WO2002102756A2

WO2002102756A2 - Polyimides comprising cf2o structural elements

Info

Publication number: WO2002102756A2
Application number: PCT/EP2002/006443
Authority: WO
Inventors: Peer Kirsch; Andreas Taugerbeck; Georg LÜSSEM; Andreas Beyer; Sieglinde Mair
Original assignee: Merck Patent Gmbh
Priority date: 2001-06-19
Filing date: 2002-06-12
Publication date: 2002-12-27
Also published as: JP2004530714A; WO2002102756A3; DE10129335A1; KR100873547B1; KR20040015744A

Abstract

The invention relates to chainlike polycyclic bisanhydrides, containing between 2 and 12 permanent-chain cyclenes, selected from 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, bicyclooctylene, cubylene, which can be mono- or polysubstituted with halogen, cyano, alkyl, fluoralkyl, alkoxy and/or fluoralkoxy. Said cyclenes are linked by bridging groups, selected from a single bond, -CF2O, -OCF2-, -O-, -S-, -SO2-, -CO-, -NH-, -(CH2)1-10-, -(CF2)1-10-, -CH(CH3)-, -CH(CCI3)-, -CH(CF3)-, -C(CH3)2-, -C(CF3)2-, -C C-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF- and the formulae in (I), with the proviso that at least one bridging group is -CF20- or -OCF2-. The polycyclenes are terminated at both ends of the chain by various groups, selected from the formulae in (II).

Description

Polyimides with CF ₂ O structural elements

The invention relates to chain-shaped polycyclic bisanhydrides and polyimides which can be obtained by polycondensation of the chain-shaped polycyclic bisanhydrides with diamines.

Liquid crystal displays (LCDs) are becoming increasingly important and are already being used for a large number of applications. Examples include wristwatches, notebook computers, TV sets and display displays in the instrument panel of motor vehicles or in the aircraft cockpit.

In its simplest form, a liquid crystal display consists of a liquid crystalline layer with opposite sides, a set of electrodes on each side of the liquid crystalline layer and a polymeric orientation layer between each set of electrodes and the liquid crystalline layer. The liquid-crystalline molecules are oriented at a certain angle, which is referred to as the angle of inclination, with respect to the plane of the inside of the two substrates, for example

Glass plates, plastic foils or quartz plates that support the electrodes. The inside of the substrates have a coating of sets of transparent electrodes (electrical conductors), usually of indium tin oxide. The orientation process is carried out by applying the organic polymer from solution to the two substrates coated with indium tin oxide. After removal of the solvents and / or curing of the polymer layers, the substrate surfaces are usually rubbed or polished in a certain direction with fabric. The rubbing or polishing serves to produce a uniform optical direction. After polishing the two substrates, they are rotated by 70 to 360 ° to one another, connected to one another with suitable spacers and using organic adhesives, and filled with a wide variety of mixtures of liquid-crystalline materials. At this stage of the manufacturing process, polarizing films are often applied to the outer substrate surfaces by lamination. Finally, the electrical connections to both substrates are made.

Polyimide films are the most commonly used orientation films today. Polyimide films are used to control the orientation and the

Tilt angle of the liquid crystal molecules in liquid crystal displays. These are very thin, their thickness is generally between 100 and 2000 A. Orientation in a single direction is induced by polishing with special textile materials. The actual angle of inclination is determined as a function of the order of the polymers on the surface of the resulting surface energy, the type of fabric used to polish the surface, and the size of the work involved in polishing.

The object of the invention is to provide new polyimide materials which are suitable for producing polymeric orientation films in liquid crystal displays.

The object is achieved by chain-shaped polycyclic bisanhydrides, containing 2 to 12 chain cycles, selected from 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, Bicyclooctylene, cubylene, which can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy, the cycles being bridged by groups selected from a single bond, -CF ₂ O-, -OCF ₂ - , -O-, -S-, -SO ₂ -, -CO-, -NH-, - (CH ₂ ) ι-ιo-, - (CF ₂ ) ι-ιo-. -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -C _≡ C-, - CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-,

are linked to the proviso that at least one bridging group - CF ₂ O- or -OCF ₂ - is, the polycycles at both chain ends selected by different groups

are scheduled.

Preferred chain-shaped polycyclic bisanhydrides are those of the general formula (I):

^{E "Z1} - ^A Ü ^Z2 - ^B Ü - Z ³ - C ^ -D ^ - ^F

(D

wherein

A, B, C and D can be the same or different and 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene and 1, 4-cyclohexylene with halogen, cyano, alkyl , Fluoroalkyl, alkoxy and / or fluoroalkoxy can be substituted one or more times,

E and F can be the same or different and

mean,

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 can be the} same or different and a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO- , -NH-, - (CH ₂ ) ι.ιo-, - (CF ₂ ) ι-ιo-, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, - C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -C≡C-, CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-,

with the proviso that at least one of the groups Z ¹ to Z ^{5 is} -CF ₂ O- or -OCF ₂ -, and

w, x, y and z are independently 0 or 1.

Preferred groups Z are a single bond - CF ₂ O-, -OCF _∑ -, -CO-, -CH ₂ -, -CH ₂ CH ₂ - ₍ -O-, -S-, -SO ₂ -, -CF ₂ CF. ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -,

Particularly preferred chain-shaped polycyclic bisanhydrides are those with a symmetrical structure of the general formula (II) - (V):

wherein

A, B are as defined above, z ¹ , z- ¹ , z ² , z- ² , z ^{3 have} the meaning of Z ¹ - Z ⁵ as defined above with the proviso that

Z ^"1 = -OCF ₂ - if Z ¹ = -CF ₂ O- and vice versa,

Z ^"2 = -OCF ₂ - if Z ² = -CF ₂ O- and vice versa,

Z ^"1 = -CH = CF- if Z ¹ = -CF = CH- and vice versa,

Z ^"2 = -CH = CF- if Z ² = -CF = CH- and vice versa,

Z ^"1 = Z ¹ and Z ^{" 2} = Z ² in all other cases.

Examples are chain polycyclic bisanhydrides of the formulas (Ha) (VI):

where Z2, Z - 3 are as defined above.

The compounds (Ha) with Z ³ = a single bond, -O- or -C (CF ₃ ) ₂ -, compounds (IIb) with Z ³ = a single bond, -O- or -C (CF ₃ ) are very particularly preferred ₂ - and compounds (IVa) with Z ² = a single bond, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -. Various processes, as listed below, are suitable for producing the -O-CF ₂ bridges. Otherwise, the chain-shaped polycyclic bisanhydrides according to the invention are obtained by the methods known per se in preparative organic chemistry, as described in Houben-Weyl, Methods of Organic Chemistry, Stuttgart, DE.

According to one method, an aromatic halide is first converted into a Grignard compound or into a lithiated compound and then converted into the dithiocarboxylic acid with carbon disulfide. The dithiocarboxylic acid is converted into a thioester with a phenol in the presence of an alkali metal hydride and iodine. The desired -O-CF ₂ bridge is then formed from the thioester using a fluorinating agent.

According to another process, a cyclohexanone is first reacted with hexamethylphosphoric triamide and dibromodifluoromethane, a difluorohexylidene derivative being obtained. Bromine is first added to this and then etherified by reaction with a phenolate with simultaneous elimination of hydrogen bromide to form a —CF ₂ —O bridge.

Disadvantages of these processes are that the reaction rates are low, the yields are unsatisfactory and the work-up and purification of the product are expensive.

According to a preferred process, a bis (alkylthio) carbenium salt is first reacted in the presence of a base with a compound having at least one hydroxyl group and then, preferably in situ, with a fluorinating agent and an oxidizing agent for connection to at least one -CF ₂ - O-bridge in the molecule is oxidatively fluorinated.

The bis (alkylthio) carbenium salts can be prepared very easily from the corresponding carboxylic acids or activated carboxylic acid derivatives. Suitable carboxylic acid derivatives are, for example, halides, carboxylic acid pseudohalides, carboxylic acid sulfonylates, which are suitably substituted, for example a trifluoromethanesulfonylate. Carboxylic anhydrides and alkyl or phenyl carboxylic acid esters can also be used. The salts precipitate out of the reaction solution in a clean form and can be used in the next stage without further purification.

The bis (alkylthio) carbenium salt is first converted to the dithioorthoester by reaction with the compound containing at least one hydroxyl group. This dithioorthoester is generally not isolated, but is immediately implemented further. The oxidative fluorination to give a compound containing a -CF ₂ -O group takes place under very mild, slightly basic conditions and, in contrast to conventional methods, is therefore compatible with a large number of unprotected functional groups, for example a nitrile group. A further advantage is that the stereochemistry of the radicals, for example an ice or trans-cyclohexylene radical, is retained in the reaction. The basic steps are summarized in Figure 1 below.

ABCD Fig. 1 Reaction scheme for the production of connections with a CF ₂ O bridge.

The carboxylic acid derivative A, in which X represents, for example, -OH, halogen, pseudohalogen, substituted sulfonate, an anhydride, alkoxy or phenoxy, is reacted with an alkylthiol to form the bis (alkylthio) carbenium salt B. Dithiols which lead to the formation of a cyclic cation are preferably used. Ethanedithiol, propanedithiol or 1,2-benzenedithiol, which lead to the formation of dithianylium or dithiolanylium salts, are therefore particularly suitable. This salt B is then converted to the orthoester C using a hydroxy compound R ^b -OH. The orthoester C is generally not isolated, but directly oxidatively to Compound D implemented. The method can be used universally, so that R ^a and R ^b are not subject to any restrictions. R ^a and R ^b can thus be, for example, independently of one another an alkyl, an aryl, a cycloalkyl or an alkenyl radical, where these radicals can in turn be substituted as desired, for example by halogen, pseudohalogen, hydroxyl or carbonyl groups.

Advantages of the process described last are that it leads to good yields with satisfactory reaction rates. Intermediate and end products are easy to clean.

The present invention further relates to polyimides having -CF ₂ O groups, which are obtainable by polycondensation of chain-shaped polycyelic bisanhydrides according to the invention and optionally further polycyelic bisanhydrides with diamines.

Suitable diamines are the diamines of the following formulas (VII) (XXXVI):

(XVIII)

CF,

(XXIII)

(XXVII)

(XXVIII)

(XXXII)

(XXXIII)

(XXXIV)

(XXXVI)

Preferred diamines are chain polycyelic diamines which are terminated at the chain ends by -NH ₂ .

Particularly preferred diamines contain 2 to 12 chain cycles selected from 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1, 4-cyclohexylene, bicyclopentylene, bicyclooctylene and cubylene, which with Halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy can be substituted one or more times, the cycles being selected by bridging groups from a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NH-, - (CH ₂ ) ι-ιo-, - (CF ₂ ) _1-10 -, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, - CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -C≡C-, -CH = CH-, CF = CH-, -CH = CF-, -CF = CF,

are linked.

Special diamines have the general formula (XXXV):

(XXXV) where

A, B, C and D may be the same or different and 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, bicyclooctylene and cubylene, the can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy,

Z ¹ Z ² Z ³

Z ⁴ and Z ^{5 can be the} same or different and are a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NH-, - (CH2) ι-ιo-, - (CF ₂ ) ι-ιo-, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, C ( CF ₃ ) ₂ -, -C≡C-, -CH = CH-, -CF = CH-, CH = CF-, -CF = CF-,

mean,

-NH _{2 is} independently bound in the 3- or 4-position, and

w, x, y and z are independently 0 or 1.

Examples are diamines of the general formulas (XXXVI) to (XL)

(XXXVII)

(XXXVIII)

(XXXXIX)

wherein

A, B are as defined above,

zzz ² ,

T \ z ^{3 have} the meaning of Z ¹ - Z ⁵ as defined above with the proviso that

Z ^"1 = -OCF ₂ - if Z ¹ = -CF ₂ O- and vice versa, Z ^{" 2} = -OCF ₂ - if Z ² = -CF ₂ O- and vice versa,

Z ^"1 = -CH = CF- if Z ¹ = -CF = CH- and vice versa, Z ^{" 2} = -CH = CF- if Z ² = -CF = CH- and vice versa, Z ^"1 = Z ¹ and Z ^'2 = Z ² in all other cases,

-NH ₂ on both chain ends in 3 or in

4-position is bound.

The present invention furthermore relates to polyimides which are obtained by polycondensation of chain-shaped polycyelic bisanhydrides and / or further polycyelic bisanhydrides with chain-shaped polycyclic diamines which are terminated by -NH ₂ at the chain ends are terminated and at least one bridging group selected from - CF ₂ O- or -OCF ₂ - are available.

The diamines can be constructed analogously to the diamines of the general formulas (XXXVI) to (XL) with the additional proviso that at least one bridging group in the diamines is -CF2O- or -OCF ₂ -.

Suitable further bisanhydrides are the compounds of the formulas (XLI) to (LVIII):

(XLVII)

(XLVIII)

Despite their comparatively high molecular weight, the monomers mentioned are notable for very good solubility in the customary organic solvents. The size of the repetitive units lowers the relative number of link positions (imide bonds). These linking positions can contribute to the binding of ionic impurities to the polymer and thus impair the usability of the polymer as a component of electronic components, for example by reducing the electrical resistance. The reduction in the number of linking positions based on the molecular weight is therefore a decisive advantage.

Advantages of the polyimides according to the invention are furthermore their high thermal, photochemical and chemical stability, their high lipophilicity, their high electrical resistance and their low affinity for ionic impurities. These properties offer particular advantages when the polyimides are used in electronic components, for example as an orientation material in LCDs or organic light-emitting diodes (OLEDs) or as an insulation material for electronic circuits. The polyimide orientation film can be produced by solution polymerization of essentially equimolar amounts of the bisanhydride and the diamine, preferably at room temperature to 50 ° C., for example in N-methylpyrrolidone or N, N-dimethylacetamide as solvent. The imide can then be formed in the polyamic acid solution obtained by chemical imidation with acetic anhydride and pyridine at 50 ° C. or by thermal imidation by heating to 70 to 250 ° C. The polyimide obtained can then be precipitated, filtered and dried in vacuo. The polyimide can then be dissolved in γ-butyrolactone as a solvent and applied by spin coating to a glass plate coated with indium tin oxide and at a temperature of, for example, 150 ° C. to 220 ° C. for a period of generally one minute to two Hours imidized and dried. The polyimide coating obtained in this way can then be polished in a manner known per se in order to obtain the orientation-controlling film. An overview of conventional techniques for adjusting the orientation can be found, for example, in I. Sage in Thermal Liquid Chrystals, edited by GW Gray, John Wiley & Sons, 1987, pages 75 to 77 and in JM Geary et al., Journal of Applied Physics, Vol. 62 (10), 1987, pages 4100-4108.

The invention is illustrated by the examples below.

Examples

Production of the monomers

example 1

2: A mixture of 0.2 mol 1 0.48 mol 1, 3-propanedithiol and 0.6 mol

Trifluoromethanesulfonic acid is heated to 120 ° C for 1 h. The mixture is allowed to cool to 80 ° C., diluted with 300 ml of acetonitrile and then diluted with 2 l of dibutyl ether. After cooling to 0 ° C., the precipitated product 2 is filtered off with suction, washed with diethyl ether and dried.

Yield: 92%

Coupling with p-nitrophenol to 3 and further conversion to 4: 0.1 mol 2 is dissolved in 500 ml of CH ₂ CI and cooled to -78 ° C. Is added dropwise at the same temperature a mixture of 0.4 mole of p-nitrophenol and 0.4 mol of NEt _3, diluted to 300 ml with CH ₂ CI _2, followed by 1 mol NEt ₃ 3HF. Then 1 mol of Br _{2 is} slowly added dropwise while keeping the temperature constant. The mixture is allowed to come to RT and is worked up with water. The reaction product is chromatographed with a suitable mobile phase and then recrystallized from MTB ether (mp = 158-159 ° C.). The nitro compound is hydrogenated to the diamine in the presence of Lindlar catalyst in THF. For purification, product 4 is crystallized from pentane (mp. = 120 ° C.). Yield: 47%

Example 2

5: The synthesis is carried out analogously to 3, 4-hydroxyphthalic anhydride being used instead of p-nitrophenol. Yield: 62%

Example 3

7: 0.3 mol 6 are dissolved in 1 l of ethanol and hydrogenated in the presence of 10 g of 5% by weight of Rh at C at 50 ° C. and 50 bar pressure. After separation with a catalyst, the crude product is repeatedly recrystallized from acetone in order to obtain the pure trans / trans-dicarboxylic acid 7 in a 22% yield.

: A mixture of 0.2 mol 7, 0.48 mol 1, 3-propanedithiol and 0.6 mol trifluoromethanesulfonic acid is heated to 120 ° C. for 1 h. The mixture is allowed to cool to 80 ° C., diluted with 300 ml of acetonitrile and then diluted with 2 l of dibutyl ether. After cooling to 0 ° C., the precipitated product 8 is filtered off, washed with diethyl ether and dried. Yield: 87%

10

Coupling with p-nitrophenol to 9 and further conversion to 10: 0.1 mol 8 is dissolved in 500 ml of CH ₂ CI ₂ and cooled to -78 ° C. A mixture of 0.4 mol of phenol and 0.4 mol of NEt ₃ diluted with 300 ml of CH ₂ CI _{2 is added} dropwise at the same temperature, followed by 1 mol of NEt ₃ 3HF. Then 1 mol of Br _{2 is} slowly added dropwise while keeping the temperature constant. The mixture is allowed to come to RT and is worked up with water. The reaction product is chromatographed with a suitable mobile phase and then recrystallized. The nitro compound is hydrogenated to the diamine in the presence of Lindlar catalyst in THF. The product is crystallized for purification. Yields: 42%

Example 4

11: The synthesis is carried out analogously to the synthesis of 9, using p-benzaldehyde instead of p-nitrophenol. Yield: 58%

Example 5

12

13

14

15 : 51.97 mmol of 2-trimethylsilyl-1,3-dithiane are dissolved in 250 ml of THF. 31.770 ml of a 15% by weight solution of butyllithium (51.97 mmol) are added dropwise to this solution at -70.degree. The mixture is allowed to gradually warm to 0 ° C. in the course of 4 h, is cooled again to -70 ° C. and 23.708 mmol of the diketone 12 in 50 ml of THF are added dropwise, a colorless precipitate being formed. When the addition is complete, the cooling is removed and the mixture is stirred overnight. Then the mixture is added to 400 ml of ice water and extracted 5 times with dichloromethane. The combined organic phases are washed twice with saturated NaCl solution and dried over sodium sulfate. The solvent is removed in vacuo and the slightly yellow crude product is recrystallized from dichloromethane. Colorless flakes of product 13 are obtained. The mother liquor from the crystallization is concentrated and the residue is recrystallized again from dichloromethane.

Yield: 77.3%

: 17.383 mmol 13 are suspended in 100 ml dichloromethane and 34.774 mmol trifluoromethanesulfonic acid are added dropwise to this suspension with ice cooling. Then you leave the clear yellow

Stir solution for 1 h at room temperature. The mixture is then cooled to -70 ° C. and a solution of 52.153 mmol of 4-nitrophenol and 62.576 mmol of triethylamine in 20 ml of dichloromethane is added dropwise. After 1 h, 151.976 mmol of triethylamine trishydrofluoride and then a portion of a suspension of 173.833 mmol of DBH in 70 ml of dichloromethane are added in portions within 30 minutes. The mixture is stirred for 60 min, then the batch is allowed to warm to -20 ° ^C. and the orange-colored suspension is carefully added to an ice-cold mixture of 500 ml of 1 M sodium hydroxide solution and 50 ml of sodium hydrogen sulfite solution. The pH is adjusted to 7 with 32% strength by weight sodium hydroxide solution, the aqueous phase is separated off and extracted three times with pentane. The combined organic phases are dried over sodium sulfate. The solvent is removed in vacuo and the residue is filtered over silica gel using dichloromethane / n-heptane 1: 1. The crude product is recrystallized from dichloromethane / n-hexane Siert. Pale yellow crystals of the trans, trans product 14 with a melting point of 164 ° C. are obtained. Yield: 57.2%

5: The nitro compound 14 is hydrogenated to the diamine 15 in the presence of Lindlar catalyst in THF. The solution obtained after the hydrogenation is filtered through silica gel. It is washed with MTB ether and the solvent is removed in vacuo. The residue is recrystallized from acetic acid. Yield: 36.3%

13

6: 17.383 mmol 13 are suspended in 100 ml dichloromethane and 34.774 mmol trifluoromethanesulfonic acid are added dropwise with ice cooling. The clear yellow solution is then left to stir at room temperature for 1 h. The mixture is then cooled to -70 ° C. and a solution of 52.149 mmol of 5-hydroxyphthalic anhydride and 62.576 mmol of triethylamine in 40 ml of dichloromethane is added dropwise. After 1 h, 151.976 mmol of triethylamine trishydrofluoride and then a suspension of 173.833 mmol of DBH in 70 ml of dichloromethane are added in portions within 30 minutes. After stirring for 60 min, the mixture is allowed to warm to -20 ° C. and the orange suspension is carefully added to an ice-cold mixture of 500 ml of 1 M sodium hydroxide solution and 50 ml Sodium bisulfite solution. The pH is adjusted to 7 with 32% strength by weight sodium hydroxide solution, the aqueous phase is separated off and extracted three times with pentane. The combined organic phases are dried over sodium sulfate. The solvent is removed in vacuo and the residue is first filtered through silica gel with dichloromethane / n-heptane 1: 1 and then chromatographed (Rf = 0.11). A pale yellow oil is obtained. Colorless, cotton-like needles crystallize from toluene / n-pentane. Yield: 60.5%.

Production of the polyimides

Example 7

The anhydride 5 and the diamine 4 are dissolved in NMP and stirred under nitrogen for 22 h at room temperature. The mixture is then heated to 100 ° C. for 6 h and the polymer is precipitated by adding 50% aqueous ethanol. The crude product is reprecipitated once from 20 ml and once from 30 ml of NMP by adding 50% aqueous ethanol.

Claims

claims

Chain-shaped polycyclic bisanhydrides, containing 2 to 12 chain cycles, selected from 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1, 4-cyclohexylene, bicyclopentylene, bicyclooctylene, cubylene can be substituted one or more times with halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy, the cycles being bridged by groups selected from a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NH-, - (CH ₂ ) ι-ιo-, - (CF2) ι-ιo-, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, - C (CF ₃ ) ₂ -, -C≡C-, -CH = CH-, -CF = CH-, -CH = CF -, -CF = CF-,

are linked to the proviso that at least one bridging group is -CF ₂ O- or -OCF ₂ -, the polycycles at both chain ends being selected by different groups

are scheduled.

Chain-shaped polycyclic bisanhydrides according to claim 1 with the general formula (I) ^{E z1} - ^A Ü ^{z2 ~ B} " ^z3 - C ^ ⁴ -D] ^ Z ⁵ -F

(I)

wherein

A, B, C and D may be the same or different and 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene and 1,4-cyclohexylene, with halogen, cyano, alkyl , Fluoroalkyl, alkoxy and / or fluoroalkoxy can be substituted one or more times,

E and F can be the same or different and

mean,

Z \ Z ² , Z ³ , Z ⁴ and Z ^{5 may be the} same or different and a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NH-, - (CH ₂ ) ι.ιo-, - (CF ₂ ) ι. ₁₀ -, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -C≡C- , CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-,

w, x, y and z are independently 0 or 1.

3. Chain-shaped polycyclic bisanhydrides according to claim 2, selected from the group consisting of compounds of the general formulas (II) - (V)

wherein

A, B are as defined in claim 2,

Z ¹ Z ^"1 z ²

Z ^'2 , Z ^{3 have} the meaning of Z ¹ - Z ⁵ as defined in claim 2 with the proviso that Z ^"1 = -OCF ₂ - if Z ¹ = -CF ₂ O- and vice versa, Z ^{" 2} = - OCF ₂ - if Z ² = -CF ₂ O- and vice versa, Z ^"1 = -CH = CF- if Z ¹ = -CF = CH- and vice versa, Z ^{" 2} = -CH = CF- if Z ² = - CF = CH- and vice versa, r ¹ = Z ¹ and Z- ² = Z ² in all other cases.

Chain-shaped polycyclic bisanhydrides according to Claim 2 or 3 of the formulas or general formulas (Ha) - (VI)

wherein Z ² , Z are as defined in claim 3.

5. Polyimides with -CF ₂ O groups, obtainable by polycondensation of chain polycyelic bisanhydrides, as defined in one of claims 1-4, and optionally further polycyelic bisanhydrides, with diamines.

6. Polyimides according to claim 5, wherein the diamines are chain polycyclic diamines which are terminated at the chain ends by -NH ₂ .

7. polyimides according to claim 6, wherein the diamines 2 to 12 chain cycles selected from 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1, 4-cyclohexylene, bicyclopentylene, Bicyclooctylene and cubylene, which can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy, and wherein the cycles by bridging groups selected from a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, - SO ₂ -, -CO-, -NH-, - (CH ₂ ) ι _-10 -, - (CF2) ι.ιo-, -CH (CH ₃ ) - , -CH (CCI ₃ ) -, - CH (CF ₃ ) -, -C (CH ₃ ) ₂ -,

-C (CF ₃ ) ₂ -, -C≡C-, -CH = CH-, CF = CH-, -CH = CF-, -CF = CF-,

are linked.

8. Polyimides according to claim 7, wherein the diamines have the general formula (XXXV)

(XXXV)

wherein

Z ¹ Z ² Z ³ Z ⁴ and Z ^{5 can be the} same or different and a single bond, -CF ₂ O-, -OCF ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NH -, - (CH2) ι.ιo-, - (CF ₂ ) _1-10 -, -CH (CH ₃ ) -, -CH (CCI ₃ ) -, -CH (CF ₃ ) -, -C (CH ₃ ) ₂ -, C (CF ₃ ) ₂ -, -C≡C-, -CH = CH-, -CF = CH-, CH = CF-, -CF = CF-,

mean,

-NH _; is independently bound in the 3- or 4-position, and

w, x, y and z are independently 0 or 1.

Polyimides according to claim 8, wherein the diamines are selected from compounds of the general formulas (XXXVI) - (XL)

(XXXVI I)

(XXXVIII)

χιχ)

wherein

A, B are as defined in claim 8,

z ¹ , r ¹ , z ² ,

Z ^"2 , Z ^{3 have} the meaning of Z ¹ - Z ⁵ as defined in claim 8 with the proviso that

Z ^"1 = -OCF ₂ - if Z ¹ = -CF ₂ O- and vice versa, Z ^{" 2} = -OCF2- if Z ² = -CF ₂ O- and vice versa, Z ^"1 = -CH = CF- if Z ¹ = -CF = CH- and vice versa, Z ^"2 = -CH = CF- if Z ² = -CF = CH- and vice versa, Z ^{" 1} = Z ¹ and Z ^'2 = Z ² in all other cases,

-NH ₂ on both chain ends in 3 or in

4-position is bound.

10. Polyimides obtainable by polycondensation of chain polycyclic bisanhydrides, as defined in one of claims 1-4, and / or further polycyelic bisanhydrides, with diamines, as defined in one of claims 7-9, with the additional Provided that at least one bridging group in the diamines is -CF ₂ O- or -OCF ₂ -, and optionally further diamines.

11. Use of polyimides, as defined in one of claims 5 to 10, as an orientation material in liquid crystal displays or organic light-emitting diodes (OLEDs).