DE2261715A1 - Polyetherimides prodn - by copolymer of bis-(nitrophthalimides) with a divalent carbocyclic arom residue - Google Patents

Abstract

A polyetherimide of formula (I) (where R is a carbocyclic arom. 6-20C residue, R' is R or, additionally xylylene or alkylene with 2-20 C-atoms, cycloalkylene, bis(4-cycloalkyl) low)-alkylene or alkylcycloalkylene; n is >1; -O-Z is a (a), (b) or (c) where R" is H, low alkyl or low alkoxy; and the oxygen may be in o- or p-posn. at any ring, and the polyetherimide is terminated by a nitro-substd. arom. or hydroxyphenyl grp. is prepd. by reacting a salt of an org. cpd. MO-R-OM (M is an alkali metal and R is a divalent carbocylic arom 2-20C residue) with a bisphthalimide e.g. 4,4'-bis-(3-nitrophthalimido)diphenylether, in a dipolar aprotic solvent. Used in mfre. of heat-resistant films, press mouldings, wire varnish.

Description

Polyetherimides and Processes for Their Preparation The Need for Heat Resistant Polymers led to the development of polyimides. These polymers are made from aromatic Acids are produced and contain imide groups in the polymer chain. The aromatic Polyimides are used to make films, molded parts, and wire waxes. In Encyclopedia of Polymer Science and Technology, Volume 11, pages 247-2i2 (1969) summarizes the manufacture, properties and uses of polyimides described. According to this reference, polyimides are made from aliphatic diamines and aromatic tetracarboxylic acids or from aromatic diamines and aromatic Dianhydrides made.

It has now been found that polyetherimides by copolymerizing Bis (nitrophthalimides) with a divalent carbocyclic aromatic radical can be produced. The resulting polyetherimides are new and can be used for the production of heat-resistant films, pressed parts and wire enamels.

The new polyetherimides have the following general formula: where: -O-Zs = one of the following groups: where R "= hydrogen, a lower alkyl or a lower alkoxy radical, where the oxygen on any of the rings can be in o- or p-position to one of the anhydride carbonyl groups, and R, R 'and n have the meanings given below, and the polyetherimides by a = Z-NO 2 or phenolic group, in which Z has the meaning given above, have ended.

Polyetherimides of the following formula are preferred: in which: R is a divalent aromatic radical having up to 20 carbon atoms; R 'is a divalent radical which is the organic component of a diamine which has been reacted with a nitro-substituted aromatic anhydride, integer and n is a number greater than 1, for example 2 to about 5000 or higher. In particular, R can be a phenylene, (lower alkylphenylene group, or where X is a divalent slipatic, cycloaliphatic or araliphatic radical (with 1 to 8 carbon atoms), -0-, -, -S- or # S # and R 'can be R, or additionally a xylylene or alkylene radical with 2 to 18 carbon atoms or a cycloalkylene radical, the polyetherimides being terminated by one. or phenolic group The invention also relates to a process for producing polyetherimides, according to which, for example, the following preferred components are reacted in the presence of a dipolar aprotic solvent: (1) a bis (nitrophthalimide) of the general formula: where R 'has the abovementioned meaning, R "= a chlorine or nitro radical, and (2) an alkali salt of an organic compound of the formula: (IV) MO-R-OM in which M is an alkali metal and R = has the meaning given above .

The bis (nitr ophthalimide) used to prepare the polymers is obtained by reacting a diamine of the formula: (V) NH2-R1-NH2 in which R 'has the above meaning with a nitro-substituted phthalic anhydride of the formula: where R "'is a chlorine or nitro radical.

The molar ratio of diamine to anhydride should ideally be around 1: 2. The primary reaction product is a bis (amic acid) which. afterward is dehydrated to the corresponding bis (nitrophthalimide).

Diamines of the formula (V) are known from the literature. For example the following diamines can be used: m-phenylenediamine; 4,4'-diaminodiphenylpropane; Benzidine; 4,4'-diaminodiphenyl sulfide; 4,4'-diaminodiphenyl sulfone; 4,4 1-diaminodiphenyl ether; 1,5-diaminonaphthalene; 3,3'-dimethylbenzidine; 3.31 dimethoxybenzidine; 2,4-bis - (# - amino-t-butyl) toluene; Bis- (p - # - amino-t-butylphenyl) ether; Bis- (p - # - methyl-o-aminopntyl) benzene; 1,3-diamino-4-isopropylbenzene; 1,2-bis (3-aminopropoxy) ethane; p-xylylenediamine; Bis (4-aminocyclohexyl) methane; Decamethylenediamine; 4,4-dimethylheptamethylene diamine; 2,11-dodecanediamine; Octamethylene diamine; 3-methoxyhexamethylene diamine; 5-methylnonamethylene diamine; 1,4-cyclohexanediamine; Bis (3-aminopropyl) sulfide; N-methyl-bis (3-aminopropyl) amine; Nonamethylene diamine.

According to the invention, phthalic anhydrides are preferably used which substituted in the 3- or 4-position by a chlorine radical or by a nitro group are. The phthalic anhydrides used according to the invention can be prepared according to known methods Process are produced. Further, for example, suitable phthalic anhydrides are 2-nitronaphthalic anhydride, 4-chloronaphthalic anhydride, 1-nitro-2,3-naphthalenedicarboxylic anhydride and 3-methoxy-6-chlorophthalic anhydride.

In the formula (IV), R can be a divalent aromatic hydrocarbon radical with 6 to 20 carbon atoms, for example a phenylene, biphenylene, Naphthylene or diarylene, whose aryl core with an aliphatic group, a Sulfoxide group, a sulfonyl group, sulfur, a carbonyl group, oxygen or -C (CH3) (CH2) 2 (COOH) group. Typical dihydroxy compounds of these Kinds are for example: Ilydroquinone Resorcinol 2,4 1-Dihydroxydiphenylmothan; Bis (2-hydroxyphenyl) methane; 2,2-bis (4-hydroxyphenyl) propane, hereinafter referred to as "bisphenol-A" or "BPA"; Bis (4-hydroxy-5-nitrophenyl) methane; Bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxy-2-chlorophenyl) ethane; 1,1-bis (2,5-dimethyl-4-hydroxyphenyl) ethane; 1,3-bis (3-dimethyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxynaphthyl) propane; 3,3-bis (4-hydroxyphonyl) pentane; 2,2-bis (4-hydroxyphenyl) heptane; Bis (4-hydroxyphenyl) cyclohexyl methane; 1,2-bis (4-hydroxyphenyl) -1,2-bis (phenyl) propane; 2,4-dihydroxybenzophenone; 4,4'-dihydroxydiphenyl sulfone; 5'-chloro-2,4'-dihydroxyphenyl sulfone; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxy-o-diphenyl ether; 4,3'-, 4,2'-, 4,1'-, 2,2'-, 2,3'- and the like dihydroxydiphenyl ethers; 4,4'-dihydroxybenzophenone; 4,4'-dihydroxy-2,6-diphenyldiphenyl ether; 2-methyl-2-carboxyethyl bis (4-hydroxyphenyl) propane; 4,4'-dihydroxy-3,2-dinitrodiphenyl ether; 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; 4,4'-dihydroxydinaphthyl ether; 4,4'-diydroxypentaphenyl ether; 4,4'-dihydroxy-2,5-diethoxy-diphenyl ether The dialkali metal salts (formula IV) ~ can be obtained from the dihydric phenols, which on the aryl nucleus by an alkyl, alkenyl, cycloaliphatic, cycloalkenyl, aryl or alkaryl groups are substituted, as well as from dihydroxytoluenes, dihydroxyxylenes, Dihydroxypyridines, dihydroxyanthraquinones, dihydroxybenzoic acids or dihydroxybenzophenones getting produced.

The dialkali metal salt of formula (IV) is preferably with equimolar Quantities of a compound of formula (III) reacted, although it is also possible is, a slight molar excess of one of the compounds, for example about 0.001 to 0.01 mol excess to be used. The reaction temperature is preferably 25 to 150 ° C. However, it is also possible, depending on the reaction components, the desired reaction product, the reaction time :, the solvent used and the like, also to work at lower or higher temperatures ..

The reaction time can preferably be about 5 minutes to about 30 minutes 40 hours for maximum yield. The obtained reaction product becomes out of the reaction mixture after the reaction severed. Therefor Usual solvents such as alcohols (for example methanol, ethanol and Isopropyl alcohol) 'and aliphatic hydrocarbons (e.g. pentane, hexane, Octane and cyclohexane) can be used.

The reaction of the compound of formula (III) with the dialkali metal salt of formula IV must be carried out in the presence of a dip @@ ren aprotic solvent will. The term "dipolar aprotic solvent" means organic Understood solvents that contain no active protons, which the invention Could interfere with the reaction. It is also possible to use mixtures of dipolar to use aprotic solvents with other inert organic solvents. Benzene, toluene, xylene and methylene chloride, for example, are suitable. These cosolvents offer the advantage of being used as a specific solvent for the manufactured Polymers can be used, solvents which are suitable and preferred according to the invention are non-acidic organic solvents containing oxygen and / or nitrogen, for example N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylformamide, Dimethyl sulfoxide, hexamethyl phosphoramide and the like.

The amount of solvent used in the reaction mixture can be approximately 0.5 to 50 parts by weight, based on 1 part by weight of the total reaction components used, be. Preferably about 2 to 20 parts by weight of solvent are used per part by weight of the total reaction components used. The polymerization will made under anhydrous conditions.

Example 1 A mixture of 2.2828 grams (0.010 moles) of bisphenol A, 0.8 g sodium hydroxide (1.5904 g 50.3 percent aqueous solution (0.02 mol)), 20 cc dimethyl sulfoxide and 6 cc of benzene was refluxed under a nitrogen atmosphere for 6 hours about a Dean Stark Separator stirred. The benzene was distilled off. The mixture was cooled to 4000 and 5.845 g (X0.010 mole)% 4,4'-bis- (3-nitrophthalimido) diphenylmethane and 30 ccm of dry dimethyl sulfoxide are added. After a reaction time of 40 At 40 ° C. for minutes, the reaction was stopped by adding 2 cc of glacial acetic acid and the reaction mixture was poured into 600 cc of methanol.

The product separating out as a fine, white, granular solid was filtered off and washed with water and methanol. After drying in vacuo 6.8 g of polymer were obtained at 60 ° C. (yield = 100%). The crude product was in Dissolved methylene chloride and reprecipitated with methanol. 6.2 g obtained from an off-white polymer.

Iodine number (CH2Cl2) 0.28; Tg 230 ° C; TGA (air) 380 ° C.

Analysis for (C44H30N2O6) n; Calc .: C 77.4; H 4.4; N 4.0.

Found: 77.1 4.6 4.6.

Example 2 A mixture of -2.2828 gj (0.010 moles) bisphenol A, 0.8 g sodium hydroxide (1.59 g of a 50.3 percent aqueous solution), 20 cc of dimethyl sulfoxide and 20 cc of benzene was refluxed under a nitrogen atmosphere for 5 hours stirred over a Dean Stark trap. The benzene was distilled off. The mixture was after cooling to 5000 with 5.5042 g (0.010 mol) of 4,4'-bis (3-nitrophthalimido) diphenyl ether and 30 cc of dimethyl sulfoxide are added.

The mixture was stirred at 80 ° C # 500 for 30 minutes, then cooled and placed in 500 cc of methanol.

The precipitate which separated out from the methanol was filtered off and washed with methanol and water. After drying in vacuo at 1100C were 6.8 g of a polymer crude product were obtained (yield 99.5%).

Iodine number (dimethylformamide) 0.26; Tg 2260C TGA (air) 3850C; analysis for (C43H28N207) n; Calc .: C 75.4; H 4.1; N 4.1 found; 74.9 4.3 4.7 e xample 3 A mixture of 2.2828 g (0.010 mole) bisphenol A, 0.8 g sodium hydroxide (1.59 g of a 50.3 percent aqueous solution (0.02 mol)), '20 ccm of dimethyl sulfoxide and 10 cc of benzene was refluxed over under a nitrogen atmosphere for 5 hours stirred a Dean Stark trap. The benzene was distilled off. The mixture was after cooling to 40 ° C. with 4.6640 g (0.010 mol) of 1,6-bis- (3-nitrophthalimido) hexane and 30 cc of dimethyl sulfoxide are added.

A resinous material deposited within minutes.

After a reaction time of 30 minutes at 5000, chloromethane was found to be finer Current bubbled through the solution and then 2 cc of glacial acetic acid was added.

After the mixture had cooled, it was poured into 600 cc of methanol and the solid which separates out is filtered off. After drying in vacuo at 11000 were 5.3 g of crude product were obtained (yield 88.4%). The polymer was in methylene chloride dissolved, filtered and precipitated again with methanol. 4.6 g of one was obtained white solid.

Iodine number (CH2C12) 0.40; Tg 135 ° C; TGA (air) 385 ° C; Analysis for (C37H32N2O6) n; Calc .: C 74.1; H 5.3; N 4.7.

Found: 73.3 5.1 5.2.

B e i s p-i e 1 4 A mixture of 2.2828 g (0.01 mole) bisphenol A, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent aqueous solution (0.02 Mol)), 20 cc of dimethyl sulfoxide and 15 cc of benzene were added under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 4 hours. The benzene was distilled off.

After cooling the mixture to 40.degree. C., 4.1029 g (0.01 mol) of 1,2-bis (3-nitrophthalimido) ethane and 30 cc of dry dimethyl sulfoxide registered. The reaction temperature was increased to 1000C within 25 minutes, and after a reaction time of 15 minutes at 100 ° C., the solution is cooled to room temperature and neutralized with glacial acetic acid.

The mixture was poured into methanol. That which is separated out in the process fine white powder was filtered off, washed with methanol and in vacuo at 110 ° C dried. 4.8 g of product were obtained (yield 88.5%). The raw polymer product was dissolved in methylene chloride, filtered and reprecipitated with methanol. Obtain 3.4 g of a white powder were obtained. Iodine number (CH2Cl2) 0.10; Tg 180 ° C TGA (air) 38800; Analysis for (C33H24H206) n; Ber: C 72.8; H. 4.4; N 5.2 Found: 72.0 4.6 7.

EXAMPLE 5 A mixture of 2.2828 grams (0.01 moles) of bisphenol A, 0.8 g of a 50.3% strength aqueous solution (0.02 mol) of sodium hydroxide, 20 cc of dimethyl sulfoxide and 8 cc of benzene were added under a nitrogen atmosphere for 4 hours stirred under reflux over a Dean Stark trap. The benzene. was distilled off. After cooling the mixture to room temperature, 5.9842 g (0.01 Möl) 4,4'-bis (3-nitrophthalimido) diphenyl sulfone and 30 cc of dry dimethyl sulfoxide registered. The mixture was stirred at 40 ° C for 30 minutes, then with chloromethane and finally treated with glacial acetic acid. The reaction mixture was poured into methanol, the polymer is filtered off, washed with methanol and dried in vacuo at 110.degree. 7.3 g of a brown powder were obtained (yield 79.5%). The crude product was dissolved in methylene chloride, filtered and again. precipitated in methanol. Obtain became a pale yellow polymer.

Iodine number (dimethylformamide) 0.13; Tg (no transitions); TGA (air) 3700C; Analysis for Cc43H28N2085) n; Calc .: C 70.5; H 3.8; S 4.4; Found: 67.8; 3.8; 4.3; N 4.5.

Example 6 A mixture of 2.0221 g (0.01 mol) of 4,4'-dihydroxydiphenyl ether, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent strength aqueous solution (0.02 mol)), 20 cc of dimethyl sulfoxide and 7 cc of benzene were added under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 4 hours. The benzene was distilled off1 until the solution was homogeneous. After cooling the mixture to 40.degree. C. were with stirring 5.5042 g (0.01 mol) of 4,4'-bis (3nitrophthalimido) diphenyl ether and 40 ccm dry dimethyl sulfoxide carried.

After stirring for 15 minutes at 40 ° C., the reaction was started by adding stopped by 2 cc of glacial acetic acid and the polymer was precipitated by adding it to methanol. The crude product (gray-white granules) was filtered off, washed with methanol and dried in vacuo at 1100C. 6.5 g of polymer were obtained (yield 99%). That Crude product was dissolved in methylene chloride, filtered and reprecipitated in methanol. A white powder was obtained.

Iodine number (CH2Cl2) 0.36; Tg (no transitions); TGA (air) 4000C.

Analysis for (C40H22N208) n; Calc .: C 73.0; H 3.3; N 4.3.

Found: 72.0; 3.4; 4.9.

EXAMPLE 7 A mixture of 2.0221 g (0.01 mol) of 4,4'-dihydroxydiphenyl ether, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent strength aqueous solution (0.02 mol)), 20 cc of dimethyl sulfoxide and 7 cc of benzene were added under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 4 hours. The Benzene "was distilled off.

The mixture was cooled to 40 ° C. while stirring, 4.4664 g (0.01 Moles) 1,6-bis (3-nitrophthalimido) hexane; and 30 cc of dimethyl sulfoxide entered. After stirring for 45 minutes at 40 ° C., the reaction was started by adding 2 cc of glacial acetic acid stopped and the mixture poured into methanol.

The product (off-white granules) was filtered off and added in vacuo Dried at 110 ° C. 5.6 g of polymer were obtained (yield 97.7%). The raw product was dissolved in methylene chloride, filtered and reprecipitated in methanol. Obtain became 4.0 g of pure polymer.

Iodine number (CH2Cl2) 0.29; Tg 12800; TGA (air) 330 ° C; Analysis for (C34H26N2O7) n; Calc .: 0'71.1; H 4.5; N 4.9.

- Found: 70.0; 4.5; 5.5.

Example 1 8 A mixture of 1.8621 g (0.01 mol) of 4,4'-dihydroxybiphenyl, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent strength aqueous solution (0.02 mol)), 30 cc of dimethyl sulfoxide and 6 cc of benzene were added a nitrogen atmosphere Stirred for 3 hours under reflux over a Dean Stark trap. The benzene was distilled off.

The suspension was cooled to 400 C and treated with 5.4845 & (0.01 Mol) 4,4h-bis (3-nitrophthalimido) diphenylmethane and 30 cem dry dimethyl sulfoxide offset. After stirring for 30 minutes at 40 ° C., 2 cc of glacial acetic acid were added and the Poured mixture into methanol.

The white powder which separated out was filtered off with water and methanol and dried in vacuo at 1100C.

6.3 g of polymer were obtained (yield 98.4X).

Iodine number (NMP, 0.1 n-LiBr) 0.36; Tg (no transitions); TGA (air) 400 ° C.

Analysis for (C41H24N2o6) n; Calc .: C 76.9; H 3.8; N 4.4.

Found: 75.2; 4.0; 4.9.

Example 9 A mixture of 1.8621 g (0.01 mole) of $ 4,4'-dihydroxybiphenyl, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent strength aqueous solution (0.02 mol)), 30 cc of dimethyl sulfoxide and 6 cc of benzene were added under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 6 hours. The benzene was distilled off. The stirred solution was cooled to 50 ° C. and added 5.5042 g (0.01 Mol) 4,4 '- (3-nitrophthalimido) diphenyl ether and 30 cc dry dimethyl sulfoxide offset. After a reaction time of 50 minutes at 50 ° C., the reaction was over Stop adding 2 cc of glacial acetic acid and pour the mixture into 600 cc of methanol.

The reaction product was filtered off, washed with methanol and dried in vacuo at 1100C. 6.1 g of a not completely white, granular material were obtained Product (yield 95%). The crude polymer was dissolved in N-methylpyrrolidone (NMP), filtered and reprecipitated in methanol, washed with methanol and dried in vacuo. 6.4 g of a brown powdery polymer were obtained.

Iodine number (NMP, 0.1 n-LiBr) 0.6; Tg (no transitions); TGA (air) 390 ° C.

Analysis for (C40H22N2O7) n; Calc .: C 74.8; H 3.4; N 4.8.

Found: 72.9; 3> 5; 4.8.

B e i 5-p i e l 10 A mixture of 1.1011 g (0.01 mol) of hydroquinone, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent strength aqueous solution (0.02 mol)), 20 cc of dimethyl sulfoxide and 6 cc of benzene were added under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 4 hours. The benzene was distilled off. The suspension of the hydroquinone salt obtained in dimethyl sulfoxide was cooled to 40 ° C. and while stirring with 5.4042 g (0.01 mol) of 4,4'-bis (3-nitrophthalimido) diphenyl ether and 30 cc of dimethyl sulfoxide are added. The mixture was 20 minutes at 4000 and Stirred for 10 minutes at 60 ° C., then cooled and acidified with acetic acid.

The mixture was introduced into methanol and the resulting precipitate filtered off, washed with water and methanol and dried in vacuo at 110.degree. 4.3 g of a somewhat brown powder were obtained, yield 76%). The raw product was dissolved in o-cresol, reprecipitated by pouring into methanol, filtered and dried. 4.2 g of a powdery polymer were obtained.

Iodine number (NMP, 0.1 n-LiBr) 0.45; Tg 2370C; TGA (air) .43000; analysis for (C34H18N2O7) n; Calc .: C 72.1; H 3.2; N 4.9.

Found: 69.8; 3.4; 5.9.

Example 11 A mixture of 5.5794 g (0.01 mol) of tetrabromotetramethylbiphenol, 5.4845 g (0.01 mol) 4,4'-bis (3-nitrophthalimido) diphenylmethane, 5.52 g (0.04 mol) Potassium carbonate, 0.5 g of dicyclohexylmethylamine and 50 cc of dry dimethylformamide was stirred at 35 to 40 ° C for one week under a nitrogen atmosphere.

The mixture was poured into methanol, the precipitate was filtered off, washed with methanol and water and dried in vacuo at 110.degree. The raw product was dissolved in methylene chloride, filtered and reprecipitated in methanol. Obtain became a gray powder.

Iodine number (CH2Cl2) 0.14; Tg (no transitions); TGA (air) 36000.

Analysis for (C45H28Br4N2O6) n; Calc .: C 53.3 H 2.8; N 2.7.

Found: 52.3 2.9 2.7 Example 12 A mixture of 2.2828 g (0.01 mol) bisphenol A, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent aqueous Solution (0.02 mol)), 20 cc of dimethyl sulfoxide and 6 cc of benzene were added under a nitrogen atmosphere Stirred for 5 hours under reflux over a Dean Stark trap. The benzene was distilled off. The stirred solution was cooled to 35 ° C. and added 5.5042 g of 01 Mol) 4,4'-bis (4-nitrophthalimido) diphenyl ether and 35 cm of dry dimethyl sulfoxide offset. The mixture was stirred at 40 ° C. for one hour and at 70 ° C. for 30 minutes and then carried in 600 cc of methanol containing 10 cc of glacial acetic acid.

The product was filtered off, washed with methanol and in vacuo dried at 11000. 6.7 g of a gray-white, granular powder were obtained (yield 9g). The crude product was dissolved in methylene chloride dissolved, filtered, reprecipitated in methanol and dried.

A fine-grained yellow solid was obtained.

Iodine number (CH2Cl2) 0.23; Tg 196 ° C; TGA (air) 4200C; Analysis for (C43H28N2O7) n; Calc .: 075.4; H 4.1; N 4.1.

Found: 74.1; 4.1; 4.1.

B e i s-p i e 1 13 A mixture of 2.2828 g (0.01 mol) of bisphenol A, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent aqueous solution (0.02 Mol)), 20 cc of dimethyl sulfoxide and 5 cc of benzene. under a nitrogen atmosphere Stirred under reflux over a Dean Stark trap for 4 hours. The benzene was distilled off. The mixture was cooled to 4000 and with stirring at 2.7521 each g (0.005 mol) of 4,4'-bis (3-nitrophthalimido) diphenyl ether and 4,4'-bis (4-nitrophthalimido) diphenyl ether and 40 ccm of dry dimethyl sulfoxide are added. The mixture was at for an hour Room temperature, 2 minutes at 60 ° C and then another 30 minutes at room temperature touched.

the acidification with 1 ccm glacial acetic acid was the reaction mixture in Entered methanol, the precipitated product filtered off, washed with methanol and dried in vacuo at 65 to 700C.

6.84 g of a gray-white granular powder (yield c 100%).

Iodine number (CH2Cl2) 0.17; ig 193 0; TGA (air) 3800C.

Analysis for (C43H28N2O7) n; Calc .: C 75.4; H 4.1, N 4.1.

Found: 72.7 4.3 4.2.

EXAMPLE 14 A mixture of 2.2828 grams (0.01 moles) of bisphenol A, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent aqueous solution (0.02 Mol)), 15 g of dimethyl sulfoxide and 8 cc of benzene was added under a nitrogen atmosphere Stirred for 5 hours under reflux over a Dean Stark trap. The benzene was distilled off. The mixture was cooled to 40 ° C. and 4.6640 g (0.01 mol) 1,6-bis- (3-nitrophthalimido) hexane and 55 cc of chlorobenzene were added. The mixture was stirred for 17 hours at room temperature, acidified with 1 cc of glacial acetic acid and then poured into 600 cc of methanol.

The product was filtered off, washed with methanol and water and dried in vacuo at 1100C. 5.5 g of an off-white powder were obtained (yield 91.6%). The crude product was dissolved in methylene chloride and reprecipitated in methanol. A snow-white granular polymer was obtained.

Iodine number (CH2Cl2) 0.28.

B e i s p i e 1 15 The disodium salt of bisphenol A was after conventional procedure from 1.666 g bisphenol A (7.306 millimoles), 1.162 g sodium hydroxide (14.61 Nillirnol, as a 50.3 percent aqueous solution), 15 ccm of dimethyl sulfoxide and 25 cc of benzene produced. When the g; Csamte water by azeotropic distillation was removed, the benzene was distilled off. The reaction mixture was 4.018 g (7.306 millimoles) of a mixture of bisimides made by reacting one equivalent 4,4'-diaminodiphenyl ether with one equivalent each of 3-nitro and 4-nitrophthalic anhydride was obtained, and 25 cc of dimethyl sulfoxide was added and the reaction mixture under Stirring heated to 55 to 60 ° C for 4 hours.

After adding 2 cc of acetic acid, the polymer was converted into methanol failed, collected on a filter, washed with methanol, and placed in a vacuum oven overnight dried at 8000 (15-20 mm Hg). The yield was 4.86 g (98%).

Iodine number (CH2Cl2) 0.21.

EXAMPLE 16 The disodium salt (dianion) of biphenol A was used by the usual method from 1.578 g of a 50.3 percent aqueous solution of Sodium hydroxide (19.85 millimoles) and 2.263 g (9.93 millimoles) of bisphenol A in 25 cc Dimethyl sulfoxide produced. To the mixture were added 25 cc of benzene and water azeotropically distilled off. When the reaction mixture was completely anhydrous, became the benzene is distilled off and the reaction flask is cooled to 55 to 6000.

Then there was 4.685 g (9.93 millimoles) of 2,4-bis (3-nitrophthalimido) toluene and 20 cc of dimethyl sulfoxide were added and the solution was heated to 55 to 60 ° C. for 1 1/2 hours heated. After adding 2 cc of acetic acid, the polymer became in a large amount Precipitated methanol, collected on a filter, washed with methanol and in a Oven dried. The yield was 5.53 g (92%).

Iodine number (CH2Cl2) 0.17.

EXAMPLE 17 Made from 1.455 g (6.38 millimoles) of bisphenol A and 1.015 g sodium hydroxide (50.3 percent aqueous solution (2.76 millimoles)) in 10 cc dimethyl sulfoxide a solution of the BPA dianion was prepared. After adding 25 cc of benzene was Water distilled off azeotropically.-The mixture was under a nitrogen atmosphere When all the water was removed, the benzene was distilled off and the reaction flask was allowed to cool to room temperature. The reaction mixture were 3.497 g of 4,4'-bis (3-nitrophthalimido) diphenylmethane, together with 30 cc of methylene chloride added and the resulting suspension about 15 hours at room temperature touched. To To add 2 cc of acetic acid the polymer was added precipitated in a large amount of methanol as a white granular solid product. The yield was 4.1 g (95%). Iodine number (0112.012) 0.20.

EXAMPLE 1 18 Using the usual procedure, the BPA dianion from 1.620 g (7.105 millimoles) bisphenol A and 1.130 g sodium hydroxide (50.3 percent aqueous solution (14.21 millimoles)) in 8 cc of dimethyl sulfoxide. After adding water was azeotropically distilled off from 25 cc of benzene. The reaction mixture was kept under a nitrogen atmosphere. After all the water has been removed, the benzene was distilled off and the reaction flask was cooled to room temperature calmly. Then there was 3.894 g of C7.105 millimoles) 4,4'-bis (3-nitrophthalimido) diphenylmethane added together with 32 cc of chlorobenzene. The reaction mixture was left overnight Stirred at 50 ° C. and resulted in a viscous solution.

As the reaction progressed, the original dark red became lighter. After adding 2 cc of acetic acid, the polymer was dissolved in a large amount of methanol failed. The fluffy white polymer was collected on a filter with methanol washed and dried overnight in a vacuum oven at 800C / 15-20 mm Hg.

The yield was 5.00 g (103%). Iodine number (CH2Cl2) 0.28.

EXAMPLE 1 19 A mixture of 2.2828 g (0.01 mole) bisphenol A, 0.8 g sodium hydroxide (1.5904 g of a 50.3 percent aqueous solution (0.02 Mol)), 20 cc of dimethyl sulfoxide and 5 cc of benzene was added under a nitrogen atmosphere Stirred for 4 hours under reflux over a Dean Stark separator and the benzene distilled off. The mixture was cooled to 40 ° C and added 5.2736 g (0.01 mol) 4,4'-bis (3-chlorophthalimido) diphenylmethane and 30 cc of dry dimethyl sulfoxide offset. The reaction mixture was stirred at 40 ° C. for 10 minutes and then at 85 ° C. for 18 hours. After cooling to 60 ° C., 1 cc of acetic anhydride was added and the mixture poured into methanol. The precipitated product was filtered off and washed with methanol and dried in vacuo at 110 ° C. 6.2 g of an off-white powder were obtained (Yield 91%). The crude product was dissolved in methylene chloride and again in methanol precipitated A white, finely powdered polymer iodine number (CH2Cl2) 0.08; Tg 174 ° C; TGA (air) 400 ° C.

Analysis for (C44H30N2O6) n; Calc .: C 77.4; H 4.4; n 4.0.

Found: 77.3; 4.6; 4.2.

B e i s p i e 1 20 Production of a polyetherimide from 1,6-bis- (3-chlorophthalimido) -hexane and bisphenol A.

A mixture of 2.2828 g (0.01 mole) bisphenol A, O "8; sodium hydroxide (1.5904 g of 50.3 percent aqueous solution (0.02 mol)), 20 ccm of dimethyl sulfoxide and 5 cc of benzene was refluxed under a nitrogen atmosphere for 5 "hours stirred a Dean Stark Absc "heider and distilled off the benzene. The mixture was cooled to 45 ° C and 4.4529 g (0.01 mol) of 1,6-bis (3-chlorophthalimido) hexane and 30 ccm of dry dimethyl sulfoxide are added. The solution was then 65 hours stirred at 70 ° C. Then 3 drops of glacial acetic acid were added and the reaction mixture given in methanol. The product which precipitated out was filtered off with methanol and water and dried in vacuo at 110 ° C. A white color was obtained fine-grain plllver.

Iodine number (CH2Cl2) 0.12; TGA (air) 400 ° C.

EXAMPLE 21 Production of a polyetherimide from 4,4'-bis- (4-chlorophthalimido) diphenyl ether.

The disodium salt (BPA dianion) was from 1.702 g (7.457 millimoles) bisphenol A and 1.186 g sodium hydroxide (50.3 percent aqueous solution (14.914 mmol)) in 25 cc of dimethyl sulfoxide. After adding benzene became water then benzene was distilled off azeotropically, / and then allowed to cool the dimethyl sulfoxide solution to 1000C. After adding 3,947 The reaction mixture was g (7.457 millimoles) of 4,4'-bis (4-chlorophthalimido) diphenyl ether heated to 100-105 ° C overnight. The reaction mixture was brought to room temperature cooled, mixed with a few drops of acetic acid and to precipitate the polymer poured into a larger amount of methanol. The polymer was filtered off with methanol washed and dried overnight at 60 ° C / 15 to 20 mm Hg. 4.57 were obtained g (91% yield).

Iodine number (dimethylformamide) 0.21.

Claims (21)

Claims .Polyetherimide of the following formula: wherein: R is a carbocyclic aromatic. Remainder with 6-20 carbon atoms; Rl R or additionally a xylylene or alkylene radical with 2 to 20 carbon atoms, a cycloalkylene radical, a bis (4-cycloalkyl) - (lower) alkylene radical or an alkylcycloalkylene radical; n = a number greater than 1; -0-Z <one of the following radicals Ca), (b) or (c) - wherein: R "denotes hydrogen, a lower alkyl or a lower alkoxy radical, it being possible for the oxygen on any of the rings to be in the o- or p-position to one of the anhydride carbonyl groups; and wherein the polyetherimide is replaced by a nitro-substituted aromatic group or a Hydroxyphenyl group is ended. 2. Polyetherimide according to claim 1, characterized in that R is one of the following radicals: phenylene, (lower) alkylphenylene -, where X is an aliphatic, cycloaliphatic or araliphatic group (having 1 to 8 carbon atoms) or -O-, # # -C-, -S- or -S- group; and n is a number from 2 to 5,000. 3. Polyetherimide according to claim 1 or 2, characterized by the following general formula: 4. Polyetherimide according to claim 3, characterized by the following general formula: 5. polyetherimide according to claim 4, characterized in that R means. 6. polyetherimide according to claim 4, characterized in that R and R ' means. 7. polyetherimide according to claim 3, characterized by the following formula: 8. polyetherimide according to claim 7, characterized in that and R 'represents an alkylene group having 2 to 20 carbon atoms. 9. polyetherimide according to claim 7, characterized in that R and R 'is an m-phenylene radical. 10. polyetherimide according to claim 7, characterized in that R and R ' means, 11. polyetherimide according to claim 7, characterized in that R and R ' means. 12. A process for the preparation of a polyetherimide, characterized in that the following components are reacted in a dipolar aprotic solvent: (1) a salt of an organic compound of the following general formula: MO-R-OM wherein M is an alkali metal and R is a divalent one carbocyclic aromatic radical having 2 to 20 carbon atoms and (2) a bisphthalimide of the following general formula: where R 'has the meaning given in claim 1, R "' is a chlorine or nitro group and R"'-Z# means one of the following groups: wherein R "can denote hydrogen, a lower alkyl or a lower alkoxy radical, and wherein R "'on any of the rings can be ortho or para to one of the carbonyl (anhydride) groups. 13. The method according to claim 12, characterized in that R is one of the following radicals phenylene, (lower) alkylphenylene and bivalent whether X is an aliphatic, cycloaliphatic or araliphatic group (with 1 to 8 carbon atoms) or -0-, -S- or And R '= R or a xylylene or alkylene radical with 2 to 20 carbon atoms, a cycloalkylene radical, a bis (4-cycloalkyl) - (lower) alkylene radical or an alkylcycloalkylene radical. 14. The method according to claim 12 or 13, characterized in that the bisphthalimide has the following formula: 1. Process according to Claim 12 or 13, characterized in that the bisphthalimide has the following formula: 16. The method according to claim 12 or 13, characterized in that the bisphthalimide has the following formula: 17. The method according to any one of claims 12 to 16, characterized in that the dipolar aprotic solvents N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylformamide, Dimethyl sulfoxide, hexamethylphosphoramide, N, N-diethylformamide, N, N-diethylacetamide or tetramethylene sulfone. 18. The method according to claim 17, characterized in that the solvent Is dimethyl sulfoxide. 19. The method according to claim 17 or 18, characterized in that the dipolar aprotic solvent with benzene, toluene, tylol-, chlorobenzene or Methylene chloride is mixed as an inert cosolvent. 20. Method according to one of claims 12 to 19? characterized, that the polymerization takes place under anhydrous conditions and under an inert atmosphere is made. 21. The method according to any one of claims 12 to 20, characterized in, that the reaction temperature is about 25 to 1500C.