RU2036934C1 - Oligomer on the basis of bis-maleinimides and azomethines and composition material on its base - Google Patents

Abstract

FIELD: oligomer compounds. SUBSTANCE: product: new oligomers on the basis of bis-maleinimides and azomethines of the general formula

where

,

,

Description

-R₁-

-

где где R₁=

CH

O

O

O

O

R₂=

n 2, а:b:c (2-6):(2-6):1; с мол.м. 1300-4000 и приведенной вязкостью в хлороформе 0,05-0,09 c улучшенной растворимостью в органических растворителях и композиционному материалу, их содержащему.The invention relates to new oligomers based on bismaleimides and azomethines of the general formula:

-R ₁ -

-

where where R ₁ =

CH

O

O

O

O

R ₂ =

n 2, a: b: c (2-6) :( 2-6): 1; with a mol.m. 1300-4000 and reduced viscosity in chloroform of 0.05-0.09 with improved solubility in organic solvents and the composite material containing them.

 The oligomers based on bismaleiminimides and azomethines in a crosslinked state are intended for use as coatings, casting compounds, as well as structural materials for products, electronic, electrical, automotive and other industries.

CH

Олигомеры получены при нагревании смеси исходных мономеров (температура 150^оС) и представляют собой желтые кристаллы с температурой плавления 136,6^оС.Known [I] oligomers based on 4,4'-bis (maleimide diphenyl) methane and N, N'-n-phenylene-dimethylidenedianiline, (N, N'-bis- [(benzylidene) -4,4'-diaminophenyl] methane taken in a ratio of 2: 1 (mol), the formula:

CH

The oligomers prepared by heating a mixture of starting monomers (temperature 150 ° ^C) and represent yellow crystals with melting point 136.6 ° ^C.

Oligomers cure (crosslink) to form heat-resistant products at a temperature of about 250 ^o C.

O

O

N CH-R₂
где
R₂=

Азометины получены взаимодействием бензальдегида, салицилового и оксинафтойного ангидрида с 2,2-бис-[4(4'-аминофенокси) фенил]-пропаном. Способ получения указанных азометинов традиционен и состоит во взаимодействии соответствующего альдегида и амина в спиртовом растворе (этиловый, изопропиловый спирт и др.) или в среде ароматических углеводородов (бензол, толуол и др.) с азеотропной отгонкой воды [2]
Вновь синтезированные олигомеры получены при более низкой температуре (130^о против 150^оС) при соотношении бисмалеинимида и азометина от (6-2):1 (мол) и характеризуются более низкой температурой плавления (72-102^оС в зависимости от значения R₁ и R₂ и улучшенной растворимостью в органических растворителях (спиртах, кетонах, ароматических углеводородах, хлорированных углеводородах и др.).The difference between the synthesized oligomers is the use of new azomethines of the general formula:
R ₂ —CH = N

O

O

N CH-R ₂
Where
R ₂ =

Azomethines are prepared by reacting benzaldehyde, salicylic and oxynaphthoic anhydride with 2,2-bis- [4 (4'-aminophenoxy) phenyl] propane. The method of obtaining these azomethines is traditional and consists in the interaction of the corresponding aldehyde and amine in an alcohol solution (ethyl, isopropyl alcohol, etc.) or in an aromatic hydrocarbon medium (benzene, toluene, etc.) with azeotropic distillation of water [2]
Newly synthesized oligomers prepared at a lower temperature ⁽¹³⁰ vs. 150 ° ^C) at a ratio of azomethine bismaleinimida and (6-2): 1 (mol), and characterized by a lower melting point (72-102 ^{° C} depending on the value R ₁ and R ₂ and improved solubility in organic solvents (alcohols, ketones, aromatic hydrocarbons, chlorinated hydrocarbons, etc.).

The lowered melting point and improved solubility oligomers makes possible their wider use of composite materials by expanding the range of auxiliary materials, some of which can not withstand a temperature of about 250 ^{° C} and better alignment conditions with reinforcing fillers from the use of a wider range rasvoriteley.

 The effect of improving the solubility of new oligomers is not obvious: the introduction of hinged ester groups into the structural chain of oligomers did not have to lead to an improvement in solubility. So, when considering the solubility of azomethines N, N'-bis [(benzylidene) -4,4'-diaminophenyl)] methane and N, N'-bis [(benzylidene) -4 (4'-aminophenoxy) phenyl] - 2,2-propane marked the best solubility of the former in acetone and isopropanol. Comparing oligomers obtained on the basis of the same bismaleimide (4,4'-bis [maleimidodiphenyl] methane and various azomethines-N, N'-bis [(benzylidene) -4,4 '- (diaminophenyl)] methane (by prototype) and N, N'-bis (benzylidene) -4,4'-diaminophenoxyphenyl] -2,2-propanol, N, N'-bis [(α-hydroxybenzylidene) -4,4 '-diaminophenoxyphenyl] -2, 2-propane and N, N'-bis [(α-oxinaphthylidene) -4,4'-diaminophenoxyphenyl] -2,2-propane (newly synthesized in accordance with the invention) it turned out that the latter are distinguished by improved solubility in acetone and isopropanol as well as chloroform and toluene (see table 1).

 The synthesized oligomers can be used as a casting compound or used to obtain a binder for the impregnation of woven, fibrous and powdery fillers and the subsequent manufacture of composite materials.

 Known [3] are composite materials based on unsaturated N, N'-bisimides and azomethines (Schiff bases) of the formula I, II, III.

N-R₄
(I)
R₃-

N-A-N=

R₃
(II)
R₄-N=

R₆-C=

R₄
(III) где R₃ и R₅ H, С_1-12 алкил, С_6-12 арил, С_7-15 алкарил или С_7-15-аралкил, хлорфенил, С_1-5-алкоксифенил, R₄ C_1-12 алкил, С_6-12арил, С_7-15 алкарил, С_7-15 аракил, хлорфенил, С_1-5-алкоксифенил, циклогексил, циклопентил, R₆ C_2-12 алкилен, фенилен, толилен, бифенилен, нафтилен или арилен формулы

X

где Х -S-, -O-, -NH-, фенилен, сульфонил или С_1-3-алкилен; А=C_2-12 алкилен, С_4-6арилциклоалкилен, ксилилен, арилен, выбранный из группы, содержащей фенилен, толилен, бифенилен, нафтилен, замещенный арилен формулы:

W

где W-сера, карбонил, -NH-, N-(низший) алкил, -О-, -N-фенил, сульфонил, С_1-3 алкилен, а R₇ и R₈=H, хлор, бром, С_1-5 (низший) алкил, C_1-5алкокси.R ₃ -

Nr ₄
(I)
R ₃ -

NAN =

R ₃
(Ii)
R ₄ -N =

R ₆ -C =

R ₄
(III) where R ₃ and R ₅ H, C _1-12 alkyl, C _6-12 aryl, C _7-15 alkaryl or C _7-15 aralkyl, chlorophenyl, C _1-5 alkoxyphenyl, R ₄ C _{1- 12} alkyl, C _6-12 aryl, C _7-15 alkaryl, C _7-15 arakyl, chlorophenyl, C _1-5 alkoxyphenyl, cyclohexyl, cyclopentyl, R ₆ C _2-12 alkylene, phenylene, tolylene, biphenylene, naphthylene or arylene formulas

X

where X is -S-, -O-, -NH-, phenylene, sulfonyl or C _1-3 alkylene; A = C _2-12 alkylene, C _4-6 arylcycloalkylene, xylylene, arylene selected from the group consisting of phenylene, tolylene, biphenylene, naphthylene, substituted arylene of the formula:

W

where W is sulfur, carbonyl, —NH—, N- (lower) alkyl, —O—, —N-phenyl, sulfonyl, C _1-3 alkylene, and R ₇ and R ₈ = H, chloro, bromo, C _{1 -5} (lower) alkyl, C _1-5 alkoxy.

These Schiff bases were obtained by traditional methods by the interaction of aldehydes or ketones with mono- or diamines in an equivalent amount in an inert solvent. These methods of obtaining Schiff bases include:
mixing the reagents in 98% ethanol, precipitating and drying the product,
or heating reagents at the boiling point in benzene or toluene with a Dean-Stark nozzle until theoretical quantitative distillation of water and the allocation of Schiff base [2]
Closest in structure to the claimed oligomers is an oligomer obtained using azomethine from benzaldehyde and 4,4'-diaminodiphenylmethane and 4,4'-bis [(maleimidiphenyl)] - methane. Obtaining an oligomer was carried out in accordance with (3) and was subsequently used to obtain a composite material.

Materials-adhesins, laminates, coatings for decorative and electrical parts, molding materials obtained by combining the oligomer with filler in a ratio of 30-50 wt. oligomers in 100 wt. material. As fillers, woven and non-woven, fibrous and powder fillers can be used. The materials are characterized by good mechanical and thermo-oxidizing properties and have a cross-linking temperature lower than for conventional polyimide materials (100-350 ^o C, preferably 100-280 ^o C) [3]
The aim of the invention is the synthesis of oligomers and the development of material with a low crosslinking temperature while maintaining high heat resistance and mechanical properties during its long-term operation.

-R₁-

-

где

O

O

R₂=

n=2, а:в:c (2-6):(2-6):1 с мол.м. 1300-4000.The problem is solved by using as a binder oligomer based on bismaleimides and azomethines of the general formula:

-R ₁ -

-

Where

O

O

R ₂ =

n = 2, a: b: c (2-6) :( 2-6): 1 s mol.m. 1300-4000.

 As bismaleinimides, 4,4'-bis [(maleimidophenyl)] methane (4), 1,3-bis [(4- (maleimidophenoxy)] - benzene (5), 2,2-bis [4 (4 '- maleinimidophenoxy) phenyl] propane, the preparation of which is carried out according to the known method [6] in two stages, where maleic acid acid is formed in the first stage and cyclization is carried out in the second, accompanied by the release of water.

 As azomethines, newly synthesized azomethines selected from the group consisting of N, N'-bis (benzylidene) -4,4'-diaminophenoxyphenyl)] -2,2-propane, N, N'-bis (α -oxybenzylidene) -4,4'-diaminophenoxyphenyl) -2,2-propane, N, N'-bis (α-oxinaphthylidene) -4,4'-diaminophenoxyphenyl] -2,2-propane. The resulting oligomer is used as a binder for the manufacture of the material. The material is made as follows: the oligomer is ground into powder, and then applied to the surface of the product by spraying (including by electrostatic method followed by heating), or a solution containing 25-50 wt. dry matter, which is then used to combine with the filler.

 As fillers, powdered substances GL-1 graphite (GOST 5279-74), aluminum oxide (TU 6-09-426-75) and other fibrous materials: fiberglass BS-10-84p (TU 6-11-240) can be used -77), carbon fiber UKN-900 (TU 6-06-06-I106-83) and other woven fillers: KT-11 fiberglass (TU 6-11-224-74) Ural-TM-4/22 carbon fabric ( TU 6-06-31-484-84) and others.

Manufacture of material is carried out by heating in the range of 100-200 ^C. temperautur obtained crosslinked, insoluble and infusible products, the formation of volatile substances during the reaction does not take place: the expansion of the final material, for example, when debinding identified starting components in the composition and quantities not different from the original.

 For experimental verification, 8 oligomers were obtained (one of them according to the prototype) and composite materials containing them, whose properties are presented in Table 1 (oligomers) in Table 2 (materials).

CH

получают сплавлением 4,4'-бис[малеинимиддифенил]метана (100 мас.ч. 2 мол), с N,N'-бис/[(бензилиден)-4,4'-диаминофенок- сифенил]-2,2-пропаном (82 мас.ч. 1 мол) при 130^оС в течение 15-50 мин. Выход олигомера 99,2%
Температура плавления полученного олигомера 86-89^оС. Структура олигомера подтверждена данными ИК- и ПМР-спектров, элементного анализа, а оценка молекулярной массы проведена с использованием метода жидкостной гель-проникающей хроматографии.PRI me R A. Oligomer structure:

CH

obtained by fusion of 4,4'-bis [maleimidiphenyl] methane (100 parts by weight of 2 mol), with N, N'-bis / [(benzylidene) -4,4'-diaminophenoxyphenyl] -2,2-propane (82 parts by weight of 1 mole) at 130 ^{° C} for 15-50 min. Oligomer yield 99.2%
The melting point of the obtained oligomer is 86-89 ^о С. The structure of the oligomer is confirmed by the data of IR and PMR spectra, elemental analysis, and the molecular weight was estimated using liquid gel permeation chromatography.

C. An oligomer previously ground to powder (37 g, 30 parts by weight 0.03 mol) is dissolved in acetone (109 ml, 70 parts by weight) to form a solution of 30% concentration. The resulting solution (123 g, 100 parts by weight) is impregnated with a filler, for example, BS-10-84 glass fiber (63 g, 51.2 parts by weight), the preform is placed in a mold and heated sequentially at a temperature of 120, 140 and 160 ^about 60 minutes and at 200 ^about for 20 hours

 To design the product, apply a pressure not exceeding 1 MPa.

 The resin content in the resulting plastic (100 g) 37 g.

 Physico-mechanical properties of composite materials obtained in accordance with this example are shown in table 2.

 In a similar manner, other oligomers and composite materials were obtained, are shown in tables 1 and 2.

 Analysis of the data presented in table 1 shows that the obtained oligomers have better solubility than the oligomer of the prototype, and also have a lower melting point.

The analysis of the data presented in table 2, indicates that:
curing temperature of the material in accordance with the invention to ^about 150 lower than the prototype material, without reducing heat resistance,
the bending strength of the developed materials (a comprehensive characteristic of the strength properties) is 45-65% higher than that of the material of the prototype.

 High heat resistance and increased mechanical strength allow us to recommend materials for the manufacture of products exposed to moisture at elevated temperatures, as evidenced by data on the preservation of strength during boiling. The proposed composition retains up to 90% of the initial strength (86-499 MPa, see examples 1B-7B), while the initial strength of the composite material according to the prototype in the case of using fiberglass as filler is only 34.7 MPa and in the case of using fiberglass 480 MPa.

High temperature began degradation in air (above 350 ^C) ensures a long and stable operation of the proposed composite material at temperatures ^of 250-300 C.

Claims (2)

1. The oligomer based on bismaleimides and nitrogenmetins of the General formula

n is 2;
abc (2 6) (2 6) 1, with a mol. 1300 4000. 2. A composite material comprising a filler and a binder based on bismaleimide and azomethine, characterized in that the binder material contains an oligomer of the general formula

n 2;
abc (2 6) (2 6) 1,
with a pier. m. 1300 4000 in the amount of 30 50 wt.h. per 100 parts by weight composite material.

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