen element, and Z or Organic compounds containing a quaternary ammonium salt of a nitrogen atom and derivatives thereof, such as salts thereof, are particularly preferable, as are organic compounds containing a tertiary amine nitrogen atom. Is an organic compound containing salts thereof and a quaternary ammonium salt of nitrogen.

 Particularly preferred is tri-n-butylamine.

c) Phosphine compounds, first-class phosphorous salts]? Selected organic compounds containing phosphorus

 The phosphine compound has the general formula

R ₂ — P— R _s

[In the formula,! ^,: ^ Is an alkyl, cycloalkyl, aryl, aryl, or arylalkyl group having 2 to 2 carbon atoms. ,

R i. R _2. R _s may be the same or different. ] A compound represented by the formula (1), for example, trimethylphosphine, triethylphosphine, triisopropylphosphine, Lufos fin, Triisobutyl phosphine, Tri-No. 2 • Butyl phosphine, Tris 2-Ethyl hexyl phosphine, Trioctylphosphine, Trioctadecylphosphine, Butyldiphenylphosphine, Methylbutyloctylphosphine, Dimethylthiophosphine Sphin, tri-fer-hos fin, tri-slip mouth xy s-fin, tri-benzyl-hos-fin, benzyl z-methyl Hos fin, Tris 《2−1 phenyl phosphine, Triss N-butyl phosphine, dimethyl phenyl phosphine, tri-tri-phenyl phosphine, tri-sulfone-butyl phenyl phenyl phosphine And the like.

Also, the first-class phosphine salt has the general formula R ₂

Ri I P— R ₃ ] ® Χ ^θ

R ₄

(Where X is a halogen atom selected from I, Br, and G, R hRR s,! ^ Is an alkyl group having a carbon number of ~, a cycloalkyl group, A reel group, an alkyl group or an aryl alkyl group.

U 4 f ΰ P May be the same or different. )

Such as, for example, methyl triphenylphosphoric acid, ethyl triphenylphosphoric acid, broth triphenylphosphine, etc. N-butyl triphenyl-N-butyl phosphate N-butyl tri-n-butyl phosphate N-decyl triphenyl-phosphine-dimethyl iodide, methyl tributyl phosphate S-dimethyl iodide, ethyl triphenylphosphonium chloride, _n -butyl triphenylphosphonium chloride, ethyl triphenylphosphonium chloride Humid substances, tetrakishydroxide methyl chloride, tetrahydrochloride, tetrachloride chloride, and the like.

 Of these, organic phosphine compounds are easily dissolved in anhydrous maleinated alcohol, so that the reaction conditions can be easily adjusted and easily available. Preferred for reasons.

 Thiocyanate

Examples of titanium thiocyanate include ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, and titanium thiocyanate. Magnesium acid, calcium thiocyanate, zinc thiocyanate, manganese thiocyanate and their pyridines, quinolines, and guanines -Amine salts such as gin, toluidine and hydrazine. , F, two: Of these, sodium thiocyanate is preferred.

 e) Solid basic compound

 Solid basic compounds include oxides such as calcium oxide, magnesium oxide, perium oxide, zinc oxide, silicon oxide; ammonium carbonate, and carbonate carbonate. Re

 Carbonates such as aluminum and carbon dioxide; hydroxides such as casei soda, casei, magnesium hydroxide, and hydroxide hydroxide; Nitrous oxide activated charcoal, Ann

 Mo-activated carbon and the like.

 Further, among these compounds of the groups a) to e), particularly preferred are sodium iodide and lithium bromide of the group a) and tree II-butylamine of the group a).

 (3) Isomerization conditions

 The solid anhydrous maleinated triene can be easily obtained by heat-treating in the presence of a compound selected from the above a) no to ii) group. A heating temperature of 1 to 10 minutes requires a long time for liquefaction at a low temperature, and a high temperature decreases the yield of the target liquefied product because the decomposition reaction and the reaction to form a resin are increased. The reaction temperature is usually

 ~: I S O, preferably / ~ 2.2 · C. In addition, the heat treatment time varies depending on the amount of the catalyst and the reaction temperature, and cannot be generally specified, but it is usually in the range of ク to ク hours, preferably to to J hours.

Μ; ΜΔτ ': The amount of the isomeric ibi medium with respect to the anhydrous maleinized dehydrated starch is determined by the weight of the anhydrous maleinized decatriene / cook.

 In comparison with part S, click on the weight part, preferably

 0.0 parts by weight. The compounds of the groups &) to e) may be added as they are to the heat-melted anhydrous maleinated decatriene, or may be dissolved in a solvent such as water or acetone. Add し て Any other method may be used. In addition, those in which these compounds are supported on a carrier are charged into a packed column, and anhydrous

 The reaction may be carried out by passing the maleated arosimene vapor at a desired reaction temperature.

 As described above, the isomerized catalysts of the groups a) to β) are supported on a carrier such as rock, activated carbon, diatomaceous earth, silica gel, and molecular sieve. The steam of anhydrous maleic acid can be passed through the column packed with the catalyst at a predetermined reaction temperature to perform continuous heat treatment. If

 2 0. ~ Heat treatment at high temperature of J-0C for a short time

ό ο

 The liquid isomerized in this way is self-stable, but the liquid obtained by isomerization in the presence of a compound selected from the groups), d) and β) I hope to increase the stability of the product to the same extent as the liquid obtained by isomerization in the presence of the selected compound.

S u 4 1, vV:? 0,-', no. At the time,),,, ») group]) After heat denaturation in the presence of the obtained compound, add an acidic catalyst or a noble metal catalyst, and heat denature to further improve liquid stability. Improve ο

 Acidic catalysts for this second stage of isomerization include, for example, boronic acid, ethyl ether salt of boron trifluoride, linoleum pentoxide, sulfuric acid, phosphoric acid, sulfuric acid chloride. Lin, pentachloride, sodium acid sulfate, pyrrolic acid, metallic acid, sulfuric acid, chlorsulfuric acid, silica, alumina, acid ion Exchange resin, aromatic sulfonate, acid clay, activated clay, aluminum chloride, titanium tetrachloride, • 2,2 tin chloride, boron trichloride, etc. Examples include rhodium, ruthenium, palladium, etc.

 The heat treatment conditions for the second stage of isomerization are as follows: liquefaction requires a long time for liquefaction when the heating temperature is too low, and decomposition reaction and resin formation reaction when the heating temperature is too high. Decrease the yield of The reaction temperature, reaction time, and amount of catalyst vary depending on the type of the medium, so general specifications can be generally made. However, the reaction temperature of the second stage is usually S 0 2 S 0 ま《2.2k

C. The heat treatment time is between minutes and ^ hours, preferably between hours and hours. In the case of a noble metal catalyst, the amount of catalyst is anhydrous maleated decatriene / quen

ΟΜΡΙ Parts / part by weight, ion-exchange tree St, silica, aluminum, etc.///parts by weight], and other acidic catalysts is there.

It should be noted,), a), «) of the compound by that the isomerization in facilities Sana or sulfuric acid anhydride Ma ray emissions of deca-door Li E down Β to? ₃ • by heating in the presence of er Te le salt only Also liquefies ο

 The product obtained by treating according to the method of the present invention can be used as it is as an epoxy resin curing agent, but it is preferable to wash with water and then distill to obtain an excellent cured product. Alternatively, it may be subjected to activated carbon treatment for decolorization, addition of a super-aid such as diatomaceous earth, and an appropriate dehydrating agent treatment for removing water, followed by filtration and distillation. .

Industrial applicability

'' Since the liquid product obtained by the method of the present invention is liquid at room temperature, it can be used as an acid component of epoxy resin hardener, alkyl resin, and unsaturated polyester resin. Can be used. In addition, this product can be converted to amide, imid, ester, chlorine addition, alkylene oxyside adduct, etc., and used as a server inhibitor. Grease base oil as magnesium salt, aluminum salt, rubber and resin as polyester (particularly vinyl chloride ~ 1P0) — —

Resin) can also be used as a plasticizer. -In particular, this liquid product is a mixture of various epoxy resins, for example,

(Where ^ is the number of carbon atoms / ~ ^ << 2 《alkylene group

 0

Or one S — group, one S — group, one group, — 0 — group and

 6

Starts selling Chino ζ one group of groups, ₂ one GH _s or one; a beauty 1 -

, And n represents ~ 2

Epoxy resin, novolac type phenolic resin, and epoxy resin obtained from ebichlorohydrin, phthalic acid and phthalic acid Epoxy resin obtained from bihydric hydrin, epoxy resin obtained from benzoyl benzoic acid and evichlorohydrin Aromatic amines such as n-phenylene and ebichlorohydrin are used as curing agents for various epoxy resins such as the obtained epoxy resins. Demonstrates performance o When this liquid product is used as a curing agent for epoxy resin, the amount used is usually ~ 7 to 7 parts per hundred parts by weight epoxy resin. , Preferably <τ ~ Z is the weight part.

 When this liquid product is used as an epoxy resin curing agent, another anhydride curing agent may be used in combination, if necessary. For example, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, phthalic anhydride Acid, anhydrous viromellitic acid, dodecyl-succinic anhydride, nadic anhydride, and chlorendic anhydride, with a carbon number of / ^ to << 2 / or J And carboxylic acid containing tricarboxylic acid as a main component.

 Furthermore, when this liquid product is used as an epoxy resin curing agent, a curing accelerator can be used in combination as needed. For example, Trialkylamine, N—Dimethylbenzilamine, Triethanolamine, Perididin, Dimethylaminomethylethylphenol And tris (dimethylaminomethyl) phenol, tris (dimethylaminomethyl) phenol, imidazole (Such as << 2-ethyl-methylimidazole), dicyandiamide and triphenylphosphine can be used in combination as a curing accelerator. . The combined use amount of the curing accelerator is preferably within the range of // to part by weight based on the epoxy resin / part by weight.

OVPI 0 Examples and application examples

 Next, the present invention will be described with reference to examples and experimental examples.o An example of production of anhydrous maleinated oxime

Maleic anhydride S-έ9 ( ⁷ · mol) was added to a four-port flask with a capacity ^ equipped with an agitator, a thermometer, a condenser, a dropping funnel, and a nitrogen inlet tube. I put it in a scooter and added Benzen / _CC . While stirring at room temperature, /0.09 (mol) of arosimene (product of Yasuhara Yushi Kogyo Co., Ltd.) was gradually added dropwise. Since the temperature rises due to the heat of reaction, the reaction temperature was kept at 7 or less by cooling at a low temperature. It took about / hour to finish the dripping of the lipstick. In order to complete the reaction further, the mixture was stirred at about 7 to about 10 hours / hour. The reaction solution was red at the time of dropping arosimine and turned light brown as the reaction was completed. ;

 After completion of the reaction, excess benzene and solvent benzene were distilled off by suction with a gas vibrator at a temperature of / 0 OC or less (decompression pressure <2 << s H?). .

 The resulting anhydrous maleinated thymine had a melting point of 7 to 0 C and was a solid at room temperature.

Example /

 The anhydrous maleinated solvent obtained in the above production example was mixed with a stirrer, thermometer, capacitor, nitrogen

_ CV, PI The mixture was placed in a four-necked flask with an inlet tube, and heated to about / C to dissolve. Cormorant by the this Kana door Li U n / a, added to the <? F, "2 in the click C" 2 hours stirred ₀ by cormorants Kana door Li c arm is not completely dissolved, was fine rather than dispersion .

 After completion of the reaction, methyl isopropyl butyl ketone cc was added, and

/ Washed with aqueous sodium cciosulfate solution (cc). After washing with water, the aqueous layer was removed, and the oil layer was dewatered by adding sodium sulfate as a dehydrating agent, followed by simple distillation at tear pressure. / ~ / <F CZ> A light yellow liquid anhydrous maleimide porcelain oscimene f (yield) was obtained as a fraction of fCZ.

This liquid anhydrous maleated mouth liquor can be stored in a refrigerator of C, in a refrigerator of 2C, and at room temperature (<< 2 to << 21:) for more than 2 months. Although left undisturbed, the slip did not crystallize. Its viscosity (E-type viscometer) is "was at C / · 2 · ί · .ρ Β. Example" J 2 ~ /

 Except that the type of the catalyst, the amount of the catalyst, the reaction time, the reaction temperature, and the method of adding the catalyst were changed as shown in Table /, the solid anhydrous maleic ester was prepared according to the method described in Example /. The osimene was heat treated.

 The viscosity and yield of the obtained liquid anhydrous maleic acid oscimene are shown in Table <2.

 The catalyst was uniformly dissolved in Examples 〜 to /, but the catalyst was dispersed without being partially dissolved in other Examples.

_ ΟΜΡΙ "W1I 0, In addition, the liquid anhydrous maleic acid simulated (distilled and purified product) obtained in each of the examples has excellent liquid stability, and can be used at a temperature of 1 << 2 U, << 2 ~. In <2 months, the crystals did not precipitate. table /

 Amount of catalyst catalyst6¾ ffi ¾: ¾ ¾§c-/ h / nP -fca "i 5¾ ± i SI / 汉 间 间 / Na I s Add as it is 200 hours 閒

 2 / εοχ / ν · hour

 3 »9 Λ20 C // hour

 K I 0 s SI 丄 ノ Snow 9 έ 3 0 /. Time then ^ 00TC 2 ^

7 0 0 TC / 3 s- 0.33

 Caroline as

 9 K 0 0 "/ o ^ aqueous solution

 Added as

 / 0 K I 0 ø

 / / N a I 0.020 ^ liquid

 Caroline as

 / 2 ø ø

 / 3 # r Acetone solution #

 Caroline as

/ ¥ ■ ø 0 Table 《2 Liquid production sensitivity Same yield

 Example

 Viscosity 2 (^)

/ / a J- f 3

 2/9

 3/2 «r f /

 / 30 9

 / 2 έ 9 3

 6 / έS? Three

 7 / ¥ ■ S? Λ

 0 6? /

 ? / <Γ 3? Three

 / 0/7 S 3

 / / /? 7 3

 / 2/3 «2

 / 3 / New 7?

 //? S? Three

note)

 «1: The weight of the original family male

«2: c p θ (· 2 C)

 Place the solid anhydrous maleinated Ossimen 0 f into a four-port flask equipped with a stirrer, thermometer, capacitor, and nitrogen inlet tube, and press Heated to dissolve. This

ΟΛ'ΡΙ ノ V, ': i 0 To this was added lithium bromide / water salt, and the mixture was stirred at 0 / time. Lithium bromide was not completely dissolved and was finely dispersed.

After the completion of the reaction, decompression was achieved. / O ~ / 6 J give the "CZ click. Te" H _f fractions and to pale yellow liquid anhydrous Ma Tray Ni匕A port clever man main emissions 9 (驭率de lambda).

 This liquid anhydrous maleated arosimene is left for at least 2 months in a refrigerator of C, a refrigerator of 1.2 C, and at room temperature (<< 2 C to << 2 C). However, none of them crystallized. Its viscosity (Ε-type viscometer) was / 76 cps.

Example / ~ 《2

 Shows the type, amount, reaction time and reaction temperature of the catalyst. The solid non-aqueous Malencia mouthpiece was liquefied in the same manner as in Example / J ", except for the changes as shown in (1).

 The viscosity and yield at 2 C of the obtained liquid are shown in the table. The liquid obtained in each example exhibited liquid stability equivalent to that of the liquid obtained in the examples.

-. table ·?

Example << 2 /

 Add the solid anhydrous maleated arosimin 0f to a four-hole flask equipped with a stirrer, thermometer, capacitor and nitrogen inlet tube, and add about / ^ C. Heated to dissolve. Add 0.3 n of tri-n-butylamine to this and add /? 0

The mixture was stirred while introducing nitrogen at C / hour. During this time, tri- _n -butylamine was uniformly dissolved.

Dark圧度click the product after processing. "To simple distillation at H, / ⁷

// C CZ ク. ^ As a fraction of Mi Hj ^, a pale yellow liquid anhydrous maleinated alosimen J " ⁷ f (anhydrous maleinated The viscosity (: E type viscometer) was << 21: 1 and T7 cps.

O PI

Wil'O This liquid anhydrous maleated mouth is at room temperature.

 («2 to 《2 C) · No crystallization occurred even if left for more than 2 weeks or left in the refrigerator (J" C). Add the above-mentioned anhydrous maleinated citrine before liquefaction to lnhia citrus / noodle / 0 and add it to the refrigerator.

When left to stand, it crystallized after J days.

Example << 2 ώ ~ 0

 Example 2 Using an anhydrous maleimide porcelain oxime produced in the same manner as in 2 /, as shown in the table, the type of the nitrogen-containing organic compound, the amount added, the reaction temperature and the reaction The time was changed variously, and the liquefaction treatment of the anhydrous maleinated alcohol was carried out according to the method in the examples otherwise.

 The result was 9 in the table.

'ΟΛίΡΙ ヽ ¾π.

Nitrogen element-containing organic compound Liquefaction product Example

 储 量 Usage reaction temperature / time Viscosity yield

 ((cps)

 a / tree n—funal chon 0 ·-/ 90Ό / / time <f 7? J-

2 リ エ 一, .0 0X) / /? <r? 3 3 ェ ¾ 塩 酸 ^

 ¾1 / .0 ΛΟ nr / / 2? V / 0 / ίΌ // {^ Ha? For cetyltrimethylammonium bromide 0? Three

2 J-triethylenetetramine /.-$·ΛΟΟΌ/hour/ 0 3? 0

 /, One mouth per one mouth [· ♦] 0 a f 7 O / l ^ fMJ? J- 9

27 Jazabicyclo [] / v-OO / / Time <r 8-?

 ENDENSEN 7

 Tree n-butylamine.s-? 3? ¥ ■ Isoquinoline / .0 // 0? S

30 • 2, one tris (dimethylaminomethyl) / ·. «2 kuku C // time / 00? S

Phenoic Λζ) · 2- ェ キ サ ン ^ xanthate

Example J /

Maleic anhydride 99 ( ⁷ cm) was charged with a stirrer, thermometer, capacitor, drip funnel, and nitrogen inlet tube. placed in a full-la scan copolymers, heated to摱拌and want a nitrogen gas introduction / 3 0~ 'Ά C, § port talent of temperature Tamochiru La click f this (.3 ⁷ molar) System A mixed solution of men and 0-terebine (purchased by Yasuhara Yushi Kogyo Co., Ltd.) / 09 (0.37 mol) having a purity of 0 was gradually added dropwise. The dripping was completed in about / hour, and the mixture was further stirred for / hour. The obtained product was purified by distillation at a reduced pressure of << 2 cubic centimeters, and the product immediately after the distillation, that is, the anhydrous male anilide, the anhydrous male and the anhydrous male ani The mixed acid anhydride consisting of rubinene was liquid, but crystallized after 3 days.

 Tri-n-butylamine.ff (acid) was added to the mixture of the maleinated maleoarosimene obtained above and the maleinated monoterbinene. To the theoretical yield of the anhydride mixture was added 0. J "weight), and the mixture was stirred at / C for · J" hours. The obtained product was subjected to simple distillation at the decompression degree, and / J "J" ~ / <ΓC / ί? · «Ηί» as a light yellow liquid mixed acid anhydride / S09 ( The yield? /) Was obtained. Its viscosity at 2 C was 260 cpe.

This liquid mixed acid anhydride can be used at room temperature (2 ~ << 2 J "C), in a J" C refrigerator, and in a << 2 C refrigerator. All were kept stable for more than 2 months. To this liquid mixed acid anhydride / 0 ^, add solid ^^ of maleic anhydride maleic acid and add it to the refrigerator.

 When it was left in (C), it was likewise kept << stable for more than 2 months.

Example "? New ~ 3 S

 In place of the mixed solution dropped in Example 1, arosimimen and α-terbiene described in the table (Example 1) were used.

3 / Same as used in) or Milsen (purity ⁷⁾

 f>)) and a maleic anhydride reaction was carried out in the same manner as in the other examples, and the resulting maleic anhydride was subjected to an isomerization reaction in the same manner. Let me know.

 The viscosity and yield of each mixed acid anhydride after liquefaction were as shown in the table. In addition, when a stability test similar to that in Example 1 was performed on the mixed acid anhydride in a liquid state with that in Example 1, the deviation was kept stable in a liquid state for 2 months or more.

Then 4 ί?

/ O: \ pr Mixture ratio of raw material unsaturated hydrocarbons (weight ^) Liquefied product

 a Binnen Milsen Viscosity 《3 Yield

Lol example \ (cps) (weight ^)

 3 / Jr 0 0 1 0? New

3 2 J "0 0? 0

3 3 ά 0 ¼ 0 a 2 Λ? Three

3 V- 7 0 3 0 / / -2? a

3 3 0 7 0 3 0 <f 7

note)

 «1: The numbers in the table indicate the purity of a-terbinene solution with / 0 conversion.

 2: The numbers in the table represent 7-purity myrcene solution in terms of 100.

3: Indicates the value measured at «2.

Example ^

 Example << Liquid anhydrous maleated aromatic compound obtained in 2 /

 (Nissan Chemical Co., Ltd., product name, silica 56, alumina / ^) / f, add the mixture with / <f ^ t: for an hour, cool to room temperature, and mix. Chillisobutyl butyl ketone

2 ^ was added to filter out and separate insolubles such as silica and alumina, and the methylisobutyl ketone in the solubles was removed using an evaporator.

 Next, the residue was distilled under reduced pressure to obtain a / 〜 / cook C fraction / 709 (yield) at a reduced pressure of ./ί.

 The viscosity of the liquefied anhydrous maleinated mouth osmine at the temperature J- was / centivoise. In addition, this liquid material is << 2 C, h C! In each of the temperature-controlled chambers, the liquid remained even after storage for 2 months.

 Further, this liquid compound was mixed with a solid anhydrous male teriyaki-shimen, and the liquid was maintained even when stored in a thermostatic chamber for a long time.

Example C ~ 2

Example 2 The liquid anhydrous maleic acid obtained from Example 2 was prepared using the acidic catalyst shown in Table 4 as the second stage isomerization catalyst. A liquid was obtained in the same manner as in Example J except that the amount of the catalyst, the second-stage treatment temperature, the treatment time, and the post-treatment method were performed under the conditions shown in the same table. ― 57

The viscosities at << 2 C of the liquid materials and the results of the liquid stability test of the same items as in Example <? / Are shown in the table together with the yield.

6

*: After adding methylisobutyl ketone / 01 ^, water was added and washed with water. The water eyebrows were separated and distilled under reduced pressure.

**: BF, content ⁷ weight ^

***: Amper list / (Roam &'Haas' product name)

Example ·

 The solid anhydrous male thiocyanate 0 was placed in a four-port flask equipped with an agitator, a thermometer, a condenser, and a nitrogen gas inlet tube, and placed under a stream of nitrogen gas. While stirring, it was heated to / C to dissolve. To this was added triphenylphosphine, and the mixture was further heated to raise the temperature to Note C. The reaction was continued for 1 hour at the same temperature.

 A pale yellow fraction of / ~ / 7 SC was obtained under decompression of ^^ Sffl H (yield? 0).

 The viscosity at «2 J * t? Of this liquefied anhydrous maleic anhydride π-year-old sim was« 2 centivoise. In addition, the thing was >> it did not crystallize even after storage at a temperature of 20 C for 2 weeks.

 To this liquid compound / f, solid anhydrous maleated arosimene was added, and the mixture was stored in a constant temperature room, and crystallized ^ days later. i

Example

 The powdery anhydrous maleinated osmotic sodium 200 ^ obtained in the example was added to the powdery silica-alumina N— <≤ J / * L

 (Nikki Chemical Co., Ltd., product name, silica * Γ7, aluminum /

56) / <≤ ¾: Heating, stirring for a time at / <TOC, cooling to room temperature, and then adding methyl isobutyl ketone /

 To remove insolubles such as silica and alumina, and to separate methylisobutyl ketone in the solubles.

 -UREAU OMPI

// V. ⁰ Removed using a rotator.

 Then, the residue was subjected to low pressure distillation to obtain a fraction of / C at a decompression pressure of / 圧 / 70 ° C (yield).

 The viscosity of the liquefied anhydrous maleinated liposome in 2SC was / centivoise. In addition, the liquid remained liquid even after being stored for two months in each of the thermostatic chambers «2,, C, and« 2.

 In addition, this liquid compound / was mixed with solid anhydrous maleinated citamine / q. / F and kept in a thermostat chamber of C for 2 months.

Example ~ ^

 In the same manner as in the Examples except that the type of the catalyst of the sintered element-containing organic compound, the amount of the catalyst, the reaction temperature and the time are as shown in Table 7, the solid maleic anhydride was prepared in the same manner. Was liquefied.

 The yield of the obtained liquid, the viscosity at <2 and the stability of the liquid when stored at room temperature for 2 weeks are shown in the same table.

OMPI

Wlf 0 7

 i Anhydrous maleated π Osimen / Amount based on parts by weight

Example

 maleic anhydride ? f was placed in the four-neck flask used in Example ^, heated to a temperature of / C while stirring under a nitrogen gas stream, and then kept at the same temperature. A mixture of terbinene / sulfur and high-purity terbinine / k was added dropwise over a period of / hour, followed by stirring at the same temperature for / minute.

 After that, triphenylphosphine was added to the flask and added to the flask. After the temperature was raised to, stirring was continued at the same temperature for J minutes to complete the isomerization.

 After completion of the reaction, a pale yellow fraction of / J "J" to / C was obtained under decompression of H. The viscosity at 2 C of this liquid was 7 centimeters. In addition, this liquid remained in the liquid state even after being stored for two months in each of the thermostatic chambers of 《2 c, J ″ cr, — 2C.

 Further, this liquid compound / 0f was mixed with a solid anhydrous maleinated arosimene. The mixture was kept in a thermostatic chamber for 2 months.

Example J

A. Stability of pale yellow liquid obtained by isomerization treatment in the same manner as in Example No. 2 except that the ratio of 1-terbinene, which is , 2 ^ υ were measured. The results are shown in Table ^ together with the yield. ' 4 Example2,

Table the Mi Le Se emissions of ⁷ S purity to the die one Te le-bi ne down such

• Examples other than using the ratio shown in 2? In the same manner as in the above, the resulting pale yellow liquid was subjected to a catabolic treatment, and the stability and the viscosity in h SC were measured. The results are shown in Table <Γ together with the yield.

 In addition, each of the liquid materials

/ 0 ^ was mixed with solid anhydrous maleinated thyme./ 9 was blended and stored in a thermostatic chamber for 2 months.The liquid stability of each was observed. It remained liquid.

δ

 »1 The numbers in the table are obtained by replacing 0-purity <<-terbinene solution with / 00.

«2 The numbers in the table are for 7 J" pure myrcene solution, converted to / 00.

Example ~

 The compounds shown in the table below are used in the amounts shown in the table, and the isomerization temperature and treatment time are as shown in the table. Solid anhydrous male urea in the same manner as in Example S. Mouth osmine is liquefied, and the viscosity of the obtained liquid in C is 2 hours. Stability was measured.

 Table of results with yield? Shown in

9

Example J

 Tri-en-hos-fink

• A pale yellow liquid (yield ^ :) was obtained in the same manner as in Example II except that i.f, conditions for isomerization, / C, and minute were set to 00 and / hour. .

ΟΛ'.ΡΙ The viscosity at << 2 J "C of this product was centimeter-voise. Also, when the liquid material was stored in a constant temperature room at 20 V ^" C, one 2.0 C In addition, this liquid compound is mixed with a solid anhydrous maleide π oxime, and the liquid compound is kept in a constant temperature room for 2 months. Was.

Example Ο

 A pale yellow liquid (yield 22 multi) was obtained in the same manner as in Example 10 except that the amount of 1-terbinene as an arosimene was changed to 09 and 1, respectively. The viscosity of the liquid material at «2 J” C was «23 centivoise. In addition, the liquid stability of the above-mentioned items remained liquid even after a deviation of 《two months.

Example ^ /

 A pale yellow liquid 犊 (yield) 得 was obtained in the same manner as in Example ク except that mirsen was used instead of terbinane. The viscosity at << 2 J "C was / q / cm.

 In addition, the stability of the liquid over a wide range of items remained in the liquid state even after a few months.

Example -2

A pale yellow liquid substance (yield) was prepared in the same manner as in Example / except that arosimene was used as / 0J-f and milsen as f. 1)) was obtained. The viscosity at 2C

 / 20 centimeters.

 In addition, the liquid stability over the items remained, but remained liquid even after 2 passes.

Example 3-S

 Same as in Example, except that the anhydrous maleic acid mouthwash obtained in Example 1 and Example 2 was used in place of the anhydrous maleinated aromatic compound obtained in Example 1. Then, reisomerization was performed using an acidic catalyst.

 The viscosity of the obtained liquid compound at 2SC is shown in Table / ^ together with the yield and liquid stability over various items. Table / 0

Example ~ Also <Γ

The liquid anhydrous maleic acid obtained from the example was prepared as follows: A liquid substance was prepared in the same manner as in the case of Jeongjeong except that the amount of catalyst used for each of the acidic catalysts and the amount of I got

 The results of the liquid stability test of the liquid material at << 2 C and various items are shown in Table // together with the yield.

OVPI 0 / /

• Second-stage reaction product

 Example Amount of catalyst Time 粘度 Viscosity of treatment Yield Liquid stability Catalyst name

 (R (C) (Time) (cps) W

 * All items are Boric acid / 2 Rinse / / s? 0

 Stable

 *

 ά 7 Sulfuric acid / o Rinse / 20

6 s- ion 錄 resin Λ 0/20 ^ excess / 20 <r

* Methyru siptil ketone /? After the addition of ^, water was added and washed with water, and water debris was separated, followed by distillation under reduced pressure.

 ** Amper list / (Roam & Haas brand name)

'

Example ^ te ~ 7 /

 • 2 The Diels-Alder reaction product (melting point ^ 0C) of 1-dimethyl // ^-octatriene and maleic anhydride was obtained in Example / under the conditions shown in Table /. A liquefaction reaction was performed.

 The viscosity and yield at 2 C of the obtained liquid are shown in the same table. Table / -2

Example 7 «2

 Solid << 2, <≤ —Dimethylo /, octatriene anti-maleic anhydride Diels-Alder adduct ^ 0f was stirred with a stirrer, thermometer, condenser and nitrogen introduced The tube was placed in a four-neck flask with a tube, and heated to about <f ^ to dissolve it. Add n-butylamine J to this,

Nitrogen was introduced at <f 0 C: stirring was performed for 5: 5 hours. Tri-η-butylamine was uniformly dissolved. processing The subsequent product is subjected to simple distillation at decompression degree /, and / ~ / 7 <Γ

CZ / · click S «: as a fraction of H _f, to give a pale yellow liquid anhydrous Ma Tray Nkaa port old sheet main emissions 9 (yield: j 0 f,). Its viscosity was << 2 ^ C and << 2 / c cpe.

 This liquid product was subjected to the same liquid stability test as that of Jeongjeong-e ^ /, and all were kept liquid for two months. Application example as epoxy resin curing agent

Experimental example /

 Web Coat << Γ J ^

Equivalent / ^ te, · 2, 2-bis (one hydroxy-file) globule of bropan] / cook part (weight part, below The same), the liquid anhydrous maleic acid mouth osmene obtained in Example / // part and the curing accelerator veneer

The rudimethylamine / part was uniformly stirred and mixed at room temperature, and defoamed under reduced pressure (under J TOH ^^) to prepare an epoxy resin composition. The viscosity of the composition with

So! ? The casting and the like were extremely easy.

 The resin composition is cured at <f <? C for ^ hours, then

When the post-curing was carried out for 2 hours at / 2 C, a tough cured resin was obtained as shown in Table / J.

 In Table / J, for comparison, the formulation of the epoxy resin composition to which a known curing agent was combined and the properties of the cured resin were added.

 ^

ΟΛίΡί

? s

5 Note on table / ·)-

* 1: The curing agent is hexahydro-free 7 '' tallic acid. * 2: The curing agent is commercially available Dodecel * Succinic

 • Anhydride (Sanyo Kasei Co., Ltd. product name DSA), which is represented by the following general formula:

 R— 0H = CH— OH— GH— C

 ヽ

 0

 OH— C

 In the formula, R and are an alkyl group or hydrogen, and the sum of the carbon numbers of κ and R ′ is で.

 «3-benzyl dimethylamine (curing accelerator).

 ^ 4 A e T M T) —6 S ^ —S I]]?

 * 5 'D- 90-¥-? Ί '

^ 6 quake έ— έ ^ <f— <i J "Τ,

»7 1 2 inch. Hex nut method (conforms to Ori 7i-ant-washer method)

8 AS TM D— / O— As is clear from the results in Table 1 and Table 2, the ethoxy resin composition of Experimental Example 2 shows a high heat distortion temperature even though the side chain of the curing agent is a short butenyl group. In other words, the comparative example using a curing agent having a long alkyl group in the side chain. Heat deformation temperature shows high value about C ^

 In addition, the composition of Experimental Example / has a higher crack resistance than the composition of Comparative Example / which uses hexahydrophthalic anhydride as a curing agent. This is presumed to be due to the fact that the liquid anhydrous maleic alcohol has an increased solubility due to the presence of a butyl group in the side chain.

 Furthermore, the mechanical properties and electrical properties of the cured product of the composition of Experimental Example / were higher than those of Comparative Example Composition / using hexahydrophthalic anhydride as a curing agent. The color of the target is dark.

Experimental example2

コ Γ Γ 商品 Γ [Chemical Co., Ltd. product name, epoxy equivalent /? «2,« 2-Glycidyl ether of bis-propane (-hydroxyl fuel) propane] / 100 parts (parts by weight, the same shall apply hereinafter) as a curing agent Example << Liquidized product of anhydrous maleic acid mouth mouth obtained in 2 / liquefied treated product / box and benzyldimethylamine as curing accelerator << 2 parts uniform mixing at room temperature mixed, "2» was defoamed by blinking pressure of H _f were prepared et poke a resin composition.

 This composition had a viscosity of about 10 / tevoise], and was extremely easy to cast.

When this resin composition was pre-cured at ^ C for ^ h, and then post-cured at / 20C, a tough-cured resin having the following properties was obtained. Experiment 3

 Mixture of anhydrous maleinated aro- simimen and anhydrous maleinized terrubin obtained in Example as a curing agent. The eboxy resin was cured in the same manner as in Experimental Example <2, except that the part was used.

 The result was as shown in Table /.

Experimental example

 As a hardening agent, a mixture of anhydrous maleinated alcohol obtained in Example and a mixture of anhydrous maleinated milsene and a liquefied anhydride / The ethoxy resin was cured in the same manner as in the experimental example.

 The king was as shown in the table.

Experimental example

 The epoxy resin was cured in the same manner as in Experimental Example except that the liquid maleic anhydride mouth / part obtained in Example ^ 7 was used as a curing agent.

 The results are shown in Table /.

OV.Pi · /

— -——. Test Example ¾ 2 3 i-Ebi Coat ^ «2/00/00/00/00 Tree Hardener

 Liquefied matter of Example / 20

Example 3 Liquid liquefied product of 1/90 1 1 part Example 3 Liquid liquefied product of ¥ ■ / 1/30 1 Example J Liquid product of 7/11/20 Curing accelerator (benzyldimethylamine) 2 2 2 2 songs Mi ge, no strong JW ^ (\, g. /, C cn〃t ¹ *) no / "o

 Bending elastic modulus () 3/0 3/0 300 3/0 Thermal deformation temperature (C) / Ά 3 / / / / / J- / / S tree Heat-resistant mouth purple (crack resistance) / / / / Fat induction rate

3.3 SS 3.2 3.3 objects / KHs 3.2 3.r 3.Λ 3.2 Properties / 00 KHz 3.3 3. / 3.Λ Water resistance (heavy increase ^) 0.3 0.3 ^ 0.33 0.3 Λ

Experimental example /

 N

 Epoxy resin "Bico-t ^" (trade name of Shell Chemical Co., Ltd .: eboxy equivalent / ^ te) / Penzyldimethylamine <2 parts by weight as a curing accelerator in parts by weight As a hardening agent, the liquid anhydrous maleic acid extract obtained in each of the examples shown in Tables 1 and 2 was blended in the amount shown in the table and uniformly stirred and mixed at room temperature. Defoaming was performed under the following decompression pressure to prepare an ethoxy resin composition.

 The resin composition was pre-cured at <τ C for a time, and then heated to / 2, and then urged to the same temperature for a time to be completely cured.

 The physical properties of the obtained cured product are shown in Table 2 together with the viscosity at 2 J "C of the epoxy resin composition before curing.

Then 'RT, ^ , J

 7? / 0 / / Anhydrous Maleny Daira ァ Oshimen ^ J ¾¾ J Te Combination (Seigei) / 20? 0 / 3,0? 0/20/30 Epoxy resin composition viscosity (ops)? S 0 Λ, 300 98-0 t / ΌΟΟ 670 Bending strength (^ / c) / ¥ -.0 / / · (? / 3./3 I / 3 ^ Hard bending elasticity (H / i) 3/0 320 3/0 300 320 3Λ0 Thermal deformation temperature (c) / 2 / / / 0/22 / / 0 / 0.3 / /

 Impact resistance / / / / / / dielectric constant (SOB.Z) 3.3 3.3 3 * 3 3.3 dielectric (/ KHz) 3.2 3.3 3.3 3

 (/ OOKEz) 3.2 3,2 3 3 3

Water resistance 0.33 0.3S 0.33 0.36 0.3V 0.3 /

Example of experiment / <2-Webcoat << Γ2 <Γ [Chemical Co., Ltd. product name, epoxy equivalent / «Γ, · 2, Glycidyl ether of bronone) / 0 parts (parts by weight, the same applies hereinafter), liquid anhydrous maleic acid obtained in Example / Interview ^ parts and homogeneously攙拌mixed pen Jiruji main Chirua unprecedented / parts of the curing accelerator at room temperature, prepared渎圧under ( "2» «less H _f) in defoamed et poke a resin composition did. The viscosities of the compositions of and were «2« i ”C and about« 2 J voice!?, Casting was extremely easy.

 When the resin composition was cured at s-0 C for ^ hours and then at / 2 ° C for 4 hours, a tough cured resin was obtained as shown in Table / ^.

Experimental example / 3

Liquid anhydrous male ? A cured product was obtained in the same manner as in Experimental Example 2 except that the liquid obtained in Example 10 was not used. The physical properties of the cured product are shown in Table / έ.

Table No. Example / «2 Example / ^ Shrimp Coat <Γ« 2ί / 0 0/0 0 Pair

 eft- naruto agent / 20/20

(Part) / / Thermal deformation temperature (C) / / 0 / / Bending strength (ι ^ / ½ / 3 _t S / V-.0

 Bending elasticity ratio 3 0 0 3 2 0

 Thermal impact / / object

 (Electricity)

 of

 6 0 Έ.Ζ 3. / 3.0

 / KHz 3,0 3,0 Properties / 0 0 KHz 3.0 3.0

Claims

The scope of the claims

/ Heat treating the Diels-Alder reaction product of maleic anhydride and decatriene solid at room temperature in the presence of a compound selected from the following groups a) to β) Liquefaction method of acid anhydride characterized by this

 a) Alkali metal salt

 ) Organic compounds containing nitrogen element

 c) Phosphine compounds, first-class phosphine salts i) Selected organic compounds containing phosphorus d) Thiocyanate

 e) Solid basic compounds (excluding compounds in group a) above).

 • 2 The method for liquefying an acid anhydride according to Claims / Claims, characterized in that the decatriene is an arosimene.

 3. The method for liquefying an acid anhydride according to claim / 3, characterized in that it is a decatriene kami << 2,1-dimethyl >>?

■ The method for liquefying an acid anhydride according to Claims / Claim, wherein the heat treatment is performed in the presence of an alkali metal salt.

 Between solid maleic anhydride and decatriene

Ruth-Alder reaction product / 0 parts by weight

a) to β) group D

 The method for liquefying an acid anhydride according to claim 5, wherein the amount is 0.0 i-part or more.

 4. The method for liquefying an acid anhydride according to claim 1, wherein the heat treatment temperature is in the range of ク to 22.

 4. The method for liquefying an acid anhydride according to claim 1, wherein the alkali metal salt is a compound selected from the group consisting of lithium oxide and iodine trioxide.