DE4129325A1 - New bis-(hydroxy- or carboxy-alkyl- or aryl)-benzophenone imino:di:imide(s) - useful as monomers for prodn. of poly:ester(s) and poly:amide(s) with high thermal stability, low Tg, good solubility and thermoplastic processability - Google Patents

Abstract

Cpds. of formula (I) are new, in (J), R1 = 1-6C alkylene, or o-, m- or p-phenylene or benzylidene (both opt. substd. with Cl or lower alk(ox)yl; R2 = OH, 1-20C satd. or unsatd. alkyl (opt. substd. with Cl, OH, NH2, CONH2, COOR3 or NHCONHR3 (with R3 = H, 1-4C alkyl, Ph or benzyl; Y = OH or COOH. Prodn. of (I), comprises reaction of the corresp. diaryl ketones (II) with amines R2NH2 (III). Pref., amts. are 1-10 (esp. 1.05-5) mols. (III)/mol. (II). Also claimed are:polyesters of formula -(CO-Z-CO-O-Ar-O)- or -(O-Z-O-CO-Ar-CO)- (with Z = opt. substd. 1-18C alkylene, o-, m- or p-phenylene or -Phe-X-Phe (with Phe = p-phenylene; X = CH2, CMe2, O, S or SO2), pref. m- or p-phenylene; Ar = residue obtd. by removing Y from (I)); and polyamides of formula -(NH-Z-NH-CO-Ar-CO)- (pref. with Z = -Phe-CH2-Phe-). USE/ADVANTAGE - (I) are useful as monomers for the prodn. of polymers (claimed). (I) are new iminodi-imide monomers, useful for the prodn. of polyesters and polyamides with high thermal stability, good solubility, low Tg and good thermoplastic processability.

Description

The invention relates to and derived from benzophenone iminodiimides thermostable polymers.

The most technically most important thermostable polymers to date are fully aromatic polyimides, polyamides and polyamideimides. Although polyimides have extremely high thermal stability, but are usually neither fusible nor soluble and therefore only complex and expensive to process. The somewhat less thermostable aromatic polyamides are also infusible and insoluble in most organic solvents or only slightly soluble, so that their processing from solutions too Fibers or foils are associated with great difficulties. By installing diamines or dianhydrides with flexible chain elements (-CH₂-, -O-, -S-, -CO-) or from steric demanding diamines, such as in EP-A 01 62 606 and US-PS 38 95 064 describes the solubility and processability of aromatic polymers improved, however Thermostability significantly reduced.

There have now been new monomers based on 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) by incorporating azomething groups found that polymers with high thermal stability, good solubility, low glass temperatures and easier thermoplastic processability.

The present invention accordingly relates to benzophenone iminodiimides of formula I.

in the
Y hydroxyl or carboxyl,
R₁ is a straight-chain or branched alkylene radical having 1 to 6 carbon atoms or an o-, m- or p-phenylene or benzylidene radical optionally substituted by Cl, lower alkyl or lower alkoxy, and
R₂ is OH, a straight-chain or branched, saturated or mono- or polyunsaturated alkyl radical having 1 to 20 carbon atoms, which can be substituted with Cl, OH, NH₂, CONH₂ or COOR₃, or a radical of the formula NH-CO -NHR₃, in which R₃ can be hydrogen, an alkyl radical having 1 to 4 carbon atoms or a phenyl or benzyl radical,
mean.

In the formula I, R₁ is a straight-chain or branched Alkylene radical with 1 to 6 carbon atoms, such as. B. a methylene, Ethylene, propylene, isopropylene, butylene, sec. Butylene or hexylene radical, or an unsubstituted or with Cl, Lower alkyl groups with 1 to 5 carbon atoms, such as. B. methyl, Ethyl or propyl groups, or lower alkoxy groups with 1 to 5 carbon atoms, such as B. methoxy, ethoxy or propoxy groups, substituted o-, m- or p-phenylene or benzylidene radical, and R₂ is OH, or a straight-chain or branched, saturated or mono- or polyunsaturated, unsubstituted or substituted with OH, Cl, NH₂, CONH₂ or COOR₃ Alkyl radical with 1 to 20 carbon atoms, such as. B. a methyl, ethyl, Hexyl, dodecyl, octadecyl, vinyl, allyl, butadienyl, Isoprenyl, hydroxyethyl, hydroxyhexyl, hydroxydodecyl, hydroxyoctadecyl, Carboxymethyl, carboxyethyl, carboxydodecyl,  Carboxyoctadecyl, carboxyhexadecenyl, aminohexyl, Aminododecyl or aminotridecenyl radical, or a radical of Formula -NH-CO-NHR₃, such as. B. semicarbazyl, methylsemicarbazyl, Ethylsemicarbazyl, phenylsemicarbazyl or benzylsemicarbazyl. R₃ is hydrogen or an alkyl radical with 1 to 4 carbon atoms, such as B. a methyl, ethyl or propyl radical.

Compounds of formula I are preferred in which R₁ is a straight-chain Alkylene radical with 1 to 4 carbon atoms, such as. B. one Methylene, ethylene or butylene radical, or an unsubstituted or with lower alkyl or lower alkoxy groups with 1 up to 4 carbon atoms, such as B. methyl, ethyl, propyl, methoxy, Ethoxy or propoxy groups, substituted m- or p-phenylene or benzylidene radical and R₂ the radical OH, or a straight-chain, saturated, unsubstituted or with OH, NH₂ or COOH substituted alkyl radical with 1 to 18 carbon atoms, such as. B. one Methyl, ethyl, hexyl, dodecyl, octadecyl, hydroxyethyl, Hydroxyhexyl, carboxymethyl, carboxyethyl, carboxyoctadecyl, Aminoethyl, or aminohexyl, or a semicarbazyl or phenylsemicarbazyl radical.

Compounds of the formula I are particularly preferred the R₁ is an ethylene or unsubstituted p-phenylene radical and R₂ is OH, or a straight-chain, saturated, unsubstituted or alkyl radical substituted by OH, NH₂ or COOH with 1 to 8 carbon atoms, such as. B. a methyl, ethyl, Propyl, hexyl, hydroxyethyl, hydroxyhexyl, carboxymethyl, Carboxyethyl, aminomethyl, aminoethyl or aminohexyl radical, or a semicarbazyl or phenylsemicarbazyl radical.  

Another object of the present invention is a Process for the preparation of compounds of formula I.

in the Y, R₁, R₂ and R₃ are as defined above, this is characterized in that compounds of formula II

in which R₁ and Y are as defined above, with compounds of Formula III

R₂-NH₂

in the R₂ is as defined above, implemented.

The benzophenonetetracarboxylic acid diimide used as starting compounds (BTDI) derivatives of the formula II can, for example in Mosher W. A.K., Chlystek, S., J. Heterocycl. Chem. Volume 9, (1972) S 319, indicated, by reaction of BTDA with an equimolar amount of an amino alcohol or one Aminocarboxylic acid, such as ethanolamine, p-aminophenol, p-aminobenzoic acid, getting produced.

The BTDI derivatives then become the amines of the formula III desired benzophenone iminodiimides (Schiff bases) implemented.  

1 to 10 moles, preferably 1.05, are used per mole of BTDI derivative up to 5 moles of amine of the formula III used.

Amines of the formula III are, for example, n-hexylamine, hydrazine, Glycine, hydroxylamine, ethanolamine, semicarbazide, phenylsemicarbazide, Hexamethylenediamine, aminopalmitic acid or aminostearic acid.

The reaction is preferably carried out in a reaction reaction inert diluents, such as. B. Dimethylacetamide (DMA), dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), tetramethylurea or hexamethylphosphoric triamide (HMP).

DMA is preferably used as the diluent. To that The reaction mixture of BTDI derivative and amine can contain small amounts, about 0.01 mole of a catalyst such as e.g. B. toluenesulfonic acid, Acetic acid, a mineral acid or an acidic ion exchanger be added. This is useful in the reaction water formed by azeotropic distillation with a solvents which are inert under the reaction conditions, such as, for. B. Benzene or toluene. The excess amine can optionally by distillation or recrystallization or can also be recovered as salt. Salts of Amines such as B. hydroxylamine hydrochloride can be used. DMA / water mixtures can also be used as diluents from which the desired connection then fails becomes. The isolation of the ship's invention Bases can go through depending on their physical properties usual methods such. B. crystallization, extraction or Failures.

The raw products isolated in this way can, if necessary, subsequently still by known methods, such as. B. recrystallization, Reprecipitation or chromatography can be cleaned.

The Schiff bases according to the invention can then be used for production of polymers can be used.  

Further objects of the present invention are accordingly Polyester of formula IVa

 CO-Z-CO-O-Ar-O

or IVb

 O-Z-O-CO-Ar-CO

in the Z a substituted or unsubstituted, straight-chain or branched alkylene radical with 1 to 8 carbon atoms, an o-, m- or p-phenyl radical or a radical of the formula V.

wherein X can be -CH₂-, -C (CH₃) ₂-, -O-, -S- or -SO₂- and Ar is a radical of formula VI

in which R₁ and R₂ are as defined above, and polyamides of formula VII

 NH-Z-NH-CO-Ar-CO

in which Ar and Z are as defined above.

The polymers can be prepared by solution polycondensation in a diluent which is inert under the reaction conditions, such as DMA, HMP, NMP.  

Polyesters of the formula IVa are made from the inventive Schiff bases of formula I, in which Y is hydroxyl, by reaction with equimolar amounts of dicarboxylic acid dichlorides, such as B. isophthalic acid dichloride (IPDCL), terephthalic acid dichloride (TPDCL).

For the production of polyesters of formula IVb from Schiff's Bases of the formula I in which Y is carboxyl must be the carboxyl group be activated, for example by conversion in the corresponding dicarboxylic acid dichlorides, anhydrides or -ester. The dicarboxylic acid dichlorides are then converted with diols, such as. B. ethylene glycol, hydroquinone or Bisphenol-A produced the desired polyester of formula IVb.

The polyamides of the formula VII are also used the Schiff bases of the formula I in which Y is carboxyl, by reaction with thionyl chloride in the corresponding Dicarboxylic acid dichlorides and then transferred with an equimolar Amount of a diamine, such as bis (4-aminophenyl) methane (MDA).

In cases where the dicarboxylic acid dichloride with a Diol or a diamine is implemented, it is necessary that to remove the hydrochloric acid produced. This is advantageously done by adding an equivalent amount of a suitable one Base such as B. triethylamine, pyridine or dimethylaniline. The reaction temperature is depending on the Schiff used Base and desired polymer between -30 ° C and 50 ° C. If necessary, the reaction is carried out under a nitrogen atmosphere carried out.

The isolation of the polymers can be done by conventional methods, e.g. B. by precipitation with water or other suitable diluents respectively.

The polyesters and polyamides are very high Thermostability and low glass temperature, resulting in a thermoplastic processing is made possible. The production of films and fibers is due to the excellent solubility relieved in DMA.

Example 1 a) Preparation of N, N'-bis (hydroxyethyl) -3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide

In a three-necked flask with magnetic stirrer, dropping funnel and Thermometer was placed in 20 g (0.062 mol) of BTDA, in 180 ml DMA dissolved and from a dropping funnel 7.58 g (0.124 mol) Ethanolamine dissolved in 20 ml DMA slowly added dropwise. The reaction mixture was then half an hour at room temperature stirred and then heated to reflux for 2 hours.

The reaction mixture was worked up after cooling poured to 2 l of water at room temperature. The fancy Crystals were then filtered off, recrystallized from DMF / benzene = 1: 1 and in a vacuum drying cabinet at 80 ° C to constant weight dried.

Yield: 22.79 g (90% of theory)
Melting point: 208-209 ° C.

b) Preparation of N, N'-bis (hydroxyphenyl) -3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide

The reaction was carried out analogously to Example 1a), where the product failed after the start of the heating phase. The yellow crystals were filtered off and after recrystallization from DMF / benzene = 1: 1 in a vacuum drying cabinet at 80 ° C dried to constant weight.

Yield: 27.21 g (87% of theory) of yellow crystals
Melting point: 441 ° C

Example 2 a) Production of the Schiff base from N, N'- Bis (hydroxyethyl) -3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide and n-hexylamine

20 g (0.049 mol) N, N′-bis (hydroxyethyl) -3.3 ′, 4.4′- benzophenonetetracarboxylic acid diimide were heated in 150 ml Section. Dimethylacetamide (DMA) dissolved and 24.78 g (0.245 mol) n-Hexylamine, dissolved in 30 ml abs. Toluene as a water tug, were slowly added dropwise. Then 2 spatula tips p-Toluenesulfonic acid as a catalyst for the reaction mixture given and the temperature 24 hours between 120 ° C and kept at 130 ° C.

Thereafter, DMA along with toluene and the water formed distilled off in vacuo, the remaining residue in methylene chloride added and with water to remove the catalyst and extractive cleaning of solvent residues. The organic phase was collected, dried over sodium sulfate and evaporated. The crude product thus obtained was by Column chromatography cleaned.

Yield: 13.2 g (55% of theory) of yellow liquid (1)

Products (3) - (7) were produced analogously to Example 2a).

The elemental analyzes and imine bands are shown in Table 1.

b) Production of the Schiff base from N, N'- Bis (hydroxyethyl) -3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide and hydroxylamine

15.14 g (0.074 mol) of hydroxylamine hydrochloride and 4.8 g (0.06 mol) Sodium acetate was dissolved in 30 ml of water and at 60 ° C warmed up. Then 20 g (0.049 mol) of N, N'- Bis (hydroxyethyl) -3,3 ', 4,4'-benzophenonetetracarboximid  dripped slowly. After 30 minutes the reaction mixture cooled to 0 ° C and the separated oxime is suctioned off. The yellow crystals were cleaned after Column chromatography at 60 ° C in a vacuum drying cabinet up to dried to constant weight.

Yield: 12.45 g (60% of theory) of yellow crystals (2)
Melting point: 250-253 ° C

Table 1

Schiff bases from the diimide

A series of Schiff bases from N, N'- Bis (hydroxyphenyl) -3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide and N, N-bis (carboxyphenyl) -3,3 ′, 4,4′-benzophenonetetracarboxylic acid diimide analogous to that described in Examples 2a and 2b Connections established.

Elemental analyzes and imine bands are from Table 2 and Table 3 evident.

Table 2

Schiff bases from the diimide

Table 3

Schiff bases from the diimide

Example 3 Preparation of a polyester from N, N′-bis (hydroxyethyl) - 3,3 ', 4,4'-benzophenonetetracarboxylic acid diimide and isophthalic acid dichloride (IPDCL)

10 g (0.025 mol) of N, N′-bis (hydroxyethyl) -3.3 ′, 4.4′- benzophenonetetracarboxylic acid diimide and 5.08 g (0.025 mol) IPDCL were 50 ml abs at room temperature. DMA solved. To the on 0- 5 ° C cooled reaction solution slowly became 5.75 g (0.057 mol) triethylamine as acid scavenger, dissolved in 10 ml abs. DMA, added dropwise. After adding a further 0.5 ml of triethylamine the viscous solution was stirred at 20 ° C. for 2.5 hours. The The resulting salt was filtered off, the polymer was precipitated with water, centrifuged, washed with water and in a vacuum drying cabinet dried at 80 ° C to constant weight.

Yield: 12.52 g (93% of theory) (22)

A number of other polyesters were made using the same method produced. Your glass transition temperatures, the inherent viscosities, thermal stability and elemental analyzes are in Table 4 summarized.  

Table 4

Example 4 Preparation of a polyamide from (15) and bis (4-aminophenyl) methane (MDA)

1.9822 g (0.01 mol) of MDA were added under a nitrogen atmosphere a mixture of 25 ml abs. N-methyl-2-pyrrolidone (NMP) and 50 ml abs. Hexamethylphosphoric triamide (HMP) Room temperature solved. The solution was cooled to -15 ° C and Let stand for 15 minutes. 6.8054 g (0.01 mol) were then Dicarboxylic acid dichloride (made from dicarboxylic acid (15) and thionyl chloride in abs. Benzene; will after manufacture used directly) added at once. The reaction mixture was slowly warmed to room temperature and then over Stirred overnight under nitrogen. The resulting viscous The mass was poured into 500 ml of hot water with stirring precipitated shredded polymer washed several times with water  and dried in vacuo at 80 ° C to constant weight.

Yield: 7.49 g (93% of theory) (37)

All other polyamides were made using the same method. Your glass temperatures, inherent viscosity, thermostability, Solubility and elemental analysis are in Table 5 summarized.

Table 5

Claims (10)

1. Compounds of formula I. in the
Y hydroxyl or carboxyl,
R₁ is a straight-chain or branched alkylene radical having 1 to 6 carbon atoms or an o-, m- or p-phenylene or benzylidene radical optionally substituted by Cl, lower alkyl or lower alkoxy, and
R₂ is OH, a straight-chain or branched, saturated or mono- or polyunsaturated alkyl radical having 1 to 20 carbon atoms, which can be substituted with Cl, OH, NH₂, CONH₂ or COOR₃, or a radical of the formula NH-CO -NHR₃, wherein
R₃ can be hydrogen, an alkyl radical with 1 to 4 carbon atoms, a phenyl or benzyl radical,
mean. 2. Compounds of formula I according to claim 1, in which R₁ is a straight-chain alkylene radical having 1 to 4 carbon atoms or one optionally with lower alkyl or lower alkoxy substituted m- or p-phenylene or benzylidene radical, and R₂ is OH, a straight-chain, saturated alkyl radical with 1 to 18 carbon atoms, which is substituted with OH, NH₂ COOH can be, or a radical of the formula NH-CO-NHR₃, wherein R₃ can be hydrogen or a phenyl radical mean.   3. Compounds of formula I according to claim 1, in which R₁ is an ethylene or p-phenylene radical and R₂ is OH, a straight-chain, saturated alkyl radical having 1 to 8 carbon atoms, which can be substituted with OH, NH₂ or COOH, or a radical of the formula NH-CO-NHR₃, wherein R₃ is hydrogen or can be a phenyl radical. 4. A process for the preparation of compounds of formula I, characterized in that compounds of formula II in which R₁ and Y are as defined in claim 1, are reacted with compounds of the formula IIIR₂-NH₂in which R₂ is as defined in claim 1. 5. The method according to claim 4, characterized in that 1 to 10 moles, preferably 1.05 to 5 moles of the compound of Formula III can be used per mole of compound II. 6. Polyesters of the formula IVa CO-Z-CO-O-Ar-O or IVb OZO-CO-Ar-CO in which Z is a substituted or unsubstituted, straight-chain or branched alkylene radical having 1 to 8 carbon atoms, or an o- , m- or p-phenyl radical or a radical of the formula V wherein X can be -CH₂-, -C (CH₃) ₂-, -O-, -S- or -SO₂- and Ar is a radical of formula VI in which R₁ and R₂ are as defined in claim 1 mean. 7. Polyester of formula IVa or IVb according to claim 6, in which Z represents an m- or p-phenylene radical and R₁, R₂ and R₃ are as defined in claim 3. 8. Polyamides of the formula VII  NH-Z-NH-CO-Ar-CO in which Ar and Z are as defined in claim 6.   9. polyamides of formula VII according to claim 7, in which Z is a radical of formula VIII means and R₁, R₂ and R₃ are as defined in claim 3. 10. Use of the monomers of the formula I for the preparation of Polymers.