JPS61215369A - Bis(hydroxyphthalimide) and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R is aromatic hydrocarbon group, alkylene, or group shown by the formula II (X is -O-, -CO-, -SO-, etc.; m is 0 or 1; n is 1-5), etc.]. EXAMPLE:1,3-bis(4-hydroxyphthalimido)benzene. USE:A monomer for polyimide. PREPARATION:4-Hydroxyphthalic anhydride is reacted with an organic diamine shown by the formula NH2RNH2 in a molar ratio of 2:1 in a phenolic solvent (e.g., cresol) or glacial acetic acid as a solvent at 100-140 deg.C to give a compound shown by the formula I.

Description

[Detailed description of the invention]

[Industrial Application Field] This invention is directed to a novel bispylene that can be used as a monomer for polyimide.

[Hydroxyphthalimide@) and its manufacturing method. [Prior art]

It is generally known that compounds containing an imide ring have excellent heat resistance, and polyimide in particular has the best heat resistance among various polymers. Taking advantage of these advantages, Polyimide Co., Ltd. has a wide range of products for use in general industries such as space and anti-aircraft manufacturing, printed boards, and packaging materials.
It is used. In addition, by introducing an imide ring into a polymer, it is possible to exploit the characteristics of the polymer itself. It is possible to impart the heat resistance that the ring has. For example, there are reports that heat resistance increases by 150°C by introducing imide rings into epoxy resins. In this way, imide ring-containing polyimide containing polyimide is one of the polys that is expected to develop in the future from the viewpoint of heat resistance. [Problems to be solved by the invention] However, although various polyimides and imide ring-containing polymers have been synthesized so far, imide ring-containing monomers such as bisphenol A, which can be used as raw materials for various polyimide rings, have not yet been synthesized. Not accepted. [Means for solving the problem] Therefore, in order to obtain an imide ring-containing monomer that can be used as a raw material for various imide ring-containing polymers, we synthesized a comprehensive range of compounds, conducted further studies, and developed a new bis-C hydroxyphthalimide. It has been found that this method is suitable for this purpose. The novel bisC hydroxyphthalimide of the present invention has the general formula (T) %C1 genated derivative,
(h) an alkylene group, a polyorganosiloxane chain-terminated with an alkylene group having 2 to 8 carbon atoms;
a cycloalkylene group having 20 carbon atoms; C) one member selected from the group consisting of the following formula and -0nH2n -, m is an integer of 0 or 1, and n is an integer of 1 to 5; )
n is a divalent organic group selected from the group consisting of n divalent groups represented by n. ] This is a compound represented by n. This new bis[hydroxyphthalimide] can be produced by condensing 4-hydroxyphthalic anhydride with an organic cyabane of the following formula. NH2RNH2(1) where R is the same as the group defined above. ) As this organic diamine, basically any number of organic diamines that can be considered can be conveniently used, and all the organic diamines defined in the above formula 1 can be used. Specifically, c is m-phenylenediamine, p-7 22-diamine, 4,4'-cya is fudiphenyl 10pan, 4,4'-cyabanodiphenylmethane, benzidine, 4゜4'-cyabano diphenyl sulfide, 4.4'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl ether, 1.5-
Diaminonaphthalene%3.3'-dimethylbenzidine,
3゜3'-dimethoxybenzidine, 2,4-bisCβ-
Amino-1-butyl)toluene, bis(p-/-a not-t-butylphenyl)ether, bis(p-β-methyl-〇-7minobentyl)benzene, 1,3-diamino-4-inpropylbenzene , 1.2~bisC3-azunobu aboxy)ethane, m-xylylenediamine, p-
xylylenediamine, 2.4-diaminotoluene, 2.
6-diaminotoluene, bisC4-aminocyclohexyl]methane% 3-methylhebutamethylenediamine, 4
゜4-dimethylhexamethylenediamine, 2.11-dodecanediamine, 2.2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine 52e5-') methylhexamethylenediamine, 2.5-dimethyl Hebutamethylenediamine, 3-methylhbutamethylenediamine, 5-methylnonamethylenecyabane, 1°4-cyclohexanediamine% 1.1
2-octadecanediamine, bis(3-abanobrovir) sulfide, N-methyl-bisC3-aminopropyl)amine, heptamethylenediamine, heptamethylenediamine, 4,4'-diaminobenzophenone, nonamethylenediamine, decamethylenediamine , bis(3-minoprobil)tetramethyldisiloxane, bisC4-
Examples include aminobutyruntetramethyldisiloxane. In this reaction, 1 mole of organic diamine is used for 2 moles of 4-hydroxyphthalic anhydride, but good results can be obtained even if the amount of arina diamine is 0.8 to 1.2 moles. is obtained. Moreover, as a reaction solvent, a phenolic solvent or glacial acetic acid can be used as a solvent. As the phenolic solvent, o-, p-, m-cresol and mixtures thereof can be used in an amount of 91 to 2 parts by weight or more based on 1 part by weight of the total reactants. The reaction temperature is preferably about 100 to 140°C. In addition, to facilitate the removal of reaction water during the production of bis[hydroxyphthalimide], low-boiling non-polar solvents such as benzene, albenzene, and toluene-IEt can also be used as azeotrope-forming agents. The time ranges from 20 minutes to 2 hours depending on factors such as the type of organic cyanogen, the degree of stirring, and the temperature.7 After the reaction is complete, the reaction mixture is allowed to cool and the solvent is removed under reduced pressure. Alternatively, the product can be isolated by adding a suspending solvent such as methanol and filtering off the resulting precipitate. When using glacial acetic acid as a solvent, all the reactants are one weight! @To9
The mixture is allowed to react under reflux of about 10 parts by weight of glacial acetic acid for about 1 to 15 hours. After the reaction is completed, the product is isolated by allowing it to cool, filtering off the precipitated precipitate, and washing with a solvent such as methanol. [Examples] The compound of the present invention and the method for producing the same will be explained in detail below using examples. However, these working examples are for illustrating the implementation of the present invention, and are not intended to limit the scope of the present invention.7CC Example 1) A mixture of 50 g of p-cresol and 30 g of toluene is
-Hydroxyphthalic anhydride 33.2 g [), 2 mol)
and m-phenylenecyazine (10.8 gjO, 1 mol) and heated at 120 to 125°C in a nitrogen atmosphere for 15 minutes.
The mixture was heated to reflux for a minute. The water produced over the next 30 minutes was removed by azeotropic distillation with toluene. The reaction mixture was left at room temperature, and the resulting solid was filtered off and washed with acetone. After drying under vacuum at 100°C for 3 hours, 37.7 g of 1,3-bis[4-hydroxyphthalibado]benzene was obtained.
r yield 944) was obtained. This book has an infrared absorption spectrum of 3300 m''''1
The absorption based on O) I i was obtained at l 700 cm-' and the absorption characteristic of the C=0 group of the imide group at 1,177Qcyn-1, and in the proton nuclear magnetic resonance spectrum, Using TMS as an internal standard, 11.0 ppm of droxy group (C broad, 2H), 7-1 to 8.0 ppm of phenyl group (loj (l), and 81
As shown in the table, the measured values and calculated values in elemental analysis almost matched, so we confirmed that it was the target compound (Example 2) 3.32 g of glacial acetic acid 30-14-hydroxyphthalic anhydride
g0.02 mol) and m-f L=V:/') amine 1
．． 7. The reaction mixture was heated under reflux at 120° C. for 8 hours. The reaction mixture was allowed to stand at room temperature, and the resulting solid was filtered off and washed with methanol. 100℃ under vacuum
When dried for 3 hours at
) Profit nine. The infrared absorption spectrum of this product showed all the same absorption spectra as the compound of Practical Example 1. CC Examples 3 to 8) gM Residue In place of m-phenylenediamine in Example 1, various organic cyamines were used, and the same extraction procedure as in Example 1 was carried out to obtain the compounds shown in Table 1. Identification of good compounds was carried out in the same manner as in Actual Example 1. Table 1 shows the yield, melting point, infrared absorption spectrum data, and elemental analysis values. It has a hydroxyl group and can be used as a monomer for imide ring-containing polymers such as polyimide and polyester 1 polyamideimide 0. For example, this bis C hydroxyphthalide can be used for condensation polymerization 9 or! The desired polymer can be obtained by addition polymerization with cyabane, by reaction with terephthalda, etc. to form polyester imide, or by reaction with an ebotashi compound such as epichlorohydrin to form imide epoxy. [Effects of the Invention] As explained above, the bisC-human mixiphthalimide of the present invention has an ibado ring and two reactive water groups in the molecule, so it is similar to the polyimide and ? It is suitable as a monomer for E imide ring-containing polymer C polyester imide y1 polyamide imide, etc.).

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (b) an alkylene group , a polyorganosiloxane chain-terminated with an alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 2 to 20 carbon atoms, (c) the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, , X is -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, One member selected from the group consisting of -S- and -C_nH_2_n-,
m is an integer of 0 or 1, and n is an integer of 1 to 5. ) is a divalent organic group selected from the group consisting of divalent groups represented by: ] Bis(hydroxyphthalimide). (2) 4-Hydroxyphthalic anhydride and the formula NH_2RNH_2 [In the formula, R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (b) an alkylene group, a carbon atom is a polyorganosiloxane chain-stopped with 2 to 8 alkylene groups or a cycloalkylene group having 2 to 20 carbon atoms, (c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, one member selected from the group consisting of -S- and -C_nH_2_n-,
m is an integer of 0 or 1, and n is an integer of 1 to 5. ) is a divalent organic group selected from the group consisting of divalent groups represented by: ] A general formula is formed by condensing an organic diamine represented by the following in the presence of a phenolic solvent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as the group described above. ] A method for producing bis(hydroxyphthalimide) shown by (3) 4-Hydroxyphthalic anhydride and the formula NH_2RNH_2 [In the formula, R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (b) an alkylene group, a carbon atom is a polyorganosiloxane chain-terminated with 2 to 8 alkylene groups or a cycloalkylene group having 2 to 20 carbon atoms, (c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, one member selected from the group consisting of -S- and -C_nH_2_n-,
m is an integer of 0 or 1, and n is an integer of 1 to 5. ) is a divalent organic group selected from the group consisting of divalent groups represented by: [In the formula, R is the same as the above-mentioned group. ] A method for producing bis(hydroxyphthalimide).