JPS6137265B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel unsaturated compound and a method for producing the same. More specifically, the present invention relates to hydantoins containing terminal allyl groups useful as raw materials for thermosetting polymers having excellent heat resistance and methods for producing the same. Diaryl phthalate resin has been known as a radically curable polymer having an unsaturated group.
It is widely used in the fields of electronic communication equipment parts, electrical parts, foods, chemical equipment parts, etc. in the form of molded products, decorative boards, laminates, enamel varnishes, impregnated varnishes, etc. However, this resin has a heat resistance of about 150° C. at most, and is not necessarily satisfactory in terms of heat resistance. The present inventors have carried out intensive research to obtain a compound that provides a cured resin with even better heat resistance, and as a result, they have arrived at the present invention. That is, the present invention is based on the following general formula [However, in the formula, R ₁ is a hydrogen atom or a lower alkyl group,
R ₂ and R ₃ are groups selected from the same or different hydrogen atoms and monovalent organic groups, R ₄ and R ₅ are the same or different divalent organic groups, and n represents a positive integer. ] These are terminal allyl group-containing hydantoins represented by: To explain in more detail the terminal allyl group-containing hydantoins represented by the above general formula of the present invention, in the above formula, R ₁ is a hydrogen atom or a lower alkyl group, such as an alkyl group having 1 to 4 carbon atoms, and the raw materials described below are Hydrogen atoms and methyl groups are particularly preferred from the viewpoint of availability and reactivity. Furthermore, R ₁ at both ends may be the same or different. Next, R ₂ and R ₃ are the same or different hydrogen atoms or monovalent organic groups, and monovalent organic groups include alkyl groups such as methyl group and ethyl group, aryl groups such as phenyl group and tolyl group, and cyclohexyl group. Examples include cycloalkyl groups such as cycloalkyl groups, and among these, hydrogen atoms and methyl groups are particularly preferred from an industrial standpoint. Further, in the present invention, R ₂ and R ₃ of each hydantoin ring forming the main chain may be the same or different between the rings. Next, in the general formula of the above compound of the present invention, R ₄ and R ₅ are divalent organic groups, but they may also be aliphatic, alicyclic, aromatic, or a mixture thereof. Specific examples include m- and R 5 . P-phenylene,

【formula】

[Formula] 44′-biphenylene

【formula】

【formula】

[Formula] m- and P-key silylene,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Examples include tetramethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene. Further, R ₄ and R ₅ may be the same or different, and R ₄ may be different between the repeating units in the above formula. The terminal allyl group-containing hydantoin of the present invention refers to a compound substantially represented by the above general formula detailed above, and the hydantoin portion of the above general formula, i.e.

For example, a part of [formula] General formula

【formula】

【formula】

[Formula] and

[Formula] (However, in the above formula, D ₁ is a tetravalent organic group, D ₂ is a trivalent organic group, and D ₃ and D ₄ are divalent organic groups). It may also be a copolymer. When D ₁ , D ₂ , D ₃ or D ₄ is represented by the corresponding tetracarboxylic dianhydride, tricarboxylic anhydride, dicarboxylic acid or aminocarboxylic acid, for example, pyromellitic dianhydride,
3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, 1, 2, 3, 4-butane tetracarboxylic dianhydride, 1, 2, 3,4-cyclopentanetetracarboxylic dianhydride, 1,4,5,8-
Tetracarboxylic dianhydrides such as naphthalenetetracarboxylic dianhydride; tricarboxylic anhydrides such as trimellitic anhydride, tricarballylic anhydride, 3,3',4-benzophenone tricarboxylic anhydride; For example, dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyl etherdicarboxylic acid, cyclohexanedicarboxylic acid, sebacic acid, adipic acid; Examples include aminocarboxylic acids such as aminocaproic acid, 4-aminomethylcyclohexanecarboxylic acid, and m- and P-aminobenzoic acid. In the terminal allyl group-containing hydantoin represented by the above formula in the present invention, n represents a positive integer, and generally n is 1 to 20, preferably 1 to 15
A range of is advantageous. According to the research conducted by the present inventors, it has been found that the terminal allyl group-containing hydantoins represented by the above general formula can be produced by the following method. That is, () general expression

[Formula] Allylamine (A) represented by (where R ₁ is a hydrogen atom or a lower alkyl group), general formula (However, R ₂ and R ₃ are groups selected from the same or different hydrogen atoms and monovalent organic groups, and R ₄ is a divalent organic group.) Bisiminoacetic acid or its carboxylic acid derivative (B), General Diamine (c) represented by the formula NH ₂ −R ₅ −NH ₂ (wherein R ₅ represents a divalent organic group) and diaryl carbonate (D) are combined into the following formulas (i), (ii), and (iii). (i) A≧2(B-C) (ii) C≧0 (iii) D≧2B (In each of the above formulas, A, B, C, and D are respectively the above-mentioned (A), (B), and (C) ) and (D) (indicates the number of moles of component) are reacted at a satisfying ratio. or () general expression (However, R ₂ and R ₃ are groups selected from the same or different hydrogen atoms and monovalent organic groups, and R ₄ is a divalent organic group.) Bisiminoacetic acid or its carboxylic acid derivative (B), General Diisocyanate (E) represented by the formula OCN-R ₅ -NCO (where R ₅ represents a divalent organic group)
and general formula

[Formula] (However, R ₁ represents a hydrogen atom or a monovalent organic group)
Allyl isocyanate (F) represented by
(iv) and (v) formulas (iv) F≧2(B-E) (v) E≧0 (B, E, and F in the above formulas are (B), (E), and (F), respectively)
(indicates the number of moles of the components) is reacted at a satisfactory ratio. First, the method () will be specifically explained. (A) General formula used as component

The allylamine represented by [Formula] is CH ₂ =CH-CH ₂ NH ₂ ,

[Formula] is particularly preferred and may also be a mixture. (B) The general formula for the component is

Bisiminoacetic acid or its carboxylic acid derivative represented by the formula is used; in the formula, R ₂ , R ₃ , and R ₄ are the same as those described above, and the carboxylic acid derivative includes esters, amides, and the like. Preferably used esters include lower alkyl esters such as methyl and ethyl;
Aromatic esters such as phenyl and tolyl are mentioned. Also, as the amide, unsubstituted amide, methyl,
Examples include lower alkyl amides such as ethyl, dimethyl, and diethyl. Next, as component (c), a diamine represented by the general formula _NH2 - _R5 - _NH2 is used, where _R5 is the same as described above. Examples of the diaryl carbonate used as component (D) of the present invention include diphenyl carbonate, ditolyl carbonate, dinaphthyl carbonate, etc. Diphenyl carbonate, which is industrially easily available as a raw material for polycarbonate, is particularly preferably used. In the present invention, the above components A, B, C, and D are reacted in proportions satisfying the following formulas (i), (ii), and (iii). (i) A≧2(B-C), (ii) C-≧0, (iii) D≧2B (Definitions of A, B, C, and D in each formula are the same as above) Does not satisfy the relational expression In this case, the desired polyhydantoin containing an end allyl group cannot be obtained, which is not preferable. In addition, each component is substantially expressed by the following formula A' = 2
(B'-C'), D'=2B' (where A', B', C', and D' are the number of moles of each component A, B, C, and D involved in the reaction). Therefore, it is not necessary to use so many A and D components, and the upper limit is, for example, A≦2.6 (B-
C), D≦26B. Since the reaction is carried out in the melt or, if necessary, in a homogeneous system under mild conditions, an inert solvent such as toluene, xylene, chlorobenzene, dichlorobenzene, anisole, tetrahydrofuran,
It is carried out in the presence of N·N-dimethylformamide, N·N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, tetramethylurea, cresol, xylenol, etc., and the reaction temperature is generally 50 to 350°C. Preferably 100-300℃
It will be held in The reaction time depends on the reaction temperature, but is generally 0.5 to 20 hours, preferably 1 to 15 hours. If it is more than that, there is no effect of prolonging the reaction, and if it is less than that, the reaction will not proceed sufficiently. Next, the other manufacturing method, method (), will be explained. Bisiminoacetic acid or its carboxylic acid derivative used as component (B) is exactly the same as component (B) in the method () above. Next, the general formula O=C=N-R ₅ -N= used as component (E)
The diisocyanate represented by C═O corresponds to the diamine that is component (C) in the method () above, and R ₅ in the formula is as described above. Corresponding stabilized isocyanates such as phenyl and tolylurethane are also suitably used. General formula used as component (F)

Allyl isocyanate represented by [Formula]
In the formula, R ₁ is as described above, and in particular, O=C=N-CH ₁ CH=CH ₂ ,

[Formula] is preferably used. Stabilized isocyanates such as phenyl and tolylurethane are also preferably used. In the method of the present invention, each component is reacted in a proportion that satisfies the following formulas (iv) and (v). (iv) F≧2(B-E), (v) E≧0 (Definitions of B, E, and F in each formula are the same as above) If the above relational expression is not satisfied, the target terminal allyl group-containing Hydantoins cannot be obtained and are not preferred. In addition, each component is substantially expressed by the following formula F'=2(B'-
E') (where F', B', and E' are the number of moles of each component involved in the reaction), so there is no need to use that much F component, and the upper limit is, for example, F≦
It is about 2.6 (B-E). The reaction is carried out under substantially the same conditions as in the method () above. In the above () and () of the method of the present invention, (B)
A portion of the components, for example up to 30 mol %, may be replaced by the polycarboxylic acids described above, or their anhydrides, or their active derivatives, such as esters. The molecular weight of the terminal allyl group-containing hydantoins obtained in the method of the present invention is determined by the molar ratio of allylamine (A) to diamines (C) in the case of () to allyl isocyanate (F) in the case of (). It can be controlled by the molar ratio with diisocyanates (E). Generally, the higher the molar ratio of allyl components (A) and (F), the lower the molecular weight, and therefore the higher the density of terminal allyl groups. In the present invention, the obtained terminal allyl group-containing hydantoins are purified by methods such as recrystallization and reprecipitation. In addition, when the protein has a statistical structure, the reprecipitation method is particularly effective as a purification method. Of course, depending on the case, it is also possible to use the reaction solution as it is for molding without isolation. Further, the structure of the terminal allyl group-containing hydantoin obtained by the present invention can be confirmed by methods such as infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy, and elemental analysis. By radically curing the terminal allyl group-containing hydantoin itself or together with other allyl compounds as described above,
It can be converted into a resin with excellent heat resistance and can be widely applied to molded products, enamel varnishes, films, impregnated varnishes, adhesives, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, all "parts" mean "parts by weight." Example 1 57 parts of allylamine, 555 parts of 4,4'-bis(carboethoxymethylamino)diphenylmethane,
198 parts of 44'-diaminodiphermethane, 642 parts of diphenyl carbonate and N-methylpyrrolidone
Charge 3000 parts as a solvent into a reactor equipped with a stirrer,
The reaction was carried out at about 200°C for 3 hours with stirring. Then,
The reaction mixture was transferred into a large excess of methanol, and the precipitated product was separated and dried. The melting point of the reactant is 171~
The temperature is 178℃, and the infrared absorption spectrum is 1770cm ^-1
The strong characteristic absorption based on hydantoin also
A characteristic absorption layer based on allyl groups was observed at 1640 cm ^-1 . Moreover, the elemental analysis value of this substance is C=
74.1%, H=5.3%, N=11.1%, theoretical value C
= 73.5%, H = 5.0%, N = 11.6%, in good agreement.
The following formula This shows the formation of a compound represented by 3 parts by weight of dicumyl peroxide was added to 100 parts by weight of the obtained powder, mixed well, and compression molded at 220°C to obtain an amber molded product. When the heat resistance of this material was investigated by thermogravimetric analysis, it was found that the heat resistance was approximately 320.
It showed no weight loss up to ℃ and showed good heat resistance. Example 2 14 parts of m-bis(carboethoxymethylamino)benzene, 6.3 parts of allylamine, and 23.5 parts of diphenyl carbonate were charged into a reactor equipped with a stirrer,
The mixture was heated and stirred at 200-230°C. After 3 hours, the final reactants and by-products remaining in the reaction system were expelled under reduced pressure to obtain a product. The melting point of the product was 195-200°C. This product was washed with hot ethanol to obtain 160 parts (90%) of white crystals. The melting point of this product was 202°C. In the infrared absorption spectrum, hydantoin absorption was observed at 1760 cm ^-1 and 1700 cm ^-1 , and characteristic absorption based on allyl group was observed at 1640 cm ^-1 . The elemental analysis value is C=
62.1%, H=5.3%, N=15.9%, theoretical value C
= 61.0%, H = 5.1%, N = 15.8%, showing good agreement, and the following formula The formation of a compound represented by is shown. Further, 50 parts by weight of this product was melt-mixed with 50 parts by weight of N-allyl-4-allyloxycarbonylphthalimide, thoroughly ground, and then 3 parts by weight of dicumyl peroxide was added and cured at 200°C. As a result, a candy-colored cured resin was obtained. In thermogravimetric analysis (in air, heating rate: 5°C/min), this product showed no weight loss up to 330°C and exhibited good heat resistance. Example 3 In Example 2, 44'-bis(carboethoxymethylamino)diphenylmethane was used instead of 14 parts of m-bis(carboethoxymethylamino)benzene.
18.5 parts at 200°C in 100 parts cresol.
I let it react over time. The obtained reaction solution was poured into a large amount of methanol under stirring, and the precipitate was separated and dried to obtain 19.5 parts (88%) of white powder. The melting point of this product was 230-235°C. or,
Elemental analysis results are C=67.9%, H=5.1%, N=12.0
It was %. Theoretical value: C = 67.6%, H = 5.4%,
N=12.6%. In addition, the infrared absorption spectrum shows the characteristic absorption based on hydantoin at 1770 and 1720 cm ^-1 and the characteristic absorption based on allyl group at 1740 cm ^-1 , and the following formula It is expressed as The generation of was confirmed. When this product was cured in the same manner as in Example 2, it exhibited good thermosetting properties and gave a molded resin. Example 4 300 parts of bis(4-aminophenyl)ether,
39.6 parts of pyromellitic dianhydride, m-cresol
3,000 parts of xylene and 1,000 parts of xylene were charged into a reactor equipped with a stirrer, heated and stirred, and water produced by the reaction was removed from the reaction system by azeotrope with xylene. Next, 57 parts of allylamine, 504 parts of m-bis(carboxymethylamino)benzene, and 856 parts of diphenyl carbonate were added, and the mixture was reacted under reflux for 4 hours. Next, the reactant was added to a large excess of methanol, and the precipitated product was filtered. The melting point of the product obtained was 205 to 215 °C, and from the infrared absorption spectrum.
Overlapping absorptions based on hydantoin and imide bonds were observed at 1770 cm ^-1 and 1710 cm ^-1 , and at 1640 cm ^-1
Absorption based on the allyl group was observed, and analysis showed the following formula: 40 mol% of the compound represented by and the following formula Formation of 60 mol% of the compound represented by was observed. Example 5 4,4'-bis(carboethoxymethylamino)
555 parts of diphenylmethane, 250 parts of 4,4'-diphenylmethane diisocyanate, 85 parts of allyl isocyanate, and 3000 parts of N-methylpyrrolidone were charged into a reactor, and the temperature was gradually raised from room temperature to 180°C over 3 hours, and then heated for another 3 hours. , the reaction was allowed to proceed at 180°C. The product was then precipitated into methanol, separated and dried to obtain a product. The melting point of the product is 170-180
℃, and the infrared absorption spectrum completely matched that of Example 1. Example 6 28 parts of m-bis(carboethoxymethylamino)benzene, 17.4 parts of allyl isocyanate, and 100 parts of cresol were charged into a reactor and reacted for 4 hours under reflux of cresol. The reaction mass was then transferred to excess methanol to precipitate the product. The product obtained had a melting point of 200-207°C and an infrared absorption spectrum that matched that of Example 2. Example 7 44'-diphenyl ether diisocyanate 378
1 part, 38.4 parts of trimellitic anhydride, and 3000 parts of N-methylpyrrolidone were charged into a reactor equipped with a stirrer.
The mixture was gradually heated to 170° C. over 1 hour, and the reaction was continued by heating for another 1 hour. Then allyl isocyanate
87 parts and 504 parts of m-bis(carboxymethylamino)benzene were added thereto, and the mixture was reacted for 4 hours under reflux of cresol. The reaction mass was then transferred to excess methanol to precipitate the product. The product obtained has a melting point of 200
~210℃, 1770cm from the infrared absorption spectrum
^-1 , an absorption based on hydantoin and amide bonds was observed at 1710 cm ^-1 , and an absorption based on allyl group was observed at 1640 cm ^-1 , and the analysis revealed that the following formula 40 mol% of the compound represented by and the following formula Formation of 60 mol% of the compound represented by was observed. Example 8 4,4'-diphenyl ether diisocyanate
378 parts, trimellitic anhydride 38.4 parts, m-di(ethoxycarbonylmethylamino)benzene 504
and 3000 parts of N-methylpyrrolidone were placed in a reactor equipped with a stirrer and heated to 170°C for 1 hour.
The reaction was further allowed to proceed at the same temperature for 1 hour. Lower the temperature to 50°C, then add allyl isocyanate and raise the temperature again to 170°C.
Heat and stir for 1 hour. The reaction was transferred to excess methanol to precipitate the product. The obtained product has a melting point of 200 to 210°C, and its infrared absorption spectrum shows characteristic absorptions based on hydantoin and imide bonds at 1770 cm ^-1 and 1710 cm ^-1 , and characteristic absorptions based on amide and allyl groups at 1640 cm ^-1 . Absorption was observed and was consistent with that of the compound of Example 7. Example 9 Reaction at about 200°C for 4 hours using 57 parts of allylamine, 555 parts of 4,4'-bis(carboethoxymethylamino)diphenylmethane, 116 parts of hexamethylenediamine, 642 parts of diphenyl carbonate and 1000 parts of m-cresol as a solvent. urge The reaction mixture was then transferred into a large excess of methanol, and the precipitated product was separated and dried. The melting point of the reactant is 230 to 240°C, and the infrared absorption spectrum shows strong characteristic absorptions based on hydantoin at 1765 cm ^-1 and 1710 cm ^-1 and a layer of characteristic absorption based on allyl groups at 1640 cm ^-1 . Admitted. The elemental analysis values of this item are C = 70.1%, H = 6.8%,
N=12.2%, theoretical value C=66.9%, H=6.3
%, N=12.5%, and the following formula Formation of a compound represented by was observed.

Claims (1)

[Claims] 1. The following general formula [] [However, in the formula, R ₁ , R ₂ and R ₃ are the same or different and represent a hydrogen atom or a methyl group, and R ₄ and R ₅
are the same or different, and the following formula [formula] [formula] (X represents -O-, -CH ₂ -), or (-CH ₂ ) - _p
(p represents an integer of 4 to 8), and Q is the following formula group [] m and n represent O or a positive integer satisfying the following conditions: O≦m+n≦5 O≦n/m+1≦3/7. ] A terminal allyl group-containing hydantoin represented by