DE4232523A1 - Thermoplastic polyimide-sulphone(s) - from mixts. of oxy-di:phthalic anhydride, di:amino:di:aryl-sulphone(s), other di:anhydride(s) and di:amine(s), and mono:anhydride(s) or -amine(s) - Google Patents

Abstract

Polyimide-sulphones (PIS) are claimed, derived from (A) a dianhydride component contg. (a1) 25-90 mole% 4,4'-oxy-diphthalic anhydride (ODPA) and (a2) 10-75 mole% dianhydrides of formula (I), (B) a diamine component contg. (b1) 50-95 mole% diamines of formula (II) and (b2) 5-50 mole% other diamines and (C) mono-anhydrides, with ratio A:B = (1:1.005)-(1:1.10) and ratio B:C = (1:1.01)-(1:1.22), or mono-amines, with ratio A:B = (1.005:1)-(1.10-1) and ratio A:C = (1:1.01)-(1:1.22). In the formulae R is benzene-1,2,4,5-tetryl, diphenylsulphone-3,3',4,4'-tetryl, benzophenone-3,3',4,4'-tetryl or biphenyl-3,3',4,4'-tetryl; n, p is 0 or 1; and X, Y, Z is O, CO, SO2 or direct bond (at least one - SO2), with amino gps. meta to X if n = p = O, and para to X/Y/Z if n and/or p = 1. Also claimed are (1) a process for the prodn. of PIS, by reacting (A) and (B) in the presence of (C) and heating the prod. in a solvent, opt. in the presence of a catalyst; esp. a mixt. of tert. amine and lower fatty acid anhydride; and (2) mouldings, fibres and coatings or film obtd. from PIS as above. Pref. (A) comprises (a1) 30-60 mole% ODPA and (a2) 40-70 mole% (I), and (B) comprises (b1) 70-90 mole% (II) and (b2) 10-30 mole% other diamines. PIS are prepd. by reacting (A) and (B) (amts. as above) in the presence of (C) a monofunctional aromatic anhydride or mono-amine. USE/ADVANTAGE - Used for the prodn. of thermoplastic moulding materials (claimed). The invention provides polyimide-sulphones with a good balance of properties, esp. good thermoplastic processability (e.g. by injection, moulding, extrusion, deep drawing etc.) and good solubility in DMF, DMA, NMP, DMSO etc., esp. NMP.

Description

The present invention relates to polyimide sulfones based on are built from

• A) a dianhydride component
  • a ₁ ) 25 to 90 mol% 4,4'-oxydiphthalic anhydride and
  • a ₂ ) 10 to 75 mol% of dianhydrides of the general formula (I) where R is a tetravalent aromatic radical selected from the structures means and
• B) a diamine component
  • b ₁ ) 50 to 95 mol% of diamines of the general formula (II) where the variables n and p independently of one another are 0 or 1, the bridge members X, Y and Z independently of one another are -O-, CO, SO ₂ or a direct bond, with the proviso that at least one of the bridge members is SO ₂ and the amino groups are meta-linked with respect to the bridge members if both variables n and p mean 0 and are para-linked if at least one of the variables means n and / or p1 and
  • b ₂ ) 5 to 50 mol% of (b ₁ ) different diamines and
• C) monoanhydrides, the ratio of components A: B 1: 1.005 to 1: 1.10 and the ratio of the components B: C is 1: 1.01 to 1: 1.22 or monoamines, which is Ratio of components A: B 1.005: 1 to 1.10: 1 and the ratio of A: C is 1: 1.01 to 1: 1.22.

Polyimidesulfones, the 4,4, -oxydiphthalic dianhydride, in The following, abbreviated as ODPA, can be included from the EP-A 2 324 288 known. However, these are relatively hydrolyzed susceptible and have glass transition temperatures which are suitable for Applications that require high heat resistance, are too low.

In addition, such polyimide sulfones are in the JP-OS 185 715/87. These have the disadvantage that they are sensitive to oxidation. Furthermore are from the JP-OS 143 924/91 polyimide sulfones' based on ODPA be knows. However, these cannot be injection molded process into molded parts.

US 4,696,994 shows polyimide sulfones which Contain bis (aminophenoxy-phenyl) sulfones as the diamine component This US patent teaches that the dianhydride component nente in addition to 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride  not more than 20 mol%, preferably not more than 10 mol% should contain other dianhydrides.

The present invention therefore lay as polyimide sulfones Task based on a balanced range of properties exhibit. In particular, they should be well thermoplastic processed.

This task is described by the above solved polyimide sulfones according to the invention.

25 to 90 mol% are preferred as the dianhydride component 30 to 60 mol%, in particular 40 to 60 mol%, based on the dianhydride component, 4,4'-oxydiphthalic dianhydride used. In addition to 4,4'-oxydiphthalic dianhydride, 10 up to 75 mol%, based on the dianhydride component or more dianhydrides of the general formula (I) with used:

where R is a tetravalent aromatic radical selected from the structures

means. The dianhydrides are generally preferred NEN formula (I) in amounts of 40 to 70 mol%, in particular 40 to 60 mol%, based on the dianhydride component puts.

Mixtures are among the preferred dianhydride components from 4,4'-oxydiphthalic anhydride with pyromellitic acid di anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride or 4,4'-sulfonyldiphthalic dianhydride.

According to the invention, the diamine component contains 50 to 95 mol%, preferably 70 to 90 mol%, based on the diamine component, a diamine or a mixture of different Diamines of the general formula (II)

where the variables n and p independently of one another represent 0 or 1, the bridge members X, Y and Z independently of one another are -O-, CO, SO ₂ or a direct bond, with the proviso that at least one of the bridge members is SO ₂ and the amino groups are meta-linked with respect to the bridge members if both variables n and p mean 0 and are para-linked if at least one of the variables means n and / or p1.

Examples of such diamines are:

3,3'-Diaminodiphenylsulfone and 4,4'-bis (4-aminophenoxy) diphenyl sulfone. Such diamino Connections are known or can be made according to known Me methods are synthesized. For example, Aminohy droxyaromatic converted into their alkali metal salts and on finally reacted with dihaloaromatics.

The diamine component also contains 5 to 50 mol%, based on the diamine component of other diamines different from (b ₁ ). It is often advantageous if the diamine component contains 10 to 30 mol%, based on the diamine component, of these diamines.

Examples of suitable diamines (b ₂ ) are 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylsulfone or 1,3-di (4-aminophenoxy) benzene. Mixtures of different diamines (b ₂ ) can also be used.

According to the invention, the polyimide sulfones contain one Dianhydride and a diamine component another monoanhy drid or monoamine component (C). Below this are mono functional aliphatic, preferably aromatic anhydrides or to understand amines. Examples include phthalic acid anhydride, naphthalene-1,2-acid anhydride, naphthalene-2,3-acid reanhydride, or called aniline. Is the ratio of Components A: B 1: 1.005 to 1: 1.10 contain the polyimide sulfones as component (C) monoanhydrides, the Ratio of components B: C is 1: 1.01 to 1: 1.22. The ratio of components A: B is 1.005: 1 to 1.10: 1 contain the polyimide sulfones as component (C) Monoamines, the ratio of A: C 1: 1.01 to 1: 1.22 is.

The polyimide sulfones according to the invention generally have a melt viscosity of less than 2000 Pa · s. The melt viscosities are preferably in a range from 100 to 1800 Pa · s, in particular 500 to 1500 Pa · s. The melt viscosities are measured at a shear frequency of 1000 s ^-1 and a temperature of 400 ° C. In general, the melt viscosities change only slightly under the processing conditions.

In order to achieve good mechanical properties, it is advantageous if the number average molecular weight _{n of} the polyimide sulfones according to the invention is at least 10,000 g / mol. For many applications, _n can range from 12,000 to 15,000 g / mol; Molekularge weights _n of more than 30,000 g / mol are usually nichterfor sary.

The polyimide sulfones are produced in accordance with the invention by reacting the dianhydride component (A) with the diamine component (B). In the course of this reaction, presumably first the anhydride rings in the corresponding amide Carboxylic acid functions converted. This polyamide carbon Acid prepolymers cyclize with elimination of water then to the corresponding polyimide sulfone as in the following is shown schematically:

At the beginning, during the reaction or after the mole is built, the monofunctional len compounds (C) added. This allows the Molecular weights of the polyimide sulfones and the flow properties and control the stability of their melts.

The elimination of water is carried out in a solvent or in a Solvent mixture made. As a solvent preferably dipolar aprotic solvents such as N, N-dimethyl formamide, N, N-dimethylacetamide, N-methylpyrrolidone,  Dimethyl sulfoxide, diphenyl sulfone, sulfolane, γ-butyrolactone or N-methylcaprolactam used. Is particularly preferred N-methylpyrrolidone. It is often advisable to use one or more Co-solvents to be used which are azeotropic with water Form mixture that allows the reaction formed remove water by azeotropic distillation. One of the suitable cosolvents is, for example, toluene.

The water takes place depending on the reactivity of the diamine component cleavage at elevated temperature, preferably under Mit using a cosolvent, or at a lower temperature in the presence of a catalyst. A measure of reactivity the diamine component has its basicity constant expresses as pKa value (see, for example, Bessonov et al .: "Polyimides - Thermally Stable Polymers ", Consultants Bureau, New York 1987, 20 ff). In general, diamines with a pKa Value greater than 4.5 the catalytic, otherwise the purely thermal Process preferred.

The elimination of water in the absence of a catalyst usually starts at 20 ° C and generally only runs off 80 ° C with noticeable speed. Becomes a cosolvent with used, temperatures of more than 190 ° C are usually not mandatory. Cycli in the presence of a catalyst the polyamide carboxylic acid prepolymer is already below 80 ° C, usually even at temperatures below 70 ° C with increased speed.

Mixtures are generally used as catalysts tertiary amines and anhydrides of lower fatty acids puts. Aliphatic amines such as tri come as tertiary amines butylamine or triisopropylamine or aromatic amines such as Pyridine, lutidine, quinoline or isoquinoline. Examples of suitable anhydrides are acetic anhydride, Hexanoic anhydride, caprylic anhydride and lauric acid anhydride. Acetic anhydride is preferably used.

The polyimide sulfones according to the invention are notable for their good solubility in the solvents mentioned. In general, they are also in concentrations above 10% by weight completely soluble in these. Usually point they reduced viscosities from 20, preferably from 30 ml / g, ge measure in N-methylpyrrolidone at a concentration of  0.5 g / 100 ml. Most often, the invention Polyimide sulfones have no reduced viscosities above one Value of 200 ml / g, measured in N-methylpyrrolidone at egg ner concentration of 0.5 g / 100 ml. Po are preferred lyimide sulfones with reduced viscosities of 130 ml / g or less, measured in terms of N-methylpyrrolidone at a concentration tion of 0.5 g / 100 ml.

The polyimide sulfones according to the invention can be customary Substitutes in up to 70 wt .-%, preferably 20 to 50% by weight, based on the mixture, are added. To the Additives include fibrous or particulate fillers or Reinforcing agents such as carbon or glass fibers, glass gels and calcium silicates such as wollastonite and kaolin.

Other additives that the polyimide sulfones according to the invention May contain, for example, stabilizers, flow improvers and dyes. These can generally be found in Amounts of 0.1 to 20 wt .-% in the poly according to the invention imide sulfones may be included.

The polyimide sulfones according to the invention can per se known processes thermoplastic to moldings, fibers or flat structures are processed. It will be before moves to process the polyimide sulfones from the melt work. But it is also possible, for example, the polyimide sulfones before processing in a dispersant disperse. The processing can, for example, by Pressing, extruding, injection molding or deep drawing consequences. But you can also use a melt or dispersion Apply reinforcing fibers or mats and the result Semi-finished product, if desired after removing the dispersant by means of deforming.

The polyimide sulfones according to the invention can also be used for Manufacture of thermoplastic molding compositions, e.g. B. by Mix with other high temperature resistant polymers like Polyaryl ethers can be used.

Examples Abbreviations

NMP: N-methyl pyrolidone

Dianhydride

ODPA: 4,4'-oxydiphthalic anhydride
PMSDA: pyromellitic dianhydride
BTDA: benzophenonetetracarboxylic acid dianhydride
DSDA: 4,4'-sulfonyldiphthalic anhydride

Diamines

BAPS: 4,4′-bis (p-aminophenoxy) diphenyl sulfone
3,3'-DDS: 3,3'-diaminodiphenyl sulfone
APB: 1,3-di (4-aminophenoxy) benzene
DAB: 1,3-diaminobenzene
1,4-DDS: 1,4-diaminodiphenyl sulfone

The reduced viscosities (η _red ) were determined on 0.5% by weight solutions of the respective polyimide sulfone in NMP at 25 ° C.

The polyimide sulfones were made using a laboratory double Hauke Rheocard screw extruder on a Zylin the temperature of 370 ° C, a speed of 100 / min and throughputs of 400 g / h extruded and then gra nulated. In each case, a transparent, yellow-brown was obtained Product.

The glass transition was determined in each case by means of DSC measurements temperatures determined after extrusion.

Examples 1, 2, 5 General working instructions

The diamines were in a mixture of 10 l NMP and 15 l Xylene completely dissolved under nitrogen. Subsequently, were initially under external water cooling 29.6 g (0.2 mol) of phthalic anhydride and then the Dianhy  Drid mixture added so that the temperature of the reaction mixture does not rise above 30 ° C. After the addition is complete the mixture was heated to boiling (approx. 150 ° C) and Stirred at this temperature for 5 hours, water being removed was divorced.

After the water separation ended, there was so much Xylene distilled off until the precipitated polysulfonimide had come off again. After cooling, 10 l were still NMP added.

The polyimide sulfone solution thus obtained was poured out in water falls and then with hot water extra 24 hours here. The polyimide sulfone was filtered off and added for 2 days Dried 140 ° C.

Example 3

The trial was working according to the general regulation was carried out, but one-tenth each the amount of NMP, xylene and phthalic anhydride used.

Example 4

The diamines were completed in 2 liters of NMP under nitrogen brought into solution. Subsequently, what was external cooling first 5.25 g (35 mmol) phthalic anhydride and then added the dianhydride mixture so that the temperature the reaction mixture did not rise above 30 ° C. After finish The addition was stirred at 30 ° C for 5 hours.

The reaction mixture was then treated with 1 l of NMP, 220 ml Pyridine and 270 ml of acetic anhydride added and a further 5 hours the stirred at 600 ° C.

The polyimide solution thus obtained was precipitated in water and then extracted with hot water for 24 hours. The polyimide sulfone was filtered off and at 140 ° C for two days dried.  

The compositions of the anhydride and amine components, and the properties of the polyimide sulfones obtained Tables 1 and 2.

Claims (10)

1. Polyimide sulfones

• A) a dianhydride component
  • a ₁ ) 25 to 90 mol% 4,4'-oxydiphthalic anhydride and
  • a ₂ ) 10 to 75 mol% of dianhydrides of the general formula (I) where R is a tetravalent aromatic radical selected from the structures means and
• B) a diamine component
  • b ₁ ) 50 to 95 mol% of diamines of the general formula (II) where the variables n and p independently of one another are 0 or 1, the bridge members X, Y and Z independently of one another are -O-, CO, SO ₂ or a direct bond, with the proviso that at least one of the bridge members X, Y or Z is SO ₂ and the amino groups are meta-linked with respect to the bridge members if both variables mean n and p 0 and are para-linked if at least one of the variables means n and / or p1 and
  • b ₂ ) 5 to 50 mol% of (b ₁ ) different diamines and
• C) monoanhydrides, where the ratio of components A: B is 1: 1.005 to 1: 1.10 and the ratio of components B: C is 1: 1.01 to 1: 1.22 or monamines, where the ratio of Components A: B is 1.005: 1 to 1.10: 1 and the ratio of A: C is 1: 1.01 to 1: 1.22.

2. polyimide sulfones according to claim 1, in which the dian hydride component (A)

• a ₁ ) 30 to 60 mol% 4,4'-oxydiphthalic anhydride and
• a ₂ ) 40 to 70 mol% of dianhydrides of the general formula (I)
  is constructed.

3. polyimide sulfones according to any one of claims 1 to 2, in which the diamino component (B)

• b ₁ ) 70 to 90 mol% of diamines of the general formula (II) and
• b ₂ ) 10 to 30 mol% of (b ₁ ) different diamines and is built up.

4. polyimide sulfones according to any one of claims 1 to 3, in where the diamines (B) are selected from the group consisting of 3,3'-diaminodiphenyl sulfone, 4,4'-bis (p- aminophenoxy) diphenyl sulfone and 1,3-diaminobenzene. 5. polyimide sulfones according to any one of claims 1 to 4, obtainable by reaction

• A) a dianhydride component
  • a ₁ ) 25 to 90 mol% 4,4'-oxydiphthalic anhydride and
  • a ₂ ) 10 to 75 mol% of dianhydrides of the general formula (I) where R is a tetravalent aromatic radical selected from the structures means with
• B) a diamine component
  • b ₁ ) 50 to 95 mol% of diamines of the general formula (II) where the variables n and p independently of one another mean 0 or 1, the bridge members X, Y and Z independently of one another are -O-, CO, SO ₂ or a direct bond, with the proviso that at least one of the bridge members X, Y or Z is SO ₂ and the amino groups are meta-linked with respect to the bridge members if both variables mean n or p 0 and are para-linked if at least one of the variables means n or p1 and
  • b ₂ ) 5 to 50 mol% of (b ₁ ) different diamines and
• C) and a monofunctional compound selected from the group of aromatic carboxylic acid anhydrides and aromatic monoamines.

6. Process for the preparation of the polyimide sulfones according to one of claims 1 to 5, characterized in that the dianhydride component (A) with the diamine compo component (B) in the presence of component (C) and the reaction product is heated in a solvent. 7. Process for the preparation of the polyimide sulfones according to one of claims 1 to 5, characterized in that the dianhydride component (A) with the diamine compo component (B) in the presence of component (C) and the reaction product in a solvent in counter were a catalyst further implemented.   8. The method according to claim 7, characterized in that a catalyst is a mixture of a tertiary Amine and an anhydride of a lower fatty acid ver turns. 9. Use of the polyimide sulfones according to one of the An Proverbs 1 to 5 for the production of thermoplastic Molding compounds. 10. Moldings, fibers and flat structures available under Use of the thermoplastic molding compositions according to one of claims 1 to 5.