FR2724168A1 - NON-SATURATED BIS-IMIDES - Google Patents

Abstract

The invention relates to novel unsaturated bis-imides of the general formula wherein A denotes a 1,2-ethenediyl group or a norborn-5-en-2,3-diyl group, Q a methylene group, 1,3-phenylenediisopropylidene. or a 1,4-phenylenediisopropylidene group, R is hydrogen or chlorine and R ** 1 and R ** 2 is a C1 -C4 alkyl group. The bis-imides according to the invention are prepared from the corresponding diamines and dicarboxylic acid anhydrides and in turn serve as starting materials for the manufacture of polyimides resistant to high temperatures.

Description

NON-SATURATED BIS-IMIDES

  The present invention relates to novel unsaturated bis-imides based on maleic anhydride or norbornenedicarboxylic acid anhydride and diamines.

  aromatic compounds and a process for their preparation.

  Unsaturated bis-imides, in particular those obtainable from the anhydride of maleic acid and substituted methylenebis-anilines (see, for example,

  EP-A 544 266) are starting materials for the preparation of

  curable compositions which contain for example phenols or novolaks as second

  component (see for example EP-A 585 205).

  The object of the present invention is to provide new unsaturated bis-imides with other diamine components.

and / or anhydride.

  According to the invention this object is achieved with the bis-imides according to claim 1 and the method of preparation according to

claim 11.

  The subject of the present invention therefore relates to the unsaturated bis-imides of the general formula

0 2 I

0 R_0

  wherein A is each a 1,2-ethylene group

  diyl or a norborn-5-en-2,3-diyl group, also a group of the formula H y or X

H

  For steric reasons, the two free valences are constant in A-cis, in the case of norborn-5-en-2,3-diyl two configurations being possible relative to the methylene group to be connected (endo and exo). In addition, thanks to the bulky substituents R 'and R2, the rotation around the

  N-aryl bond may possibly be prevented (atropic

  somérie). General formula I encompasses every time all

  possible stereo-isomers and their mixtures. Q means

  a methylene group, a 1,3-phenylenediisopropyl

  lidene or a 1,4-phenylenediisopropylidene group, i.e.

say H. o0 or CH3%

  to the extent that A is not simultaneously a 1,2-group

  ethenediyl and a methylene group. R represents in each case hydrogen or chlorine and R 'and R2 each represent independently of each other a C 1 -C 4 alkyl group. R1 and R2 may therefore be identical or

  different and mean methyl, ethyl, propyl, isopropyl

  butyl, isobutyl, sec-butyl or tert-butyl. Except for the composition in which A = norborn-5-en-2,3-diyl, Q = methylene, R = hydrogen, R '= methyl and R2

= isopropyl.

  Preferred are compositions in which R 'and R2 are the same or different and represent each time

methyl, ethyl or isopropyl.

  Especially preferred are the compositions

  4,4 '- (1,3-phenylenediisopropylidene) bis [N- (2-ethyl-6-methyl-

  phenyl) maleinimide], of the formula

  N, N '- [4,4' - (1,3-phenylenediisopropylidene) bis (2,6-diisopropyl

  pylphenyl] bis [norborn-5-ene-2,3-dicarboxylic imide] of the formula [[) [_, _CIkcH,) 2 OCHCCJ. (I

0

0% C) CH% C CICCE

  4,4 '- (1,4-phenylenediisopropylidene) bis [N- (2,6-diéthylphé-

nyl) maleinimide], of the formula

NOT

o c Aix Ado

  4,4 '- (1,4-phenylenediisopropylidene) bis [N- (2-isopropyl-6-

  methylphenyl) maleinimide], of the formula

O0

- ^ ChcH C "e

  NN '- [4,4' - (1,4-phenylenediisopropylidene) bis (2-ethyl-6-

  methylphenyl]] bis [norborn-5-ene-2,3-dicarboxylic imide], of the formula o

  N, N '- [4,4' - (1,4-phenylenediisopropylidene) bis (2,6-diethyl)

  phenyl]] bis [norborn-5-ene-2,3-dicarboxylic imide], of the formula

7X

3,045M o -C CA a

  NN '- [4,4'-methylene-bis (2,6-diethylphenyl)] bis [norborn-5-

  ene-2,3-dicarboxylic imide], of the formula

I

  N, N '- [4,4'-methylene-bis (3-chloro-2,6-diethylphenyl)] bis [nor-

  born-5-ene-2,3-dicarboxylic imide], of the formula

0 0

  The bis-imides according to the invention can be prepared from the corresponding dicarboxylic anhydrides and

  corresponding aromatic diamines.

  The dicarboxylic anhydrides which can be used according to the invention have the general formula II

A 0

  Y o wherein A has the above meaning. These are maleic acid anhydride and norborn-5-ene-2,3-dicarboxylic acid anhydride, DielsAlder adduct from

  maleic acid and cyclopentadiene.

  These two compositions are marketed.

  The aromatic diamines that can be used according to the invention have the general formula

2 I

R R

HINNH

1R R

  in which Q, R, R 'and R' have the precise meanings

  Tees. Preferably, R 1 and R 2 are identical or different and represent, independently of each other, methyl, ethyl or isopropyl. Particularly preferred are diamines such as

  4,4 '- (1,3-phenylenediisopropylidene) bis (2-ethyl-6-

methylaniline)

  4,4 '- (1,3-phenylenediisopropylidene) bis (2,6-diisopropyl

propylaniline)

  4,4 '- (1,4-phenylenediisopropylidene) bis (2,6-diethyl

laniline)

  4,4 '- (1,4-phenylenediisopropylidene) bis (2-isopropyl-

6-methylaniline)

  4,4 '- (1,4-phenylenediisopropylidene) bis (2-ethyl-6-

  methylaniline) 4,4'-methylenebis (2,6-diethylaniline)

  and 4,4'-methylenebis (3-chlor-2,6-diethylaniline).

  These diamines are known compositions. The five diamines mentioned first are described in EP-A 594 156, the diamine mentioned last is described in

EP 220,641.

  The preparation of the bis-imides according to the invention is preferably carried out in two stages. First, the anhydride of the dicarboxylic acid (II) is reacted with the diamine (III) to obtain a bis-imide acid of the following formula:

SOOC-A ------ NH, -COOH V

R R

  consecutively, it is cyclized in the presence of an acid catalyst bisimide (I). As an acid catalyst for cyclization, in principle any strong acid is suitable. Preferably, sulphonic acids, for example methanesulfonic acid or benzene acid, are used.

  sulfonic acid. P-toluenesulphonic acid is particularly

  preferably in the anhydrous form or as hydrate.

  The reaction of the anhydride (II) with the diamine (III) is preferably carried out in an aromatic hydrocarbon as a solvent at a temperature of 20 ° C to 140 ° C. Suitable aromatic hydrocarbons are, for example, benzene, toluene, xylenes, ethylbenzene, cumene, mesitylene, methylnaphthalene or mixtures of these solvents. The cyclization of the bis-amide acid (IV) to bis-imide is preferably also carried out in an aromatic hydrocarbon as a solvent, however at a temperature of

from 90 to 200 C.

  Preferably, the same solvent as in the first step is used here and this is selected so as to boil at the reaction temperature or at a temperature above the reaction temperature. Preferably, the cyclization is conducted under reflux conditions and the water produced during the reaction is

  removed by azeotropic distillation by means of a

appropriate tif (water separator).

  The bis-imide acid (IV) formed in the first step is preferably not isolated, but after addition of the catalyst

  of cyclisation, it is directly transformed back into

  imide. The bis-imides according to the invention are suitable for the preparation of synthetic resins, especially high temperature resistant polyimides and copolymers of

imide structure.

  The following examples illustrate the realization of the process

according to the invention.

Example 1

  4,4 '- (1,3-phenylenediisopropylidene) bis [N- (2-ethyl-6-methyl-

  phenyl) maleinimide] (A = 1,2-ethenediyl, Q = phenylene-1,3-diisopropylidene, R H, R '= Me, R2 = Et): In a reactor with a capacity of one liter, equipped with a

  stirrer, a thermometer and a pressure compensator

  23.6 g of maleic anhydride (0.241 mol) was dissolved by heating in 110 ml of xylene. In a dropper funnel a metered addition is made at -80 ° C for about 60 minutes of a solution of 51.6 g.

  4,4 '- (1,3-phenylenediisopropylidene) bis (2-ethyl-6-

  methylaniline) (0.121 mol) in 350 ml of xylene. We shake

  the white suspension obtained for an additional 30 minutes

  6.8 p-toluenesulphonic acid-monohy-

  drate (0.04 mol), the dropper funnel on the apparatus is replaced by a water separator with reflux cooler and heated to the reflux temperature. After 4 hours, 5 ml of water was removed and a clear yellowish solution was produced in the reactor. Cooling and allowing to stand at 0 ° C precipitated white crystallizate. This crystallizate was collected on a suction filter or funnel-filter, rinsed with xylene and dried at 70 ° C. in a vacuum dryer.

  57.2 g of 4,4- (1,3-phenylenediisopropylidene) were obtained.

  bis [N-2-ethyl-6-methylphenyl) maleinimide] in the form of

  fine crystalline powder, practically white.

  Yield 80.3%, melting point 180 ° -181 ° C.

Example 2

  4,4 '- (1,4-phenylenediisopropylidene) bis [N- (2-6-diethyl

  phenyl) maleinimide] (A = 1,2-ethenediyl, Q = phenylene-1,4-diisopropylidene, R = H, R1 = R2 = Et):

  As in Example 1, 6.4 g of anhydride were reacted.

  maleic anhydride (0.065 mole) and 13.7 g of 4,4 '- (1,4-phenylene)

  nediisopropylidene) bis (2,6-diethylaniline) (0.030 mole) in

  ml of xylene and after addition of 1.90 g of p-acid

  toluene sulfonic monohydrate (0.01 mole) was heated until complete separation of water at

  reflux. The product crystallized during the cooling

  dissement. 15.1 g of 4,4 '- (1,4-phenylene diisocyanate) were obtained.

  propylidene) bis [N-2,6-diethyl-phenyl) maleimide].

  Yield 81.8%, mp about 2500 ° C (decomposed)

tion).

Example 3

  N, N '- [4,4' - (1,3-phenylenediisopropylidene) bis (2,6-diisopropyl

  pylphenyl]] bis [norborn-5-en-2,3-dicarboxylic imide]

  (A = norborn-5-ene-2,3-diyl, Q = phenylene-1,3-diisopropyl)

lidene, R = H, R '= R2 = iPr):

  As in Example 1, 14.2 g of anhydrite were reacted.

  5-norbornene-2,3-dicarboxylic acid druid (0.087

  mole) and 20.5 g of 4,4 '- (1,3-phenylene diisopropylidene) -

  bis (2,6-diisopropylaniline) (0.040 mol) in 160 ml of xylene and after addition of 2.7 g of p-toluenesulphonic acid monohydrate (0.014 mol) was heated until complete separation of the water at the reflux temperature. The clear reaction solution obtained was concentrated by evaporation on a rotary evaporator to dryness. The evaporation residue was isolated by precipitation in 100 ml of 5% aqueous sodium bicarbonate solution, wringing, rinsing with water and drying at 80 ° C. and 30 mbar. We

  obtained 20 g of N, N '- [4,4' - (1,3-phenylenediisopropylidene) -

  bis-imide (2,6-diisopropylphenyl) bis [norborn-5-ene-2,3

dicarboxylic].

  Yield 74.5%, mp 251 ° -254 ° C.

Example 4

  N, N '- [4,4' - (1,4-phenylenediisopropylidene) bis (2-ethyl-6-

  methylphenyl] bis [norborn-5-ene-2,3-dicarboxylic imide]

  (A = norborn-5-en-2,3-diyl, Q = phenylene-1,4-diisopropyl)

lidene, R = H, R '= and, R2 = Me):

  In a similar manner to Example 3, starting from 7.0 g of anhy-

  5-norbornene-2,3-dicarboxylic acid druid (0.043

  mole) and 9.3 g of 4,4 '- (1-3-phenylenediisopropylydene) bis (2-

  ethyl-6-methylaniline) (0.22 mole) with the aid of 1.3 g of p-toluenesulphonic acid monohydrate (0.007 mole),

  11.7 g of N, N '- [4,4' - (1,4-phenylenediisopropylidene) bis)

  imide (2-ethyl-6-methylphenyl)] bis [norborn-5-ene-2,3-dicarboxylic

boxylique].

  Yield 73.8%, m.p. 290.degree.

Example 5

  N, N '- [4,4'-methylene-bis (2,6-diéthyphényl)] bis [norborn-5-

  Ene-2,3-dicarboxylic imide] (A = norborn-5-ene-2,3-diyl, Q = methylene, R = H. R '= R2 = Et) In a reactor according to Example 1, at 16 4 g of 5-norbornene-2,3-dicarboxylic acid anhydride (0.10 mole) in 150

  ml of toluene at 80 ° C., 15.5 g of 4,4'-methylene

  bis (2,6-diethylaniline) (0.050 mol) in 50 ml of toluene and the reaction mixture was heated after addition of 1.9 g of p-toluenesulphonic acid monohydrate (0.010 mol) and ml of toluene at reflux temperature and was dehydrated by azeotropic distillation. The clear solution obtained was allowed to cool, extracted twice.

  each time with 50 ml of a bicarbonate solution

  5% aqueous sodium nitrate, rinsed with water and the xylene phase was concentrated to dryness. We got 18.3

  N, N '- [4,4'-methylene-bis (2,6-diethylphenyl)] bis [norborn-

2,3-ene-2-dicarboxylic imide].

  Yield 94.0%, mp 226.7-228.1 C.

2724168.

Claims (10)

  1. Unsaturated bis-imides of the general formula 2 I AZ0 R 0 0 R. 0   in which A signifies a 1,2-ethene group each time   diyl or a norbon-5-ene-2,3-diyl group,   Q represents a methylene, 1,3-phenylene diisopropyl   denene or a 1,4-phenylene diisopropylidene group, R is each hydrogen or chlorine, R 'and R2 each independently signify a C1-C alkyl group. with the proviso that A is not simultaneously 1,2-ethenediyl and Q is methylene, and with the exception of the composition wherein A is norborn-5-ene-2,3-diyl, Q is methylene, R 'the group hydrogen, R' methyl and R2 the isopropyl group.   2. Bis-imides according to claim 1, characterized in that R 'and R2 each mean independently one of   on the other a methyl, ethyl or isopropyl group.   3. 4,4 '- (1,3-phenylenediisopropylidene) bis [N- (2-   ethyl-6-methylphenyl) maleimide] of the formula O O 0O   as well as N, N '- [4,4' - (1,3-phenylene diisopropyl)   dene) bis (2,6-diisopropylphenyl)] bis [norborn-5-ene-2,3   dicarboxylic imide] of formula 0 0 Es ( (H3C) CH% C   as well as 4,4 '- (1,4-phenylenediisopropylidene) -   bis [N- (2,6-diethylphenyl) maleinimide], of formula 0 ^^ C ^^ CIA O C C # t o   as well as 4,4 '- (1,4-phenylenediisopropylidene) -   bis [N- (2-isopropyl-6-methylphenyl) maleinimide], of formula O C% O o% c (HA C) aH CH ^^%)   as well as N, N '- [4,4' - (1,4-phenylenediisopropyl)   dene) bis (2-ethyl-6-methylphenyl)] bis [norborn-5-ene-2,3   dicarboxylic imide], of formula o C o   as well as N, N '- [4,4' - (1,4-phenylenediisopropyl)   dene) bis (2,6-diethylphenyl) Ibis [norborn-5-ene-2,3-dicarboxy- lique imide], of formula o uz zh C% '.0 IN   as well as NN '- [4,4'-methylene-bis (2,6-diethyl)   phenyl)] bis [norborn-5-ene-2,3-dicarboxylic imide], of 20. formula o O   and N, N '- [4,4'-methylene-bis (3-chlor-2,6-diethyl)   phenyl) bis [norborn-5-ene-2,3-dicarboxylic imide], of   A process for the preparation of unsaturated bis-imides according to formula I, characterized in that a dicarboxylic acid anhydride of the general formula is reacted.   in which A has the meaning given in the claim   1 with an aromatic diamine of general formula 2 m R R R Q NQ NU m i 2 R R R   wherein R, R 'and R2 have the meanings given in claim 1, to obtain a bis-amide acid of the general formula! in which A, Q, R, R 'and R2 have the abovementioned meanings, and the bis-amide acid (IV) is cyclized in   presence of an acid catalyst to give bis-imide (I).   5. Process according to claim 4, characterized in that, as acid catalyst, an acid is used   sulfonic acid, preferably para toluenesulphonic acid.   6. Method according to one of claims 4 and 5,   characterized in that the reaction of the anhydride (II) with the diamine (III) is carried out in an aromatic hydrocarbon   as a solvent at a temperature of 10 to 140 C.   7. Method according to one of claims 4 and 5,   characterized in that the cyclization of bis-amide acid (IV) to bis-imide (I) takes place in a hydrocarbon   aromatic solvent at a temperature of 90 to 200 C.   8. Method according to claim 7, characterized in that the water produced during the cyclization is eliminated   of the reaction mixture by azeotropic distillation.   9. Process according to one or more of the   Claims 4 to 7, characterized in that the acid of bis-   amide (IV) is not isolated but is directly transformed back into bis-imide (I).   10. Use of bis-imides according to   claim 1 for the preparation of synthetic resins.