HK1206005B - Photocrosslinkable materials - Google Patents

Description

Photocrosslinkable materials

This application is a divisional application of Chinese patent application 200680048708.8. The present invention relates to diamine compounds represented by general formula (I), as well as oligomers, polymers, and copolymers of polyamic acid, polyamic acid ester, or polyimide (and any mixtures thereof) obtained by reacting the diamine compounds represented by general formula (I) and, optionally, one or more additional diamines, with one or more tetracarboxylic anhydrides, and to the use of these diamine compounds, oligomers, polymers, and copolymers for preparing liquid crystal alignment layers and for constructing unstructured and structured optical elements and multilayer systems.

Liquid crystal displays (LCDs) are becoming increasingly important in advanced visual devices. LCDs offer advantageous characteristics in terms of image quality (high brightness, high resolution, color and grayscale capabilities), power consumption, and size and weight (for flat panel displays). Commercial LCDs are widely used, for example, in automotive and telecommunications equipment, as well as monitors for notebooks, desktop computers, televisions, and the like. Currently, demand for LCDs in television applications is rapidly increasing. Recently developed LCD modes offer great potential for achieving fast response times, wide viewing angles, and high brightness. Among other recently developed LCD modes, the MVA (Multi-Domain Vertical Alignment) mode appears to be the most promising for modern television applications.

In the MVA mode, liquid crystal molecules are typically aligned nearly vertically relative to the substrate surface. By using protrusions (or other alignment features) on the substrate surface, the liquid crystal molecules are locally pretilted in more than one direction within a single cell, resulting in domains that can be switched in different directions. This multi-domain configuration exhibits very good display performance, with wide viewing angles of up to 160° in any direction, short response times (less than 20ms), high contrast ratios (up to 700:1), and high brightness.

However, by using only protrusions, it is difficult to clearly define the domain space within a single pixel. Therefore, the MVA mode requires additional manufacturing steps to ensure the shape effect and electric field effect on the upper and lower substrates; therefore, it always leads to complicated manufacturing steps.

To circumvent this technical challenge, the availability of an alignment film would be desirable, which directly results in a predetermined alignment direction within each pixel domain and has a well-controlled off-axis angle relative to the substrate perpendicular axis.

Methods for preparing alignment layers for liquid crystal materials are well known to those skilled in the art. However, commonly used uniaxially rubbed polymer alignment layers, such as polyimide, suffer from a number of drawbacks, including the formation and deposition of dust during the rubbing process and the attendant partial destruction of thin-film transistors. Scratching caused by brushing is another problem with this technology, particularly pronounced when pixels are approximately 10 microns or even smaller, as in microdisplay applications. Due to the high optical magnification required to visualize the displayed information, scratches become readily visible and contribute to a decrease in contrast levels. Furthermore, rubbing processes do not permit the production of structured layers.

The production process for obtaining an alignment layer in which the orientation direction is induced by irradiation with polarized light does not face the problems inherent in rubbing processes. Using radiation techniques, it is also possible to produce regions with different orientations and thus structure the alignment layer, as described, for example, in Jpn. J. Appl. Phys., 31 (1992), 2155-64 (Schadt et al.).

Using linear photopolymerizable alignment (LPP) technology, four-domain vertically aligned nematic (VAN) LCDs have been realized for several years (K. Schmitt, M. Schadt; Proceedings of EuroDisplay 99, September 6-9, 1999). Four-domain VAN-LCDs have excellent off-state angular brightness performance.

In addition to meeting current display performance requirements for modern TV applications, the use of suitable LPP materials is also considered necessary to achieve specific optical and electro-optical properties, such as compatibility with TFTs (thin-film transistors). Other important material characteristics must also be considered, namely those decisive parameters that are directly related to and dependent on the material's molecular properties.

These features are mainly:

●High voltage holding ratio (VHR), i.e. VHR>90% (measured at 80°C)

High stability of pre-tilt angle induced by light and heat

● Low alignment energy distribution (short irradiation time and/or low irradiation energy)

In thin-film transistor LCDs, a certain amount of charge is applied to the electrodes of a pixel for a very short period of time and must subsequently be maintained against the resistance of the liquid crystal. The ability to maintain this charge, and therefore the voltage drop across the liquid crystal, is quantified by the so-called "voltage holding ratio" (VHR). This is the ratio of the RMS voltage (root mean square voltage) across the pixel during one frame period to the initial value of the applied voltage.

Photoreactive materials for alignment layers with improved voltage holding ratio (VHR) are described in WO-A-99/49360, US 6,066,696, US 6,027,772, WO-A-99/15576 and WO-A-99/51662. In WO-A-99/49360, US 6,066,696 and US 6,027,772, polymer blends are described, which comprise a photoreactive polymer and a polyimide.

WO-A-99/15576 and WO-A-99/51662 describe polyimides having photoreactive cinnamate groups incorporated into their side chains. WO-A-99/15576, for example, discloses photoactive polymers containing specific photocrosslinkable groups as side chains, a typical monomer unit of which is 6-{2-methoxy-4-[(1E)-3-methoxy-3-oxoprop-1-enyl]phenoxy}hexyl 3,5-diaminobenzoate.

The references cited above generally suggest that, in order to achieve the aforementioned important parameters, molecular structures that incorporate, first, a polyamide/polyimide backbone (i.e., imparting molecular polarity) and, second, side chains with introduced photoreactive groups, such as cinnamic acid residues, are suitable for the general concept of planar alignment (requiring only a slight pretilt angle, such as used in TN (twisted nematic) devices). However, these types of molecular structures, developed primarily for TN applications, are not directly applicable to MVA applications.

Therefore, the present invention relates to diamine compounds of the general formula (I):

wherein A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring containing 5 or 6 atoms, two adjacent monocyclic rings containing 5 or 6 atoms, a bicyclic ring system containing 8, 9 or 10 atoms or a tricyclic ring system containing 13 or 14 atoms; and

wherein the following compound residue of general formula (I), namely compound residue (Ia)

represents a linear or branched C ₁ -C ₁₆ fluoroalkyl group, wherein

F is fluorine, and

x ₁ is an integer of 1-15, preferably 1-10; more preferably 1, 2, 3, 4, 5, 6, 7, 8 or 9, most preferably 3, 4, 5 or 7;

B represents a straight-chain or branched C ₁ -C ₁₆ alkyl group which, apart from its fluorine group, is unsubstituted or substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may independently be replaced by a linking group;

D represents an unsubstituted or substituted aliphatic, aromatic and/or alicyclic diamine radical containing 1 to 40 carbon atoms,

Preferably, D represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine containing 1 to 40 carbon atoms, wherein the diamine group comprises an aliphatic group, which may contain one or more heteroatoms and/or bridging groups; and/or an aromatic group; and/or an alicyclic group;

E represents an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N(C ₁ -C ₆ alkyl)-, -CR ² R ³ , wherein R ² and R ³ are independently hydrogen or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl group, wherein one or more -CH ₂ - groups may be replaced independently by a linking group, and with the proviso that at least one of R ² and R ³ is not hydrogen;

S ¹ and S ² each independently represent a spacer unit;

X and Y each independently represent hydrogen, fluorine, chlorine, cyano, unsubstituted or fluorine-substituted C ₁ -C ₁₂ alkyl, wherein one or more -CH ₂ - groups may be replaced by a linking group;

n, n1 each independently represent 1, 2, 3 or 4, preferably n1 is 1 and n is 1 or 2; provided that if n is 2, 3 or 4, each A, B, x ₁ , E, S ¹ , S ² , X, Y is the same or different; if n1 is 2, 3 or 4, each B, x ₁ is the same or different;

Preferably, wherein, if n>1, compound (I) has several side chains [wherein the side chains have the meaning of structure (I) without the group D], which are attached to the residue D at one atomic position within the group D, for example two or three side chains are attached to a single carbon atom within the group D, or they may be attached to the group D at different atomic positions within the group D, for example at adjacent atomic positions within the group D, or/and they may be attached remotely.

In a preferred embodiment, the present invention relates to diamine compounds of the general formula (I):

wherein A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring containing 5 or 6 atoms, two adjacent monocyclic rings containing 5 or 6 atoms, a bicyclic ring system containing 8, 9 or 10 atoms or a tricyclic ring system containing 13 or 14 atoms;

F is fluorine, and

_x1 is an integer from 1 to 15,

B represents a linear or branched C ₁ -C ₁₆ alkyl group, which is unsubstituted or substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine or fluorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linking group;

D represents an unsubstituted or substituted aliphatic, aromatic and/or alicyclic diamine group containing 1 to 40 carbon atoms,

E represents an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N(C ₁ -C ₆ alkyl)-, -CR ² R ³ , wherein R ² and R ³ are independently hydrogen or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl group, wherein one or more -CH ₂ - groups may be replaced by a linking group, and with the proviso that at least one of R ² and R ³ is not hydrogen;

S ¹ and S ² each independently represent a spacer unit;

X and Y each independently represent hydrogen, fluorine, chlorine, cyano, unsubstituted or fluorine-substituted C ₁ -C ₁₂ alkyl, wherein one or more -CH ₂ - groups may be replaced by a linking group;

n is 1, 2, 3, or 4,

Provided that if n is 2, 3 or 4, each A, B, x ₁ , D, E, S ¹ , S ² , X, Y may be the same or different.

The term "linker" as used in the context of the present invention is preferably selected from -O-, -CO, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ -, -CH=CH-, -C≡C-, -O-CO-O- and -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms of the linking group are not directly connected to each other.

The term "spacer unit" as used in the context of the present invention is preferably a single bond, cyclic, linear or branched, substituted or unsubstituted _C1 - _C24- alkylene, wherein one or more, preferably non-adjacent _-CH2- groups may be replaced independently of one another by the above-mentioned linking groups and/or non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups connected via a bridging group.

More preferably, the spacer unit is a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ -alkylene group, wherein one or more, preferably non-adjacent -CH ₂ - groups can be replaced independently of one another by a linker and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via a bridging group.

The bridging group used in the context of the present invention is preferably selected from -CH(OH)-, -CO-, _-CH2 (CO)-, -SO-, _-CH2 (SO)-, _-SO2- , _-CH2 ( _SO2 )-, -COO-, -OCO-, _-COCF2- , -CF2CO, _-S- CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -O-CO-O, _-CH2-CH2- , _-OCH2- , _-CH2O- , -CH=CH-, _-C≡C- , -CH=CH-COO-, -OCO-CH=CH-, -CH=N-, -C( _CH3 )=N-, -N=N- or a single bond; or cyclic, linear or branched, substituted or unsubstituted _C1 - _C24- alkylene, where one or more _-CH2- groups may independently of one another be replaced by a linking group as mentioned above.

Alkyl, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkenyl, alkoxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkenyl, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylallyloxy and alkylene as used in the context of the present invention represent together with their alkyl radicals their alkylene radicals, respectively cyclic, linear or branched, substituted or unsubstituted alkyl, alkylene, where one or more, preferably non-adjacent _-CH2- groups may be replaced by a linking group.

Furthermore, the alkyl residue is, for example, a C ₁ -C ₄₀ alkyl group, particularly a C ₁ -C ₃₀ alkyl group, preferably a C ₁ -C ₂₀ alkyl group, more preferably a C ₁ -C ₁₆ alkyl group, most preferably a C ₁ -C ₁₀ alkyl group, and especially most preferably a C ₁ -C ₆ alkyl group. Thus, the alkylene group is, for example, a C ₁ -C ₄₀ alkylene group, particularly a C ₁ -C ₃₀ alkylene group, preferably a C ₁ -C ₂₀ alkylene group, more preferably a C ₁ -C ₁₆ alkylene group, most preferably a C ₁ -C ₁₀ alkylene group, and especially most preferably a C ₁ -C ₆ alkylene group.

In the context of the present invention, the definition of alkyl given below applies analogously to alkylene.

C ₁ -C ₆ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl or hexyl.

Examples of C ₁ -C ₁₀ alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

C ₁ -C ₁₆ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.

Examples of C ₁ -C ₂₀ alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.

Examples of C ₁ -C ₂₄ alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.

C ₁ -C ₃₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl.

C ₁ -C ₄₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl or tetracontyl.

The C ₁ -C ₂₀ acryloyloxyalkylene group, preferably the C ₁ -C ₁₀ acryloyloxyalkylene group, the C ₁ -C ₆ acryloyloxyalkylene group is, for example, an acryloyloxymethylene group, an acryloyloxyethylene group, an acryloyloxypropylene group, an acryloyloxyisopropylene group, an acryloyloxybutylene group, an acryloyloxy-sec-butylene group, an acryloyloxypentylene group, an acryloyloxyhexylene group, an acryloyloxyheptylene group, an acryloyloxyoctylene group, an acryloyloxynonylene group, an acryloyloxydecylene group, an acryloyloxyundecylene group, an acryloyloxydodecylene group, an acryloyloxytridecylene group, an acryloyloxytetradecylene group, an acryloyloxypentadecylene group, an acryloyloxyhexadecylene group, an acryloyloxyheptadecylene group, an acryloyloxyoctadecylene group, an acryloyloxynonadecylene group, and an acryloyloxyeicosylene group.

The C ₁ -C ₂₀ methacryloxyalkylene group, preferably the C ₁ -C ₁₀ methacryloxyalkylene group, the C ₁ -C ₆ methacryloxyalkylene group is, for example, methacryloxymethylene, methacryloxyethylene, methacryloxypropylene, methacryloxyisopropylene, methacryloxybutylene, methacryloxy-sec-butylene, methacryloxypentylene, methacryloxyhexylene, methacryloxyheptylene, methacryloxyoctylene, methacryloxynonylene, methacryloxydecylene, methacryloxyundecylene, methacryloxydodecylene, methacryloxytridecylene, methacryloxytetradecylene, methacryloxypentadecylene, methacryloxyhexadecylene, methacryloxyheptadecylene, methacryloxyoctadecylene, methacryloxynonadecylene, methacryloxyeicosylene.

The C ₁ -C ₂₀ acryloyloxyalkoxy group, preferably the C ₁ -C ₁₀ acryloyloxyalkoxy group, the C ₁ -C ₆ acryloyloxyalkoxy group is, for example, an acryloyloxymethoxy group, an acryloyloxyethoxy group, an acryloyloxypropoxy group, an acryloyloxyisopropoxy group, an acryloyloxybutoxy group, an acryloyloxy-sec-butoxy group, an acryloyloxypentyloxy group, an acryloyloxyhexyloxy group, an acryloyloxyheptyloxy group, an acryloyloxyoctyloxy group, an acryloyloxynonyloxy group, an acryloyloxydecyloxy group, an acryloyloxyundecyloxy group, an acryloyloxydodecyloxy group, an acryloyloxytridecyloxy group.

The C ₁ -C ₂₀ methacryloxyalkoxy group, preferably the C ₁ -C ₁₀ methacryloxyalkoxy group, the C ₁ -C ₆ methacryloxyalkoxy group is, for example, a methacryloxymethoxy group, a methacryloxyethoxy group, a methacryloxypropoxy group, a methacryloxyisopropoxy group, a methacryloxybutoxy group, a methacryloxysec-butoxy group, a methacryloxypentyloxy group, a methacryloxyhexyloxy group, a methacryloxyheptyloxy group, a methacryloxyoctyloxy group, a methacryloxynonyloxy group, a methacryloxydecyloxy group, a methacryloxyundecyloxy group, a methacryloxydodecyloxy group, a methacryloxytridecyloxy group.

The aliphatic group is, for example, a saturated or unsaturated, mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- or decavalent alkyl group, an alkylene group, an alkoxy group, an alkylcarbonyloxy group, an acryloyloxy group, an alkylacryloyl group, an alkylmethacryloyl group, an alkyl(ene)acryloyl(ene), an alkyl(ene)methacryloyl(ene), an alkoxycarbonyloxy group, an alkoxycarbonyloxymethacryloyloxy group, an alkylvinyl group, an alkylvinyloxy group or an alkylallyloxy group, which may contain one or more heteroatoms and/or a bridging group.

The alicyclic group is preferably a non-aromatic group or unit. Preferably, the alicyclic group is a non-aromatic carbocyclic or heterocyclic group and represents a ring system having 3 to 30 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decahydronaphthalene, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroidal backbone such as cholesterol.

The term "aromatic" as used in the present invention preferably refers to unsubstituted or substituted carbocyclic and heterocyclic groups containing 5, 6, 10 or 14 ring atoms, such as furan, benzene or phenylene, pyridine, pyrimidine, naphthalene, which can form ring combinations, such as biphenylene or terphenylene, which are continuous or interrupted by at least one heteroatom and/or at least one bridging group; or fused polycyclic ring systems, such as phenanthrene, tetralin. Preferably, the aromatic group is benzene, phenylene, biphenylene or terphenylene. More preferred aromatic groups are benzene, phenylene and biphenylene.

The carbocyclic or heterocyclic aromatic group preferably contains 5, 6, 10 or 14 ring atoms, for example furan, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, most preferably phenylene.

Carbocyclic or heterocyclic aromatic groups are, for example, unsubstituted or mono- or polysubstituted. Preferred substituents for carbocyclic or heterocyclic aromatic groups are at least one halogen, hydroxyl, polar group, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, vinyl, vinyloxy, and/or allyloxy, wherein the alkyl residue preferably contains 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Preferred polar groups are nitro, cyano, or carboxyl groups, and/or cyclic, linear, or branched _C1 - _C30 alkyl groups, which are unsubstituted, mono- or polysubstituted. Preferred substituents for _C1 - _C30 alkyl groups are methyl, fluorine, and/or chlorine, wherein one or more, preferably non-adjacent, _-CH2- groups may be replaced independently by a linker. Preferably, the linker is selected from -O-, -CO-, -COO-, and/or -OCO-.

Monocyclic rings containing 5 or 6 atoms are, for example, furan, benzene, preferably phenylene, pyridine, pyrimidine.

Bicyclic ring systems containing 8, 9 or 10 atoms are, for example, naphthalene, biphenylene or tetralin.

A tricyclic ring system containing 13 or 14 atoms is, for example, phenanthrene.

The term "phenylene" as used in the context of the present invention preferably refers to optionally substituted 1,2-, 1,3- or 1,4-phenylene. Preferably, the phenylene group is a 1,3- or 1,4-phenylene group. A 1,4-phenylene group is particularly preferred.

The term "halogen" refers to a chlorine, fluorine, bromine or iodine substituent, preferably a chlorine or fluorine substituent.

The term "polar group" as used in the context of the present invention primarily denotes groups such as nitro, cyano or carboxyl.

The term "heteroatom" as used in the context of the present invention primarily denotes oxygen, sulfur and nitrogen, preferably oxygen and nitrogen, in the latter case preferably in the form -NH-.

The term "optionally substituted" as used in the context of the present invention primarily refers to substitution with lower alkyl, such as C ₁ -C ₆ alkyl, lower alkoxy, such as C ₁ -C ₆ alkoxy, hydroxy, halogen or polar groups as defined above.

The term "diamine" or "diamine compound" is understood to mean a chemical structure having at least two amino groups, i.e., also three or more amino groups. The at least two amino groups are preferably capable of reacting, for example, with an acid anhydride, as described in more detail below.

The term "dinitro" or "dinitro compound" is understood to mean a chemical structure having at least two nitro groups, i.e., also three or more nitro groups, wherein the dinitro group is a precursor compound of a "diamino compound". The dinitro compound is usually converted into the diamino compound by reduction methods known in the art.

With respect to linear or branched, alkylene, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyolefin, alkoxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyolefin, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, alkylallyloxy and alkylene groups, it is reiterated that some or several -CH2- groups may be replaced, for example, by _heteroatoms , as well as other groups, preferably bridging groups. In such cases, it is generally preferred that these replacement groups are not directly linked to one another. Alternatively, it is preferred that the heteroatoms, in particular the oxygen atoms, are not directly linked to one another.

Preferably, A is unsubstituted or substituted phenanthrenyl, naphthylene, biphenylene or phenylene, wherein preferred substituents are halogen atoms, hydroxyl groups and/or polar groups, wherein the polar groups are preferably nitro, cyano, carboxyl groups; and/or acryloyloxy, alkylacryloyl, alkylmethacryloyl, alkyl(ene)acryloyl, alkyl(ene)methacryloyl, acrylenacryl, methacrylenalkyl, methacryloyloxy, vinyl, vinyloxy, allyl, allyloxy and/or cyclic, linear or branched alkyl groups, which are unsubstituted, mono- or polysubstituted by fluorine and/or chlorine, and have 1 to 20 carbon atoms, wherein one or more, preferably non-adjacent, _-CH2- groups may be independently replaced by a linker and/or an aromatic or alicyclic group, preferably the linker being selected from -O-, -CO-, -CO-O-, -O-CO-.

More preferably, A is a substituted or unsubstituted naphthylene, biphenylene or phenylene group, wherein preferred substituents are halogen atoms, hydroxyl groups and/or acryloyloxy groups, alkylacryloyl groups, alkylmethacryloyl groups, acryloylalkenylacryloyl groups, methacryloylalkenylalkyl groups, methacryloyloxy groups, linear or branched alkyl groups, alkoxy groups, alkylcarbonyloxy groups and/or alkoxycarbonyl groups, wherein the alkyl residue has 1 to 20 carbon atoms.

Most preferably, A is a substituted or unsubstituted phenylene group, preferably a 1,4-phenylene group, wherein preferred substituents are halogen atoms, and/or an acryloyloxy group or a methacryloyloxy group, and/or an alkoxy group, an alkylacryloyl group, an alkylmethacryloyl group, an acryloylalkenylacryloyl group, a methacryloylalkenylalkyl group, an alkylcarbonyloxy group and/or an alkoxycarbonyl group, wherein the alkyl residue has 1 to 10 carbon atoms.

A preferred embodiment of the present invention relates to a diamine compound of the above general formula (I), wherein the following compound residue (Ia)

represents a linear or branched C ₁ -C ₁₆ fluoroalkyl group having a terminal unit selected from -CF ₂ H and -CF ₃ , preferably selected from -CF ₂ H or -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₂ CHF ₂ , -(CF ₂ ) ₃ CHF ₂ , -(CF ₂ ) ₃ CF ₃ , -CF(CF ₃ ) ₂ and -CF ₂ (CHF)CF ₃ .

Preferably, B is a straight-chain or branched C ₁ -C ₁₂ alkyl group, in which one or more, preferably non-adjacent -CH ₂ - groups may be replaced independently of one another by a group selected from the group consisting of: -O-, -CO, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ -, -CH=CH-, -C≡C-, -O-CO-O-, and -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, aromatic and alicyclic groups; wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms are not directly bonded to each other.

More preferably, B is a straight-chain or branched C ₁ -C ₁₂ alkyl group, wherein one or more, preferably non-adjacent -CH ₂ - groups may be replaced by a group selected from: -O-, -CO, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - or -CH=CH- wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms are not directly bonded to each other.

Most preferably, B is a straight-chain or branched C ₁ -C ₈ alkyl group, wherein one or more, preferably non-adjacent -CH ₂ - groups may be replaced by a group selected from: -O-, -CO, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - or -CH=CH- wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms are not directly bonded to each other.

Most preferably, B is a straight-chain or branched C ₁ -C ₈ alkyl group, wherein one or more, preferably non-adjacent -CH ₂ - groups may be replaced by a group selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, and -CH=CH-, with the proviso that the oxygen atoms are not directly attached to each other.

Preferably, the residue of compound (Ia) is: trifluoromethyl; 2,2,2-trifluoroethyl; difluoromethyl; pentafluoroethyl; 2,2-tetrafluoroethyl; 3,2-tetrafluoroethyl; 3,3,3-trifluoropropyl; 2,2,3,3-tetrafluoropropyl; 2,2,3,3,3-pentafluoropropyl; hexafluoropropyl; heptafluoropropyl; 4,4,4-trifluorobutyl; tetrafluorobutyl; 3,3,4,4,4-pentafluorobutyl; hexafluorobutyl; 2,2,3,3,4,4,4-heptafluorobutyl; 5,5,5-trifluoropentyl; tetrafluoropentyl; 4,4,5,5,5-pentafluoropentyl; hexafluoropentyl; 3,3,4,4,5,5,5-heptafluoropentyl; 6,6,6-trifluorohexyl; tetrafluorohexyl; 5,5,6,6,6-pentafluorohexyl; hexafluorohexyl; 4,4,5,5,6,6,6-heptafluorohexyl; nonafluorohexyl; 1-trifluoro-1,2,2,2-tetrafluoroethoxy, 2-trifluoro-2,3,3,3-tetrafluoropropoxy, 3-trifluoro-3,4,4,4-tetrafluorobutoxy, 4-trifluoro-4,5,5,5-tetrafluoropentyloxy, 5-trifluoro-5,6,6,6-tetrafluorohexyloxy, 6-trifluoro-6,7,7,7-tetrafluoroheptyloxy, 7-trifluoro-7,8,8,8-tetrafluorononyloxy; fluoroalkoxy derivatives, for example, trifluoromethoxy; 2,2,2-trifluoroethoxy; difluoromethoxy; pentafluoroethoxy; 1,1,2,2-tetrafluoroethoxy; 2,2,2, 1-Tetrafluoroethoxy; 3,3,3-trifluoropropoxy; 2,2,3,3-tetrafluoropropoxy; 2,2,3,3,3-pentafluoropropoxy; hexafluoropropoxy; heptafluoropropoxy; 4,4,4-trifluorobutoxy; tetrafluorobutoxy; 3,3,4,4,4-pentafluorobutoxy; 2,2,3,3,4,4-hexafluorobutoxy; 2,2,3,3,4,4,4-heptafluorobutoxy; 5,5,5-trifluoropentyloxy; tetrafluoropentyloxy; 4,4,5,5,5-pentafluoropentyloxy; hexafluoropentyloxy; 3,3,4,4,5,5,5-heptafluoropentyloxy; 6,6,6-trifluorohexyloxy; tetrafluorohexyloxy; 5,5,6,6,6-pentafluorohexyloxy; hexafluorohexyloxy 4,4,5,5,6,6,6-heptafluorohexyloxy; nonafluorohexyloxy; trifluoromethylene carbamate; 2,2,2-trifluoroethylene carbamate; difluoromethylene carbamate; pentafluoroethylene carbamate; 2,2-tetrafluoroethylene carbamate; 3,2-tetrafluoroethylene carbamate; 3,3,3-trifluoropropylene carbamate; 2,2,3,3-tetrafluoropropylene carbamate; 2,2,3,3,3-pentafluoropropylene carbamate; hexafluoropropylene carbamate; heptafluoropropylene carbamate; 4,4,4-trifluorobutylene carbamate; tetrafluorobutylene carbamate; 3,3,4,4,4-pentafluorobutylene carbamate; hexafluorobutylene carbamate esters; 2,2,3,3,4,4,4-heptafluorobutylenecarbamate; 5,5,5-trifluoropentylenecarbamate; tetrafluoropentylenecarbamate; 4,4,5,5,5-pentafluoropentylenecarbamate; hexafluoropentylenecarbamate; 3,3,4,4,5,5,5-heptafluoropentylenecarbamate; 6,6,6-trifluorohexylenecarbamate; tetrafluorohexylenecarbamate; 5,5,6,6,6-pentafluorohexylenecarbamate; hexafluorohexylenecarbamate; 4,4,5,5,6,6,6-heptafluorohexylenecarbamate; nonafluorohexylenecarbamate; fluoroalkanoyloxy derivatives, for example, trifluoroacetyloxy; 2,2,2-trifluoroacetyloxy; pentafluoroacetyloxy; 1,1,2,2- Tetrafluoroacetyloxy; 2,2,2,1-tetrafluoroacetyloxy; 3,3,3-trifluoropropionyloxy; tetrafluoropropionyloxy; 2,2,3,3,3-pentafluoropropionyloxy; hexafluoropropionyloxy; 1,1,2,2,3,3, 3-heptafluoropropionyloxy; 4,4,4-trifluorobutyryloxy; tetrafluorobutyryloxy; 3,3,4,4,4-pentafluorobutyryloxy; hexafluorobutyryloxy; 2,2,3,3,4,4,4-heptafluorobutyryloxy; 5,5,5-trifluoropentanoyloxy; tetrafluoropentanoyloxy; 4,4,5,5,5-pentafluoropentanoyloxy; hexafluoropentanoyloxy; 3,3,4,4,5,5,5-heptafluoropentanoyloxy; 6,6,6-trifluorohexanoyloxy; tetrafluorohexanoyloxy acyloxy; 5,5,6,6,6-pentafluorohexanoyloxy; hexafluorohexanoyloxy; 4,4,5,5,6,6,6-heptafluorohexanoyloxy; trifluoroacetyl; nonafluorohexanoyloxy; 4,4,4-trifluorobut-2-enyl; 5,5,5-trifluoropent-1-enyl; 6,6,6-trifluorohex-1-enyl; 7,7,7-trifluorohept-1-enyl; trifluoroacetylaminomethoxy; trifluoroacetylaminoethoxy; trifluoroacetylaminopropoxy; trifluoroacetylaminobutoxy; 2-fluoroethyl; 3-fluoropropyl; 4-fluorobutyl; 5-fluoropentyl; 6-fluorohexyl; 2-fluoroethoxy; 3-fluoropropoxy; 4-fluorobutoxy; 5-fluoropentyloxy; 6-fluorohexyloxy; 4-fluorobut-1-enyl; 5-fluoro Fluoropent-1-enyl; 6-fluorohex-1-enyl; 7-fluorohept-1-enyl; 4,4,4-trifluoro-3-(trifluoromethyl)butoxy; 4,5,5-trifluoropent-4-enyloxy; 4,5,5-trifluoropentan-4-yloxy; 5,6,6-trifluorohex-5-enyloxy or 5,6,6-trifluoropentan-5-yloxy.

Especially preferred are fluoroalkoxy groups, preferably trifluoro- and pentafluorofluoroalkoxy derivatives, particularly preferred are 5,5,5-trifluoropentoxy and 4,4,5,5,5-pentafluoropentoxy.

D is preferably selected from the general formula (III):

H(R ⁵ )N-(Sp ¹ ) _k1 -(X ¹ ) _t1 -(Z ³ -C ³ ) _a3 -(Z ⁴ -C ⁴ ) _a4 -(X ² ) _t2 -(Sp ² ) _k2 -N(R ⁶ )H (III)

in:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

Sp ¹ and Sp ² each independently represent an unsubstituted or substituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be replaced by a linking group independently of each other, and

k ¹ , k ² are each independently an integer having a value of 0 or 1; and

X ¹ and X ² each independently represent a linking spacer, preferably selected from -O-, -S-, -NH-, N(CH ₃ )-, -CH(OH)-, -CO-, -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH＝CH- or -C≡C-, or a single bond;

t ¹ , t ² are each independently an integer having a value of 0 or 1; and

C ³ and C ⁴ each independently represent a non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group, which may have a side chain T, and

Z ³ represents a bridging group; and

Z ⁴ represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups; and/or heteroatoms and/or the above-mentioned bridging groups;

Preferably, Z ⁴ has one of the meanings of Z ³ or represents unsubstituted or substituted straight-chain or branched C ₁ -C ₁₄ alkylene, in which one or more, preferably non-adjacent -CH ₂ - groups may be replaced by an oxygen atom and/or one or more carbon-carbon single bonds may be replaced by a carbon-carbon double or carbon-carbon triple bond; and

a3 and a4 are independently integers from 0 to 3, satisfying a3+a4≤4; and

wherein D is connected at least once to at least one group S ¹ in the general formula (I) via a group Sp ¹ and/or a group Sp ² ; and/or is connected via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of C ³ and/or a group C ⁴ , and/or is connected via at least one side chain T of a group C ⁴ and/or a group C ³ ; and/or is connected via a group Z ⁴ ; and at least one of k ¹ , k ² , a ³ and a ⁴ is not equal to zero; wherein the linking group and the bridging group are as described above,

Preferably, compounds of formula (I), wherein, if n>1, the side chains [i.e. structure (I) without group D] can be attached to group D at one atomic position within group D, for example two or three side chains are attached to a single carbon atom within group D, or they can be attached to group D at different atomic positions within group D, for example at adjacent atomic positions within group D, or/and they can be attached remotely.

The term "side chain" T represents a substituted or unsubstituted straight-chain or branched _C1 - _C20 alkylene group, wherein one or more _-CH2- groups may be replaced independently of one another by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, or heteroatoms and/or bridging groups, which are connected at least once to at least one group ^S1 in the general formula (I).

Preferably, D is selected from the general formula (III), wherein:

C ³ and C ⁴ are independently selected from the group G ² , wherein G ² is:

in:

"-" represents the bond between C ³ and C ⁴ and the adjacent groups of the compound of the above general formula (III); and

L is -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH _{2 ═C} (CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, -NR ⁵ R ⁶ , CH ₂ ═C(CH ₃ )-(CO)O-, CH ₂ ═C(CH ₃ )-O-, wherein:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

T represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be replaced independently of one another by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or a bridging group;

m is an integer of 0-2; preferably 1 or 0; more preferably 0;

u1 is an integer from 0 to 4, provided that m+u1≤4; and

u2 is an integer from 0 to 3, provided that m+u2≤3; and

u3 is an integer from 0 to 2; the condition is m+u3≤2.

D is more preferably selected from the following structures: substituted or unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, benzyldiamine, aminophenylene-Z ⁴ -phenyleneamino, wherein Z ⁴ has the same meaning and preference as above; naphthalene diamine, benzyldiamine, diaminofluorene, 3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol dihydrochloride, 2,4-diaminobenzoic acid, L-(+)-threonine-2-amino-1-(4-aminophenyl)-1,3-propanediol, p-aminobenzoic acid, [3,5-3h]-4-amino-2-methoxybenzoic acid, L-(+)-threonine-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol, 2,7-diaminofluorene, 4,4'- Diaminooctafluorobiphenyl, 3,3'-diaminobenzidine, 2,7-diamino-9-fluorenone, 3,5,3', 5'-tetrabromobiphenyl-4,4'-diamine, 2,2'-dichloro[1,1'-biphenyl]-4,4'-diamine, 3,9- Diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cycloheptan-6-one, dibenzo(1,2)dithiine-3,8-diamine, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4-bis(3-amino-4-hydroxyphenyl)-pentanoic acid, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, tetrabromomethylenediphenylamine, 2,7-diamino-9-fluorenone, 2,2-bis(3-aminophenyl)hexafluoropropane, bis(3-amino-4-chloro-phenyl)-methanone, bis(3-amino-4-dimethylamino-phenyl)-methanone, 3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline, 1,5-diaminonaphthalene, benzidine-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-binaphthyl, 4,4'-diaminodiphenyl-3,3'-diglycolic acid, dihydroethidium, o-dianisidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 3-methoxybenzidine, 3,3'-dichlorobenzidine (diphenyl-d6), 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 3,3'- Dichlorobenzidine-d6, tetramethylbenzidine, di-(aminophenyl)alkylene and amino compounds selected from the group consisting of aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid, 4-Aminobenzoic acid, 4-aminophthalic acid, 1-(4-aminophenyl)ethanol, 4-aminobenzyl alcohol, 4-amino-3-methoxybenzoic acid, 4-aminophenylpropanol, 4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid, 4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid hydrochloride, parastigmine, 4-amino-5-chloro-2-methoxybenzoic acid, 4-(hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-aminobenzoate, 4-amino-3,5-dibromobenzoic acid, isoniazid-p-aminosalicylate, 4-amino-3,5-diiodosalicylic acid, 4-amino-2-methoxybenzoic acid, 2-[2-(4- [0014] 4-Aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindole-1,3-dione, 4-amino-2-nitrobenzoic acid, ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropionate, ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropionate, ethyl 2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropionate, 4-aminonaphthalene-1,8-dicarboxylic acid, 4-amino-3-chloro-5-methylbenzoic acid, 4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid, 4-amino-5-bromo-2-methoxybenzenecarboxylic acid, 3,3'-tolidine-5-sulfonic acid or derivatives thereof, with the proviso that the listed compounds which do not carry two amino groups are considered to be derivatives containing at least one additional amino group.

The diamine group D can be purchased or obtained by known methods. The second amino group can be obtained, for example, by a substitution reaction.

D is further more preferably selected from the following compounds:

in

L, L ₁ , L ₂ and L ₃ are independently -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, -NR ⁵ R ⁶ , CH ₂ ═C(CH ₃ )-(CO)O- or CH ₂ ═C(CH ₃ )-O-,

T, T ₁ , T ₂ and T ₃ are independently substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkylene groups, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, and/or heteroatoms and/or bridging groups;

"-" is a single bond,

q is an integer of 1 or 2; and

q1, q2 and q3 are independently 0-2; preferably an integer of 1 or 2;

m is an integer of 1 or 2;

m1, m2 and m3 are independently 0-2; preferably an integer of 1 or 2;

u3, u3' and u3" are independently integers from 0 to 2;

R ⁵ , R ⁶ and Z ⁴ are as described above; wherein

D is connected at least once to at least one group S ¹ in the general formula (I) via a single bond "-"; or via a side chain T, T ₁ , T ₂ or T ₃ ; or via a group Z ⁴ ; provided that

u3+q or u3+m≤4;

u3+q1 and/or u3'+q2 or/and u3+ml, or/and u3'+m2 or/and u3"+q3 or/and u3"+m3≤4;

q1+q2 and ml+m2 and q1+q2+q3 and ml+m2+m3≥1.

Most preferred are diamine compounds according to the present invention, wherein D is selected from the following compounds:

"-" represents the bond connecting D and ^S1 in compound (I) and represents a single bond; and

L is _-CH3 , _-COCH3 , _-OCH3 , nitro, cyano, halogen, _CH2 =CH-, _CH2 =C( _CH3 )-, _CH2 =CH-(CO)O-, _CH2 =CH-O-, ^-NR5R6 , _CH2 =C( _CH3 )-(CO)O-, or _CH2 =C( _CH3 )-O- wherein ^:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

u3 is an integer from 0 to 2.

E preferably represents a phenylene group, an oxygen atom or -N(H)-, more preferably E is oxygen or -N(H)-, and most preferably E is oxygen.

Preferably, S ¹ and S ² each independently represent a single bond or a spacer unit, the spacer unit being a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, wherein one or more, preferably non-adjacent -CH ₂ - groups may be independently replaced by a linker, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of the general formula (IV):

-(Z ¹ -C ¹ ) _a1 -(Z ² -C ² ) _a2 -(Z ^1a ) _a3 - (IV)

in:

C ¹ and C ² each independently represent a non-aromatic, aromatic, optionally substituted carbocyclic or heterocyclic group, preferably connected to each other via a bridging group Z ¹ and Z ² and/or Z ^1a , preferably, C ¹ and C ² are connected via a bridging group Z ¹ and Z ² and/or Z ^1a at opposite positions so that the groups S ¹ and/or S ² have a long molecular axis, and

Z ¹ , Z ² , and Z ^1a each independently represent a bridging group, preferably selected from -CH(OH)-, -CH ₂ -, -O-, -CO-, -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -OCO-, -COCF ₂ -, -CF ₂ CO-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, -CH═N-, -C(CH ₃ )═N-, -O-CO-O-, -N═N-, or a single bond; and

a1, a2, and a3 each independently represent an integer of 0-3, satisfying a1+a2+a3≤6, wherein preferably S ² is connected to A via Z ¹ ; preferably a3 is 0 and a1+a2≤4.

More preferably, ^S1 represents a linear or branched _C1 - _C24 alkylene group, wherein one or more _-CH2- groups may be independently replaced by a linker or/and a group represented by the general formula (IV), wherein:

C ¹ and C ² are selected from compounds of group G ¹ , wherein group G ¹ is:

in:

"-" represents the bond between ^C1 and ^C2 and the adjacent groups in the general formula (IV); and

L is -CH ₃ , -OCH ₃ , -COCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, CH ₂ ═C(CH ₃ )-(CO)O- or CH ₂ ═C(CH ₃ )-O-,

u1 is an integer from 0 to 4; and

u2 is an integer from 0 to 3; and

u3 is an integer from 0 to 2; and

Z ¹ , Z ² , and Z ^1a each independently represent -O-, -CO-, -COO-, -OCO-, -COCF 2 -, -CF ₂ CO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, _-CH =CH-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or a single bond; provided that heteroatoms are not directly connected to each other, and

a1, a2, and a3 each independently represent an integer from 0 to 3, satisfying a1+a2+a3≤6; preferably, a3 is 0 and a1+a2≤4.

Most preferably ^S1 represents a single bond or a spacer unit such as a linear or branched _C1 - _C14 alkylene group, wherein one or more, preferably non-adjacent _-CH2- groups may be independently replaced by a linker and/or a group represented by the general formula (IV), wherein:

C ¹ and C ² each independently represent 1,4-phenylene, 2-methoxy-1,4-phenylene, 1,4-cyclohexylene or 4,4'-biphenylene; and

Z ¹ , Z ² , and Z ^1a each independently represent -COO-, -OCO-, -CH _{2 -CH 2} -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond; and

a1, a2, and a3 are independently 0 or 1, and preferably a3 is 0.

Especially preferred S ¹ represents a straight-chain C ₁ -C ₁₂ alkylene group, wherein one or more -CH ₂ - groups may be replaced by -O-, -O(CO)-, -(CO)O-, -NR ¹ CO-, -CONR ¹ -, wherein R ¹ is hydrogen or C ₁ -C ₆ alkyl or a group of the general formula (IV), wherein:

C ¹ and C ² each independently represent 1,4-phenylene; and

Z ¹ , Z ² , and Z ^1a each independently represent -COO-, -OCO-, -CH _{2 -CH 2} -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond; and

a1, a2, and a3 are independently 0 or 1, and preferably a3 is 0.

More preferably, S ² represents a spacer unit such as a linear or branched C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ - groups are independently replaced by a group represented by the general formula (IV), wherein:

C ¹ , C ² are selected from the group G ¹ having the meanings given above; and

Z ¹ , Z ² , and Z ^1a each independently represent -O-, -CO-, -COO-, -OCO-, -COCF 2 -, -CF ₂ CO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, _-CH =CH-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or a single bond; provided that heteroatoms are not directly connected to each other, and

a1, a2, and a3 each independently represent an integer of 0-3, satisfying a1+a2+a3≤6, preferably a1+a2≤4, and a3 is 0; wherein S ² is preferably connected to A via Z ¹ .

Most preferably, S ² represents a linear or branched C ₁ -C ₁₂ alkylene group, wherein one or more -CH ₂ - groups are independently replaced by a group represented by the general formula (IV), and more preferably, S ² represents a group represented by the general formula (IV), wherein

C ¹ and C ² each independently represent a 1,4-phenylene group which is unsubstituted or mono- or poly-substituted by a halogen atom, and/or an alkoxy group, an alkylcarbonyloxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms, a 1,4-cyclohexylene group or a 4,4'-biphenylene group; and

Z ¹ , Z ² , and Z ^1a each independently represent -COO-, -OCO-, -CH _{2 -CH 2} -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond; and

a1, a2, a3 are independently 0 or 1, wherein preferably S2 is connected to A via ^Z1 .

The most preferred S ² represents a group of formula (IVa)

-(Z ¹ -C ¹ ) _a1 -(Z ^1a ) _a3 - (IVa)

in:

C ¹ represents a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, preferably a compound selected from the group G1,

Z ¹ and Z ^1a each independently represent -COO-, -OCO-, -OCO(C ₁ -C ₆ )alkyl, -COOCH ₂ (C ₁ -C ₆ )alkyl-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH- or a single bond, or a linear or branched, substituted or unsubstituted C ₁ -C ₈ alkylene group, where one or more -CH ₂ - groups may, as described above, be replaced independently by a linking group, preferably -O-;

a1 and a3 independently represent 1, wherein preferably S ² is linked to A via Z ¹ .

In addition, the most preferred S ² represents a group of general formula (IVa)

-(Z ¹ -C ¹ ) _a1 (Z ^1a ) _a3 - (IVa)

in:

^C1 represents a 1,4-phenylene group which is unsubstituted or mono- or poly-substituted by a halogen atom, and/or an alkoxy group, an alkylcarbonyloxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms,

Z ¹ and Z ^1a each independently represent -COO-, -OCO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH＝CH-, -C≡C-, -CH＝CH-COO-, -OCO-CH＝CH- or a single bond, or a linear or branched, substituted or unsubstituted C ₁ -C ₈ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by the above-mentioned linking groups, preferably -O-, -COO-, -OCO-,

a1 and a3 independently represent 1, wherein preferably S ² is linked to A via Z ¹ .

Another preferred embodiment of the present invention relates to diamine compounds (I), with reference to any of the above definitions comprising these diamine compounds, wherein A represents a phenanthrenyl, biphenylene, naphthylene or phenylene group, which is unsubstituted or mono- or polysubstituted by halogen atoms, hydroxyl groups and/or polar groups, preferably nitro, cyano, carboxyl groups; and/or an acryloyloxy, methacryloyloxy, vinyl, vinyloxy, allyl, allyloxy and/or a cyclic, linear or branched C ₁ -C ₁₂ alkyl residue, which is unsubstituted, mono- or polysubstituted by fluorine and/or chlorine, wherein one or more -CH ₂ - groups may independently be replaced by a linking group and/or an aromatic or alicyclic group, and wherein the compound residue (Ia) of the compound of the above general formula (I)

represents a linear or branched C ₁ -C ₁₂ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 10,

B represents a straight-chain or branched C ₁ -C ₁₂ alkyl group which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be replaced independently of one another by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH-, wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group;

provided that the oxygen atoms are not directly bonded to each other; and

wherein the C ₁ -C ₁₂ fluoroalkyl group has a terminal unit selected from -CF ₂ H and -CF ₃ , preferably selected from -CF ₂ H or -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₂ CHF ₂ , -(CF ₂ ) ₃ CHF ₂ , -(CF ₂ ) ₃ CF ₃ , -CF(CF ₃ ) ₂ and -CF ₂ (CHF)CF ₃ ,

D represents an optionally substituted aliphatic, aromatic or alicyclic diamine group containing 1 to 40 carbon atoms selected from the general formula (III),

HN(R ⁵ )-(Sp ¹ ) _k1 -(X ¹ ) _t1 -(Z ³ -C ³ ) _a3 -(Z ⁴ -C ⁴ ) _a4 -(X ² ) _t2 -(Sp ² ) _k2 -N(R ⁶ )H (III)

in

k ¹ , k ² are 0 or 1, and

t ¹ and t ² are 0, and

R ⁵ and R ⁶ are the same and represent a hydrogen atom, a methyl group, an ethyl group or an isopropyl group; and

C ³ and C ⁴ are independently selected from the compounds of the above group G ² ;

Z ³ represents a group selected from -CH(OH)-, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CO-, -COO-, -OCO-, -COCF ₂ -, -CF ₂ CO-, or a single bond; and

Z ⁴ has one of the meanings of Z ³ or represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more, preferably non-adjacent -CH ₂ - groups may be replaced independently of one another by cyclohexylene, phenylene, aromatic or non-aromatic N-heterocycles; or by heteroatoms and/or oxygen atoms; and/or one or more carbon-carbon single bonds may be replaced by carbon-carbon double or carbon-carbon triple bonds;

a3 and a4 each independently represent an integer from 0 to 2 satisfying a3+a4≤3;

Sp ¹ , Sp ² , X ¹ , and X ² have the same meanings as above;

E represents a phenylene group, an oxygen atom or -N(H)-;

S ¹ represents a single bond or cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by the above-mentioned linking groups;

^S2 represents a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of the general formula (IV):

-(Z ¹ -C ¹ ) _a1 -(Z ² -C ² ) _a2 -(Z ^1a ) _a3 - (IV)

in:

C ¹ and C ² each independently represent a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and

Z ¹ , Z ² , and Z ^1a each independently represent a bridging group, and

a1, a2, and a3 each independently represent an integer from 0 to 3, satisfying a1+a2+a3≤6, preferably a1+a2≤4, and a3 is 0;

wherein the bridging groups Z ¹ , Z ^1a and Z ² are as described above,

X and Y are hydrogen atoms, and

n is 1, 2 or 3, n1 is 1 or 2; preferably n1 is 1.

Provided that if n is 2 or 3, each of A, B, x ₁ , D, E, S ¹ and S ² may be the same or different, and if n 1 is 2, each of B and x ₁ may be the same or different.

A more preferred embodiment of the present invention relates to diamine compounds (I), with reference to any of the above definitions, and to alignment materials comprising these diamine compounds, wherein

A represents a biphenylene group, a naphthylene group or a phenylene group, which is unsubstituted or mono- or poly-substituted by a halogen atom, a hydroxyl group and/or an acryloyloxy group and/or a methacryloyloxy group and/or a linear or branched alkyl group, an alkoxy group, an alkylcarbonyloxy group and/or an alkoxycarbonyl group having 1 to 20 carbon atoms, and wherein the compound residue (Ia) of the compound of the general formula (I) as claimed in claim 1 is

represents a linear or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 9,

B represents a straight-chain or branched C ₁ -C ₈ alkyl group, which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH-, wherein:

^R1 represents a hydrogen atom or a _C1 - _C8 alkyl group; provided that the oxygen atoms are not directly bonded to each other; and

D represents an optionally substituted aliphatic, aromatic or alicyclic diamine group represented by the general formula (III) containing 1 to 40 carbon atoms and is most preferably a group selected from the following structures: substituted or unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, aminophenylene-Z ⁴ -phenyleneamino, m-phenylenediamine containing a substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, or heteroatoms and/or bridging groups; wherein Z ⁴ has the same meaning as above; benzidine, diaminofluorene, 3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol dihydrochloride, 2,4-diaminobenzoic acid, L-(+)-threonine-2-amino-1- (4-Aminophenyl)-1,3-propanediol, p-aminobenzoic acid, [3,5-3h]-4-amino-2-methoxybenzoic acid, L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol, 2,7-diaminofluorene, 4,4'-diaminooctafluorobiphenyl, 3,3'-diaminobenzidine, 2,7-diamino-9-fluorenone, 3,5,3',5'-tetrabromobiphenyl-4,4'-diamine, 2,2'-dichloro[1,1'-biphenyl]-4,4'-diamine, 3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cycloheptan-6-one, dibenzo(1,2)dithiine-3,8-diamine, 3,3'- Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4-bis(3-amino-4-hydroxyphenyl)-pentanoic acid, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, tetrabromomethylenediphenylamine, 2,7-diamino-9-fluorenone, 2,2-bis(3-aminophenyl)hexafluoropropane, bis(3-amino-4-chloro-phenyl)-methanone, bis(3-amino-4-dimethylamino-phenyl)-methanone, 3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline, 1,5-diaminonaphthalene, benzidine-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-binaphthyl, 4,4'-diaminodiphenyl-3,3'-diglycolic acid, dihydroethidium, o- dianisidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 3-methoxybenzidine, 3,3'-dichlorobenzidine (diphenyl-d6), 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-dichlorobenzidine-d6, tetramethylbenzidine, di-(aminophenyl)alkylene and amino compounds selected from the group consisting of aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid, 4-aminobenzoic acid, 4-aminophthalic acid, 1-(4-aminophenyl) Ethanol, 4-aminobenzyl alcohol, 4-amino-3-methoxybenzoic acid, 4-aminophenylpropanol, 4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid, 4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid hydrochloride, parastigmine, 4-amino-5-chloro-2-methoxybenzoic acid, 4-(hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-aminobenzoate, 4-amino-3,5-dibromobenzoic acid, isoniazid p-aminosalicylate, 4-amino-3,5-diiodosalicylic acid, 4-amino-2-methoxybenzoic acid, 2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindole-1,3-dione, 4-Amino-2-nitrobenzoic acid, ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropionate, ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropionate, ethyl 2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropionate, 4-aminonaphthalene-1,8-dicarboxylic acid, 4-amino-3-chloro-5-methylbenzoic acid, 4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid, 4-amino-5-bromo-2-methoxybenzenecarboxylic acid, 3,3'-tolidine-5-sulfonic acid or derivatives thereof, with the proviso that the listed compounds which do not carry two amino groups are considered to be derivatives containing at least one additional amino group.

E represents an oxygen atom or -N(H)-;

^S1 represents a spacer unit such as a linear or branched _C1 - _C14 alkylene group, wherein one or more _-CH2- groups may be independently replaced by a group represented by the general formula (IV) defined above, wherein:

C ¹ and C ² each independently represent 1,4-phenylene, 2-methoxy-1,4-phenylene, 1,4-cyclohexylene or 4,4'-biphenylene; and

Z ¹ , Z ² , and Z ^1a each independently represent -COO-, -OCO-, -CH _{2 -CH 2} -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond; and

a1, a2, a3 are independently 0 or 1; preferably a3 is 0,

^S2 represents a spacer unit of the general formula (IV) as defined above, wherein preferably, ^S2 is connected to A via ^Z1 ; wherein

C ¹ and C ² each independently represent a 1,4-phenylene group which is unsubstituted or mono- or poly-substituted by a halogen atom, and/or an alkoxy group, an alkylcarbonyloxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms, a 1,4-cyclohexylene group or a 4,4'-biphenylene group; and

Z ¹ , Z ² , and Z ^1a each independently represent -O-, -COO-, -OCO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond; and

a1, a2, and a3 are independently 0 or 1; preferably, a3 is 0.

n is 1 or 2, n1 is 1 or 2, preferably 1; provided that if n is 2 or 3, each A, B, _x1 , D, E, ^S1 , ^S2 , X, Y may be the same or different; if n1 is 2, each B, _x1 may be the same or different.

Another more preferred embodiment of the present invention relates to a diamine compound represented by one of the general formula (I), with reference to any of the above definitions, and preferably to an alignment material comprising such a diamine compound, wherein

A represents 1,4-phenylene, which is unsubstituted or mono- or poly-substituted by halogen atoms and/or acryloyloxy or methacryloyloxy and/or alkoxy, alkylcarbonyloxy or alkoxycarbonyl groups having 1 to 10 carbon atoms, wherein the compound residue (Ia) of the compound of the above general formula (I) is

represents a linear or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 9,

B represents a straight-chain or branched C ₁ -C ₈ alkyl group, which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH-, wherein:

^R1 represents a hydrogen atom or a _C1 - _C6 alkyl group; provided that the oxygen atoms are not directly bonded to each other; and wherein the _C1 - _C12 fluoroalkyl group has a terminal unit _{selected from -CF2H} and _-CF3 , preferably selected _from -CF2H or _-CF3 , _-CF2CF3 , _-CF2CHF2 , -( _CF2 ) _2CF3 , -( _CF2 ) _2CHF2 , -( _CF2 ) _3CHF2 , -( _CF2 ) _{3CF3 , -CF(CF3)2 and -CF2 ( CHF ) CF3 ,}

D represents unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, benzylenediamine, aminophenylene-Z ⁴ -phenyleneamino, naphthalenediamine or a substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, or heteroatoms and/or bridging groups; wherein

Z ⁴ is as defined above;

E represents an oxygen atom;

S ¹ represents a single bond or a straight-chain C ₁ -C ₈ alkylene group, wherein one -CH ₂ - group may be replaced by -O-, -OCO-, -COO-, -NR ¹ CO-, or -CONR ¹ -, wherein R ¹ is hydrogen or C ₁ -C ₆ alkyl,

^S2 is replaced by a group of the above general formula (IVa), wherein:

^C1 represents a 1,4-phenylene group which is unsubstituted or mono- or poly-substituted by a halogen atom, and/or an alkoxy group, an alkylcarbonyloxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms,

Z ¹ and Z ^1a represent -O-, -COO-, -OCO-, -COO(C ₁ -C ₆ )alkylene, -OCO(C ₁ -C ₆ )alkylene, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -O≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond;

X and Y are hydrogen atoms, and

n is 1 or 2, n1 is 1 or 2, preferably 1; provided that if n is 2, each of A, B, _x1 , D, E, ^S1 and ^S2 may be the same or different; and if n1 is 2, each of B and _x1 may be the same or different.

A most preferred embodiment of the present invention relates to diamine compounds represented by one of the general formula (I), with reference to any of the above definitions, and to alignment materials comprising these diamine compounds, wherein

^S2 is replaced by a group of formula (IV), wherein:

C ¹ represents 1,4-phenylene; and

Z ¹ and Z ^1a each independently represent -COO-, -OCO-, -CH _{2 -CH 2} -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond;

a1 represents 1 and a3 represents 0.

^S2 is connected to A via ^Z1 .

The most preferred embodiment of the present invention relates to compounds of the general formula (VI), (VII), (VIII), (IX), (X), (XI), (XIa) and (XIb)

in

A, B, x ₁ , n, n1, D, E, S ² , S ¹ , X and Y, R ⁵ , R ⁶ and Z ⁴ have the meanings and preferences given above; preferably n1 is 1;

L is _-CH3 , _-OCH3 , _-COCH3 , nitro, cyano, halogen, _CH2 =CH-, _CH2 =C( _CH3 )-, _CH2 =CH-(CO)O-, _CH2 =CH-O-, _CH2 =C( _CH3 )-(CO)O- or _CH2 =C( _CH3 )-O-,

u3 is an integer from 0 to 2.

In addition, the most preferred embodiment of the present invention relates to diamine compounds of the general formula (XII)

wherein x ₁ , n, n1 , D, E, S ¹ , X, Y, Z ¹ , L, u1 and u2 have the meanings and preferences given above.

Preferred diamine compounds of the general formula (XII) are compounds in which ^Z1 is -COO-, -OCO-, -OCO( _C1 - _C6 )alkylene or -COC( _C1 - _C6 )alkylene single bond, or linear or branched, substituted or unsubstituted _C1 - _C8alkylene , wherein one or more _-CH2- groups may be replaced independently of one another by a linking group, preferably -O-.

In addition, the most preferred diamine is a compound of the general formula (XIIa)

wherein n, n1, D, E, ^S1 , ^Z1 , L, u1 and u2, X and Y have the meanings and preferences given above, and wherein the following compound residues

represents a linear or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 9,

B represents a straight-chain or branched C ₁ -C ₈ alkyl group, which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH-, wherein:

^R1 represents a hydrogen atom or a _C1 - _C6 alkyl group; provided that the oxygen atoms are not directly connected to each other; and

wherein the C ₁ -C ₁₂ fluoroalkyl group has a terminal unit selected from -CF ₂ H and -CF ₃ , preferably selected from -CF ₂ H or -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₂ CHF ₂ , -(CF ₂ ) ₃ CHF ₂ , -(CF ₂ ) ₃ CF ₃ , -CF(CF ₃ ) ₂ and -CF ₂ (CHF)CF ₃ .

The most preferred diamine is

wherein S ¹ has the meanings and preferences given above; particularly preferably S ¹ represents a straight-chain C ₁ -C ₁₂ alkylene group, wherein one or more -CH ₂ - groups may be replaced by -O-, -O(CO)-, -(CO)O-, -NR ¹ CO-, -CONR ¹ -, wherein R ¹ is hydrogen or C ₁ -C ₆ alkyl or a group of the general formula (IV) wherein:

C ¹ and C ² each independently represent 1,4-phenylene; and

Z ¹ , Z ² , and Z ^1a each independently represent -COO-, -OCO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO-CH═CH-, or a single bond, and

a1, a2, a3 are independently 0 or 1, preferably a3 is 0; wherein the following compound residue

represents a linear or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 9,

B represents a straight-chain or branched C ₁ -C ₈ alkyl group which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH- wherein:

^R1 represents a hydrogen atom or a _C1 - _C6 alkyl group; provided that the oxygen atoms are not directly connected to each other; and

wherein the C ₁ -C ₈ fluoroalkyl group has a terminal unit selected from -CF ₂ H and -CF ₃ , preferably selected from -CF ₂ H or -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₂ CHF ₂ , -(CF ₂ ) ₃ CHF ₂ , -(CF ₂ ) ₃ CF ₃ , -CF(CF ₃ ) ₂ and -CF ₂ (CHF)CF ₃ .

Another preferred embodiment of the present invention relates to diamine compounds represented by general formula (I), which can be used in subsequent manufacturing processes as such or in combination with one or more additional other diamines, preferably those of general formula (L) given below.

Diamine (L) represents an optionally substituted aliphatic, aromatic or alicyclic diamino group containing 1 to 40 carbon atoms and is preferably derived from or selected from the following structures: aniline, p-phenylenediamine, m-phenylenediamine, benzidine, diaminofluorene or derivatives thereof, with the proviso that the listed compounds which do not carry two amino groups are considered to be derivatives with at least one additional amino group, more preferably derived from or selected from the following commercially available amino compounds (examples of suppliers: Aldrich, ABCR, ACROS, Fluka), which can also be used as comonomers:

4-Amino-2,3,5,6-tetrafluorobenzoic acid

4-amino-3,5-diiodobenzoic acid,

3,4-Diaminobenzoic acid

4-amino-3-methylbenzoic acid,

4-Amino-2-chlorobenzoic acid

4-aminosalicylic acid

4-aminobenzoic acid

4-Aminophthalic acid

1-(4-aminophenyl)ethanol

4-Aminobenzyl alcohol

4-Amino-3-methoxybenzoic acid

4-Aminophenylpropanol

4-Amino-3-nitrobenzoic acid

4-Amino-3,5-dinitrobenzoic acid

4-Amino-3,5-dichlorobenzoic acid

4-Amino-3-hydroxybenzoic acid

4-Aminobenzyl alcohol hydrochloride

4-Aminobenzoic acid hydrochloride

Pararubine

4-Amino-5-chloro-2-methoxybenzoic acid

4-(Hexafluoro-2-hydroxyisopropyl)aniline

Piperazine-p-aminobenzoate

4-Amino-3,5-dibromobenzoic acid

Isoniazid p-aminosalicylate

4-Amino-3,5-diiodosalicylic acid

4-Amino-2-methoxybenzoic acid

2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindole-1,3-dione

4-Amino-2-nitrobenzoic acid

2,4-Diaminobenzoic acid

p-Aminobenzoic acid,

[3,5-3h]-4-amino-2-methoxybenzoic acid

L-(+)-Threonyl-2-amino-1-(4-aminophenyl)-1,3-propanediol

L-(+)-Threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol

Ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropionate

Ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropionate

2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropionic acid ethyl ester

3,4-Diaminobenzyl alcohol dihydrochloride

4-Aminonaphthalene-1,8-dicarboxylic acid

4-Amino-3-chloro-5-methylbenzoic acid

4-Amino-2,6-dimethylbenzoic acid

4-Amino-3-fluorobenzoic acid

4-Amino-5-bromo-2-methoxybenzenecarboxylic acid

2,7-diaminofluorene

4,4'-Diaminooctafluorobiphenyl

3,3'-Diaminobenzidine

3,3',5,5'-Tetramethylbenzidine

3,3'-Dimethoxybenzidine

o-Tolidine

3,3'-Dinitrobenzidine

2-Nitrobenzidine

3,3'-Dihydroxybenzidine

o-Tolidine sulfone

Benzidine,

3,3'-Dichlorobenzidine

2,2',5,5'-Tetrachlorobenzidine,

Benzidine-3,3'-dicarboxylic acid

4,4'-Diamino-1,1'-binaphthyl

4,4'-Diaminodiphenyl-3,3'-diglycolic acid

Dihydroethidium

o-Dianisidine

2,2'-Dichloro-5,5'-dimethoxybenzidine

3-Methoxybenzidine

3,3'-dichlorobenzidine (diphenyl-d6),

2,7-Diamino-9-fluorenone

3,5,3',5'-Tetrabromobiphenyl-4,4'-diamine

2,2'-Bis(trifluoromethyl)benzidine

2,2'-Dichloro[1,1'-biphenyl]-4,4'-diamine

3,9-Diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cycloheptan-6-one

3,3'-Bis(trifluoromethyl)benzidine

Dibenzo(1,2)dithiine-3,8-diamine

3,3'-Tolidine-5-sulfonic acid

3,3'-Dichlorobenzidine-d6

Tetramethylbenzidine

3,3'-Diaminobenzophenone,

3,3'-diaminodiphenylmethane,

4,4-Bis(3-amino-4-hydroxyphenyl)-pentanoic acid

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane

2,2-Bis(3-amino-4-methylphenyl)hexafluoropropane

Tetrabromomethylenedianiline

2,7-Diamino-9-fluorenone

2,2-bis(3-aminophenyl)hexafluoropropane

Bis(3-amino-4-chloro-phenyl)-methanone

Bis(3-amino-4-dimethylamino-phenyl)-methanone

3-[3-Amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline

1,5-Diaminonaphthalene

or their derivatives, with the proviso that the listed compounds which do not carry two amino groups are considered to be derivatives having at least one additional amino group.

Preferred examples of the additional other diamines (L) are: ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, α,α'-diamino-m-xylene, α,α'-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine, 1,2-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(methylamino)cyclohexane, 4,9-dioxadodecane-1,12-diamine, 3,5-diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid methyl ester, Hexyl diaminobenzoate, dodecyl 3,5-diaminobenzoate, isopropyl 3,5-diaminobenzoate, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-2,2'-dimethylbibenzyl, bis[4-(4-aminophenoxy)phenyl] Sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 4,4'-bis(4-aminophenoxy)biphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(1,4-phenyleneisopropylidene)diphenylamine, 4,4'-(1,3-phenyleneisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl] propane, 2,2-bis[3-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-methylphenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl and 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2',3',5',6'-octafluorobiphenyl, and diamines (L) disclosed in US Pat. No. 6,340,506, WO 00/59966 and WO 01/53384, all of which are expressly incorporated herein by reference;

The diamine compound (L) according to the present invention can be prepared using methods known to those skilled in the art.

Furthermore, preferred diamines (L) are those listed below which are commercially available:

polymer

Poly(3,3',4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline/1,3-phenylenediamine), amic acid solution

Poly(3,3',4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline/1,3-phenylenediamine), amic acid solution

Poly(pyromellitic dianhydride-co-4,4'-oxydianiline), amic acid solution Aromatic diamine

2,7-diaminofluorene

1,5-Diaminoanthraquinone

2,6-Diaminoanthraquinone

Parafuchsin hydrochloride

3,6-Acridiniumdiamine

4,4'-Diaminooctafluorobiphenyl

2,2'-diphenyldisulfide

3,3',5,5'-Tetramethylbenzidine

3,3'-Diaminodiphenyl sulfone

4,4'-Diamino-2,2'-dimethylbibenzyl

4,4'-Diaminodiphenyl ether

4,4'-diphenyldisulfide

4,4'-Diaminodiphenyl sulfone

4,4'-diaminodiphenylmethane

4,4'-ethylenediphenylamine

3,3'-Dimethoxybenzidine

2,2'-Dithiobis(1-naphthylamine)

3,7-Diamino-2-methoxyfluorene

3,6-Diamino-10-methylacridinium chloride

Propidium iodide

o-Dianisidine dihydrochloride

2,7-Diaminofluorene dihydrochloride

Pararosaniline acetate

3,6-Diamino-10-methylacridinium chloride hydrochloride

Bisaminoacridine dihydrochloride

o-Tolidine dihydrochloride

3,3',5,5'-Tetramethylbenzidine dihydrochloride

3,3'-Diaminobenzidine tetrahydrochloride

4,4'-Diaminostilbene dihydrochloride

4,4'-Diaminodiphenylamine sulfate

Diaminoacridine hemisulfate

2,2'-Ethylenediamine diphosphate

1,5-Diamino-4,8-dihydroxyanthraquinone

o-Tolidine

3,3'-Diaminobenzophenone,

3,3'-diaminodiphenylmethane,

3,4'-diaminodiphenylmethane

2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane

4,4'-Diamino-1,1'-anthramide

3,3'-Dinitrobenzidine

4,4'-Diamino-5,5'-dimethyl-2,2'-biphenyldisulfonic acid

4,4'-Diaminostilbene-2,2'-disulfonic acid

3-Amino-4-hydroxyphenyl sulfone

4,4-Bis(3-amino-4-hydroxyphenyl)-pentanoic acid

2,2'-Diamino-4,4'-difluorobibenzyl

2-Amino-4-chlorophenyl disulfide

3,3'-(Decamethylenedioxy)diphenylamine

3,3'-(Pentamethylenedioxy)diphenylamine

4-(p-Aminoanilino)-3-sulfoaniline

4-[3-(4-aminophenoxy)propoxy]aniline

2-Nitrobenzidine

Benzidine-3-sulfonic acid

4,4'-Diaminodiphenyl sulfide

4,4'-Diaminobenzanilide

N,N'-bis(3-aminophenylsulfonyl)ethylenediamine

2,2'-Biphenylenediamine

3,4'-Diaminodiphenyl ether

Diaminoacridine hemisulfate

Phenosafranin

4,4'-Diaminobenzophenone

2,2-bis(4-aminophenyl)hexafluoropropane

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane

2,2-Bis(3-amino-4-methylphenyl)hexafluoropropane

3,3'-Dihydroxybenzidine

3,3'-Diamino-4,4'-dihydroxybiphenyl

4,4'-Bis(4-aminophenoxy)biphenyl

2,2-Bis[4-(4-aminophenoxy)phenyl]propane

1,4-Bis(4-aminophenoxy)benzene

1,3-Bis(4-aminophenoxy)benzene

Bis[4-(4-aminophenoxy)phenyl]sulfone

9,9-bis(4-aminophenyl)fluorene

o-Tolidine sulfone

Benzidine

3,3'-Dichlorobenzidine dihydrochloride

Benzidine dihydrochloride

3,6-Thioxanthendiamine-10,10-dioxide

4,4'-Diamino-2,2'-biphenyldisulfonic acid

4,4'-Azodiphenylamine

2,5-bis(4-aminophenyl)-(1,3,4)oxadiazole

3,3'-Dimethylbinapthylamine

Benzidine sulfate

1,3-Bis(3-aminophenoxy)benzene

3,3'-Dichlorobenzidine

2,2',5,5'-Tetrachlorobenzidine

4,4'-Diamino-1,1'-binaphthyl

Diamine wine red

Benzoflavin

Corydaline

2,2'-Thiobis(5-aminobenzenesulfonic acid)

4,4'-Methylenebis(2-chloroaniline)

Tetrabromomethylenedianiline

4,4'-Diamino-3,3'-dinitrophenyl ether

Benzidine pyrophosphate

3,6-Diaminothioxanthene-10-dioxide, dihydrochloride

4,4″-diamino-p-terphenyl

1,8-Diamino-4,5-dihydroxyanthraquinone

Bis(p-aminophenoxy)dimethylsilane

Bis[4-(3-aminophenoxy)phenyl]sulfone

4,4'-Methylenebis-2,6-dimethylaniline

2-Aminobenzaldehyde-ethylenediimine

3-Methylbenzidine dihydrochloride

3,3'-Diethylbenzidine dihydrochloride

3,6-Diaminoacridine hydrochloride

4,4'-Diamino-5,5'-dimethyl-2,2'-biphenyldisulfonic acid disodium salt

4,4'-Methylenebis(3-chloro-2,6-diethylaniline)

4,4'-Methylenebis-(2,6-diethylaniline)

4,4'-Methylenebis-(2,6-diisopropylaniline)

Tolylene diamine

3,8-Diamino-6-phenylphenanthridine

Thionine perchlorate

dihydroethidium

Thionine

4,4-phenylenediaminesulfonylanilide

o-Dianisidine hydrochloride

2,2'-Dichloro-5,5'-dimethoxybenzidine

3-Methoxybenzidine

2,2'-(hexamethylenedioxy)diphenylamine

2,2'-(Pentamethylenedioxy)diphenylamine

2,2'-(ethylenedioxy)diphenylamine

4-[4-(4-aminophenoxy)butoxy]aniline

2,2'-Diamino-4'-methoxy-4-methylbenzanilide

5,5'-Dimethyl-2,2'-dinitrobenzidine

N,N'-Bis(2-aminophenyl)-1,3-propanediamine

3,4'-diaminochalcone

2,3',4,5',6-pentaphenyl-3,4'-diphenylenediamine

2-([1-(4-(1-[(2-aminophenyl)thio]-2-nitroethyl)phenyl)-2-nitroethyl]thio)aniline

2-((2-[(2-aminophenyl)thio]ethyl)thio)aniline

2-((4-[(2-aminophenyl)thio]but-2-enyl)thio)aniline

4,4'-Diamino-3,3'-dimethyldiphenylmethane

2,2'-Diamino-bibenzyl

Trimethylene bis(4-aminobenzoate)

fluoresceinamine

Benzidine mixture

3-Nitro-4,4'-methylenedianiline

4,4-Diamino-2,2'-dichlorodiphenyl disulfide

1,6-Diaminopyrene

1,8-Diaminopyrene

3,6-Diaminocarbazole

4,4'(5')-Diamino-[2,4]-dibenzo-18-crown-6-ol, dihydrochloride

4,4'-Diaminostilbene-2,2'-disulfonic acid, disodium salt

(r)-(+)-2,2'-Diamino-1,1'-binaphthyl

Diaminoacridine hemisulfate dihydrate

3,6-Diaminoacridine hemisulfate hemihydrate

Mephenthrine bromide monohydrate

o-Tolidine dihydrochloride hydrate

3,3',5,5'-Tetramethylbenzidine dihydrochloride hydrate

3,3'-Diaminobenzidine tetrahydrochloride dihydrate

3,6-[bis(4-amino-3-(sodiumsulfonyl)phenylamino)]-2,5-dichloro-4-benzoquinone

2,2'-Dimethylbenzidine hydrochloride

2,2'-(phenylmethylenebis)bis(4-methylaniline)

3,4'-Diaminobenzidine

2,7-Diamino-9-fluorenone

N,N'-bis(2-aminophenyl)oxalamide

2-[2-(2-aminophenyl)diazen-1-yl]aniline

3,5,3',5'-Tetrabromobiphenyl-4,4'-diamine

N,N'-Bis(4-aminophenyl)-1,3-bis(aminomethyl)benzene dihydrochloride

4',4"(5")-diaminodibenzo-15-crown-5

2,2'-Bis(trifluoromethyl)benzidine

Bis(4-amino-2,3-dichlorophenyl)methane

α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene

2,2-bis(3-aminophenyl)hexafluoropropane

3,10-Diamino-6,13-dichlorobenzo[5,6][1,4]oxazin[2,3-b]phenazine-4,11-disulfonyl

n1-(2-amino-4-methylphenyl)-2-aminobenzamide

n1-(2-amino-4-chlorophenyl)-2-aminobenzamide

2,2'-Dichloro[1,1'-biphenyl]-4,4'-diamine

4,4'(5')-Diaminodibenzo-15-crown-5-dihydrochloride

rcl S19,413-1

Bis(4-amino-3-nitrophenyl)-methanone

Bis(3-amino-4-chloro-phenyl)-methanone

Bis(3-amino-4-dimethylamino-phenyl)-methanone

N,N'-Bis(4-amino-2-chloro-phenyl)-isophthalamide

N,N'-Bis(4-amino-2-chloro-phenyl)-terephthalamide

3,9-Diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cycloheptan-6-one

2-Aminobenzaldehyde n-[(Z)-(2-aminophenyl)methylene]hydrazone

3,3'-Bis(trifluoromethyl)benzidine

dimethylformamide dihydrochloride

4,4'-(1,3-phenylenediisopropylidene) dianiline

1,4-phenylenebis[[4-(4-aminophenoxy)phenyl]methanone]

2-((5-[(2-aminophenyl)thio]-3,4-dinitro-2-thienyl)thio)aniline

n'1-(2-aminobenzoyl)-2-aminobenzene-1-carbohydrazide

2-[4-(5-amino-1h-benzimidazol-2-yl)phenyl]-1h-benzimidazol-5-amine

4-[4-(4-Aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline

3,3'-Dinitro-4,4'-diaminodiphenyl sulfone

3,3',4,4'-Tetraaminodiphenyl sulfone

4-[1-(4-Aminophenyl)-1-methylethyl]aniline

3,3-Diaminodiphenylurea

Bis(4-aminophenyl)acetylene

Dibenzo(1,2)dithiirane-3,8-diamine

3,8-Diamino-5-ethyl-6-phenylphenanthridine homodimer-2

4.4'-Bis(2-aminophenylsulfonyl)bisphenolate

Neopentyl glycol bis(4-aminophenyl) ether

2,2'-oxydiphenylamine

4,4'-Diaminodiphenylamine-2,2-disulfonic acid

4,4-Diaminodiphenylurea

3,3'-Tolidine-5-sulfonic acid

n1-(3-[(2-aminobenzoyl)amino]propyl)-2-aminobenzamide

2-((6-[(2-aminophenyl)sulfanyl]-5-nitro-2-pyridyl)sulfanyl)aniline

2-((6-amino-1,3-benzothiazol-2-yl)disulfide)-1,3-benzotriazol-6-ylamine tetramethylbenzidine

2-([6-[(2-aminophenyl)sulfanyl]-3,5-bis(trifluoromethyl)-2-pyridyl]sulfanyl)aniline

3,6-Diaminothioxanthene-10-dioxide dihydrochloride

m-Tolidine dihydrochloride hydrate

2-Amino-n-[2-amino-4-(trifluoromethyl)phenyl]-5-methylbenzamide

2-([2-[(2-aminophenyl)sulfanyl]-6-nitro-4-(trifluoromethyl)phenyl]sulfanyl)aniline

2-[(3-([(2-aminophenyl)thio]methyl)-2,4,6-trimethylbenzyl)thio]aniline

3-[3-Amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline

2-((5-[(2-aminophenyl)thio]-4-chloro-2-nitrophenyl)thio)aniline

4-(1-(4-aminophenyl)-2-[4-(dimethylamino)phenyl]vinyl)aniline

1,5-Bis(4-aminophenoxy)pentane

2,3'-Dichlorobenzidine dihydrochloride

3,3'-Diamino-4,4'-dichlorodiphenyl sulfone

3-(Bis(4-amino-phenyl)-methyl)-2,3-dihydro-isoindol-1-one

4,4-Diaminodiphenyl-2-sulfonic acid

4,4'-Diamino-diphenylene-cyclohexane

4. 5'-diamino-(1,1')dianthracenyl-9,10,9',10'-tetraone

Alicyclic diamines

4,4'-Methylenebis(cyclohexylamine)

4,4'-Methylenebis(2-methylcyclohexylamine)

Aliphatic diamines

1,8-Diamino-p-menthane

4,4'-Methylenebis(cyclohexylamine)

d-Cystine

L-Cystine dimethyl ester dihydrochloride

Neomycin

Bis(2-aminopropyl)amine

(H-cys-beta-na)22 hydrochloride

l-Cystine dibenzyl ester ditosylate

1.4-Diaminocyclohexane

(h-cys-pna)2

dl-2-aminopropionic anhydride

L-Cystine (di-b-naphthylamide) hydrochloride

l-Cystine-bis-p-nitroanilide dihydrobromide

L-Cystine diethyl ester dihydrochloride

trans-1,4-cyclohexanediamine

4,4'-Methylenebis(2-methylcyclohexylamine)

l-Leucine thiol, oxidized dihydrochloride

1,3-Diaminoadamantane dihydrochloride

l-Leucine thiol disulfide 2 hydrochloride

L-Cystine disodium salt, monohydrate

L-Homocystine methyl ester hydrochloride

1,3-adamantanediaminetetracyclo[8.2.1.1(8,11).0(2,7)]tetradeca-2,4,6-triene-10,11-diamine

Tricyclooctane[3.3.1.0(3,7)]nonane-3,7-diamine

From the class of commercially available diamines (L), preference is given to those listed below:

Alicyclic diamines

4,4'-Methylenebis(cyclohexylamine)

4,4'-Methylenebis(2-methylcyclohexylamine)

Aliphatic diamines

4,4'-Methylenebis(cyclohexylamine)

1.4-Diaminocyclohexane

trans-1,4-cyclohexanediamine

4,4'-Methylenebis(2-methylcyclohexylamine)

1,3-adamantanediamine

Aromatic diamines

2,7-diaminofluorene

2,6-Diaminoanthraquinone

4,4'-Diaminooctafluorobiphenyl

4,4'-Diaminodiphenyl ether

4,4'-diphenyldisulfide

4,4'-Diaminodiphenylmethane

4,4'-ethylenediphenylamine

3,3'-Dimethoxybenzidine

o-Tolidine

3,3'-Diaminobenzophenone

3,3'-Diaminodiphenylmethane

3,4'-Diaminodiphenylmethane

2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane

4-[3-(4-aminophenoxy)propoxy]aniline

4,4'-Diaminodiphenyl sulfide

4,4'-Diaminobenzophenone

2,2-bis(4-aminophenyl)hexafluoropropane

4,4'-Bis(4-aminophenoxy)biphenyl

2,2-Bis[4-(4-aminophenoxy)phenyl]propane

1,4-Bis(4-aminophenoxy)benzene

1,3-Bis(4-aminophenoxy)benzene

Bis[4-(4-aminophenoxy)phenyl]sulfone

9,9-bis(4-aminophenyl)fluorene

Benzidine

4,4'-Azodiphenylamine

1,3-Bis(3-aminophenoxy)benzene

4,4'-Diamino-1,1'-binaphthyl

4,4"-Diamino-p-terphenyl

Bis(p-aminophenoxy)dimethylsilane

4-[4-(4-aminophenoxy)butoxy]aniline

3,4'-diaminochalcone

Trimethylene bis(4-aminobenzoate)

3,4'-Diaminobenzidine

2,7-Diamino-9-fluorenone

4',4"(5")-diaminodibenzo-15-crown-5

2,2'-Bis(trifluoromethyl)benzidine

α,α'-Bis(4-aminophenyl)-1,4-diisopropylbenzene

3,3'-Bis(trifluoromethyl)benzidine

4,4'-(1,3-phenylenediisopropylidene) dianiline

1,4-phenylenebis[[4-(4-aminophenoxy)phenyl]methanone]

4-[4-(4-Aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline

4-[1-(4-Aminophenyl)-1-methylethyl]aniline

Neopentyl glycol bis(4-aminophenyl) ether

4,4-Diaminodiphenylurea

1,5-Bis(4-aminophenoxy)pentane

From the class of commercially available diamines (L), more preferred are those listed below: Aromatic diamines

2,7-diaminofluorene

4,4'-Diaminooctafluorobiphenyl

4,4'-Diaminodiphenyl ether

4,4'-diaminodiphenylmethane

4,4'-ethylenediphenylamine

3,3'-Diaminobenzophenone

4-[3-(4-aminophenoxy)propoxy]aniline

4,4'-Diaminodiphenyl sulfide

4,4'-Diaminobenzophenone

2,2-bis(4-aminophenyl)hexafluoropropane

4,4'-Bis(4-aminophenoxy)biphenyl

2,2-Bis[4-(4-aminophenoxy)phenyl]propane

1,4-Bis(4-aminophenoxy)benzene

1,3-Bis(4-aminophenoxy)benzene

9,9-bis(4-aminophenyl)fluorene

Benzidine

Bis(p-aminophenoxy)dimethylsilane

4-[4-(4-aminophenoxy)butoxy]aniline

3,4'-diaminochalcone

Trimethylene bis(4-aminobenzoate)

3,4'-Diaminobenzidine

2,7-Diamino-9-fluorenone

4',4"(5")-diaminodibenzo-15-crown-5

4-[4-(4-Aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline

4-[1-(4-Aminophenyl)-1-methylethyl]aniline

1,5-Bis(4-aminophenoxy)pentane

Aliphatic diamines

4,4'-Methylenebis(cyclohexylamine)

1.4-Diaminocyclohexane

Alicyclic diamines

4,4'-Methylenebis(cyclohexylamine)

Another embodiment of the present invention is a composition comprising at least one diamine (I) and optionally at least one further diamine different from (I) and/or additives.

Preferably, the further diamine has the general formula (L).

Additives such as silane-containing compounds and epoxy-containing crosslinking agents may be added.

Suitable silane-containing compounds are described in Plast Eng. 36 (1996), (Polyimides, Fundamentals and Applications), Marcel Dekker, Inc.

Suitable epoxy-containing crosslinking agents include 4,4'-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N'-diglycidyl diimide, polyethylene glycol diglycidyl ether, N,N-diglycidylcyclohexylamine, and the like.

Additional additives are photosensitizers, photoradical generators, and cationic photoinitiators.

Suitable photoactive additives include 2,2-dimethoxyphenyl acetone, a mixture of diphenyl ketone and N,N-dimethylbenzenamine or ethyl 4-(dimethylamino)benzoate, xanthones, thioxanthones, 184, 369, 500, 651 and 907 (Ciba), Michler's ketone, triarylsulfonium salts and the like.

In addition, the present invention relates to a process for preparing the diamine compound (XII) defined above, comprising making a compound of the general formula (XIV)

Preferably

Contact with a dinitro compound of formula (XVI)

The obtained dinitro compound of general formula (XVIa) is then converted into the corresponding diamino compound of general formula (XII)

wherein F, _x1 , n1, n, B, D, X, Y, ^Z1 , L, u1, u2 and ^S1 have the same meanings and preferences as given above, wherein D1 has the same meanings and preferences as given above for D, with the proviso that the two amino groups of D are replaced by two nitro groups.

The reaction between compounds (XIV) and (XVI) can be carried out by many known methods (see J. March, Advanced Organic Chemistry, 2nd edition, pages 363 and 365).

Typically, compounds (XIV) and (XVI) are contacted with a dehydrating agent.

Commonly known dehydrating agents can be used, preferably EDC, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or DCC, dicyclohexylcarbodiimide, trifluoroacetic anhydride, H ₃ BO ₃ —H ₂ SO ₄ , polymer-protected AlCl ₃ , pyridinium salt-Bu ₃ N, or N,N-carbonyldiimidazole.

Generally, the reaction of compounds (XIV) and (XVI) is carried out in a solvent.

Typically, an organic solvent is used, such as toluene, xylene, pyridine, a halogenated alkane, such as dichloromethane, trichloroethane, acetone or dimethylformamide.

The conversion of nitro compounds to amino compounds is generally known and is described, for example, in J. March, Advanced Organic Chemistry, 1977, pages 1125 and 1126. In addition, the conversion can be carried out analogously to the methods described in WO 98/13331 and WO 96/36597.

Furthermore, the present invention relates to compounds of the general formulae (XIV) and (XVI), and (XVIa) given above.

Furthermore, the present invention relates to polymers, copolymers and oligomers comprising diamine (I) as one of the essential building blocks.

Preferred polymers, copolymers and oligomers comprise diamine (I) and tetracarboxylic anhydride as basic building blocks.

Preferably, the polymer, copolymer or oligomer comprising diamine (I) as a basic building block in the context of the present invention is a polyamic acid, a polyamic acid ester, a polyimide or a mixture thereof, preferably a mixture of a polyamic acid and a polyamic acid ester and/or a polyimide. More preferably, a mixture of a polyamic acid and a polyimide.

In the context of the present invention, the term "polyimide" has the meaning of partially or fully imidized polyamic acid or polyamic acid ester. Similarly, the term "imidization" has the meaning of partially or fully imidized in the context of the present invention.

Preferably, the tetracarboxylic anhydride has the general formula (V)

in:

T represents a tetravalent organic group.

The tetravalent organic radical T is preferably derived from an aliphatic, cycloaliphatic or aromatic tetracarboxylic dianhydride.

Preferred examples of aliphatic or alicyclic tetracarboxylic dianhydrides are:

1,1,4,4-Butanetetracarboxylic dianhydride, ethylenemaleic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene -1,2-dicarboxylic acid-dianhydride, bicyclo[2.2.2]octane-7-yl-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 1,8-dimethylbicyclo[2.2.2]octane-7-yl-2,3,5,6-tetracarboxylic dianhydride,

Pyromellitic dianhydride,

3,3',4,4'-Benzophenonetetracarboxylic dianhydride,

4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride,

3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)phenylene sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, ethylene glycol bis(trimellitic acid) dianhydride,

4,4'-(1,4-phenylene)bis(phthalic) dianhydride, 4,4'-(1,3-phenylene)bis(phthalic) dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 4,4'-oxybis(1,4-phenylene)bis(phthalic) dianhydride and 4,4'-methylenebis(1,4-phenylene)bis(phthalic) dianhydride.

Preferred examples of aromatic tetracarboxylic dianhydrides are:

Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dicarboxylic acid anhydride, 3,3',4,4'-biphenyltetracarboxylic acid anhydride, ethylene glycol di(1,2,4-trimellitic acid) anhydride, 4,4'-(1,4-phenylene)di(phthalic acid) anhydride, 4,4'-(1,3-phenylene)di(phthalic acid) anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, 4,4'-oxybis(1,4-phenylene)di(phthalic acid) anhydride, 4,4'-methylenebis(1,4-phenylene)di(phthalic acid) anhydride, and the like.

More preferably, the tetracarboxylic dianhydride used to form the tetravalent organic group T is selected from:

1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic dianhydride and bicyclo[2.2.2]octan-7-yl-2,3,5,6-tetracarboxylic dianhydride.

The polymers, copolymers or oligomers, in particular polyamic acids, polyamic acid esters and polyimides and mixtures thereof can be prepared in-line using known methods, such as those described in Plast. Eng. 36 (1996), (Polyimides, Fundamentals and Applications), Marcel Dekker, Inc.

For example, amidation, the polycondensation reaction used to prepare polyamic acid, is carried out in solution in a polar aprotic organic solvent such as γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone, or N,N-dimethylformamide. In most cases, equimolar amounts of anhydride and diamine are used, i.e., one amino group/anhydride group. If it is necessary to stabilize the molecular weight of the polymer, copolymer, or oligomer, an excess or substoichiometric amount of one or both components or a monofunctional compound in the form of a dicarboxylic acid monoanhydride or monoamine may be added for this purpose. Examples of such monofunctional compounds include maleic anhydride, phthalic anhydride, aniline, and the like. Preferably, the reaction is carried out at a temperature below 100°C.

Imidization, i.e., cyclization of the polyamic acid to form the polyimide, can be carried out by heating, i.e., condensation by removal of water, or by other imidization reactions using suitable reagents. For example, if the imidization is carried out purely thermally, partial imidization is achieved, and the imidization of the polyamic acid may not always be complete, i.e., the resulting polyimide may still contain some polyamic acid. The complete imidization reaction is carried out at a temperature of 60-250°C, preferably less than 200°C.

To achieve imination at a relatively low temperature, additional reagents that aid in water removal are added to the reaction mixture. These reagents are, for example, mixtures of anhydrides such as acetic anhydride, propionic anhydride, phthalic anhydride, and trifluoroacetic anhydride, or tertiary amines such as triethylamine, trimethylamine, tributylamine, pyridine, N,N-dimethylaniline, lutidine, and collidine. The amount of the additional reagents that aid in water removal is preferably at least 4 equivalents of anhydride and 2 equivalents of amine per equivalent of polyamic acid to be condensed.

The degree of imidization of each polymer used in the liquid crystal alignment agent of the present invention can be arbitrarily adjusted by controlling the amount of catalyst, reaction time and reaction temperature used to prepare the polymer. In this specification, the "degree of imidization" of a polymer refers to the ratio (expressed in %) of the number of repeating units of the polymer forming an imide ring or an isoimine ring to the total number of repeating units of the polymer. In this specification, the degree of imidization of a polyamic acid that is not dehydrated and ring-closed is 0%. The degree of imidization of each polymer is determined as follows: the polymer is dissolved in deuterated dimethyl sulfoxide, and the resulting solution is subjected to ¹ H-NMR measurement using tetramethylsilane as a standard substance at room temperature, and calculated from the following formula.

Imidization degree (%) = 1-(A ¹ /A ² × B) × 100

^A1 : Peak area based on protons of NH groups (around 10 ppm)

A ² : Peak area based on one proton of the acrylate double bond (around 6.5 ppm).

B: Ratio of the number of acrylate protons to one proton of the NH group in the polymer precursor

The degree of imidization is usually 1-99%, preferably 5-50%, more preferably 10-40%.

The present invention relates to a process for the preparation of polymers, copolymers or oligomers comprising the polymerization of a diamine (I).

Preferably, the polymerization of diamine (I) comprises

a) amidating at least one diamine (I) to form a polyamic acid or polyamic acid ester, and

b) imidizing the obtained polyamic acid or ester to form polyimide, or

c) Imidizing the diamine (I) to form a polyimide.

In a more preferred embodiment of the present invention, the polymerization of the diamines comprises amidation and/or imidization of at least one diamine (I) with tetracarboxylic anhydride, preferably tetracarboxylic anhydride (V), preferably by elevated temperature.

In a more preferred embodiment of the present invention, the polymerization of the diamine comprises amidation and/or imidization of the diamine (I) with tetracarboxylic anhydride, preferably tetracarboxylic anhydride (V), preferably by elevated temperature, and wherein the amidation and/or imidization is optionally carried out as follows given above.

- in the presence of additives, and/or

- in the presence of another diamine different from the general formula (I), preferably in the presence of at least one diamine (L) and/or

in the presence of another polymer, copolymer or oligomer comprising a diamine (L) as a basic building block, or another polymer, copolymer or oligomer other than polyamic acid, polyamic acid ester or polyimide, more preferably another polymer, copolymer or oligomer selected from the group consisting of polymers including polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyvinyl ethers and polyvinyl esters, polyallyl ethers and esters, polystyrenes, polysiloxanes, polyimides, polyamic acids and their esters, polyamideimides, polymaleic acid, polyfumaric acid, polyurethanes and their derivatives.

Preferably, the further polymer, copolymer or oligomer comprises as basic building blocks a diamine (L) and a tetracarboxylic anhydride, preferably a tetracarboxylic anhydride of the general formula (V).

This polymer, copolymer or oligomer is prepared analogously to the polymer, copolymer or oligomer of the invention comprising diamine (I). The imidization is carried out after or during the amidation. Generally, the imidization is carried out after the amidation.

Partial imidization of polyamic acid or polyamic acid ester is preferred.

If the polymer is to be prepared solely by imination, the diamine (I) will be contacted with an iminating compound containing at least two polymerisable functional groups, such as carbonyl or halogen groups.

More preferably, the present invention relates to a process for the preparation of polymers, copolymers or oligomers comprising polymerizing a diamine (I) and a tetracarboxylic anhydride, preferably a tetracarboxylic anhydride (V).

Another embodiment of the present invention relates to copolymers comprising diamines (I). Preferred are copolymers comprising at least two diamines (I).

Another embodiment of the present invention relates to polymers, copolymers or oligomers, or blends obtainable according to the process and preferred processes of the present invention.

Preferably, the blend is obtainable by reacting at least two different diamines (I) or by reacting at least one diamine (I) with a polymer, copolymer or oligomer comprising at least one diamine (L) as basic building block.

Preferably, the present invention relates to polymers, copolymers or oligomers comprising at least one photoreactive group in their polymer, copolymer or oligomer side chain. Preferably, the photoreactive group of the side chain is photoisomerized and/or crosslinked, more preferably photodimerized, by exposure to collimated light.

The term photoreactive group has the meaning of a group which is capable of reacting by interaction with light.

The treatment with the collimated light can be performed in a single step or in several separate steps.In a preferred embodiment of the invention, the treatment with the collimated light is performed in a single step.

In the context of the present invention, photoreactive groups preferably have the meaning of dimerizable, isomerizable, polymerizable and/or crosslinkable groups.

In the context of the present invention, alignment light is light having a wavelength that can induce photoalignment. Preferably, the wavelength is in the UV-A, UVB, and/or UV/C range, or in the visible range. Which wavelength is suitable depends on the photoaligning compound. Preferably, the photoreactive group is sensitive to visible and/or UV light. Another embodiment of the present invention involves generating the alignment light by laser.

The instantaneous direction of the collimated light can be perpendicular to the substrate or at any oblique angle.

To generate the tilt angle, preferably the collimated light is emitted from an oblique angle.

More preferably, the collimating light is at least partially linearly polarized, elliptically polarized, such as circularly polarized, or unpolarized; most preferably, it is at least circularly or partially linearly polarized light, or unpolarized light emitted at an angle. In particular, the most preferred collimating light is significantly polarized light, in particular linearly polarized light; or the collimating light is unpolarized light applied by oblique radiation.

In a more preferred embodiment of the present invention the polymer, copolymer or oligomer is treated with polarized light, in particular linearly polarized light, or by oblique irradiation with unpolarized light.

Further preferred are the polymers, copolymers or oligomers of the present invention,

- wherein at least 30%, preferably at least 75%, of the repeating units comprise a side chain comprising a photoreactive group; and/or

- wherein the photoreactive group is capable of photodimerization, preferably photocyclization, especially [2+2] photocyclization; and/or

- wherein the polymer or oligomer is a polymer gel or a polymer network, or an oligomer gel or an oligomer network, respectively; and/or

- wherein the polymer, copolymer or oligomer has an intrinsic viscosity of 0.05-10 dL/g, preferably 0.05-5 dL/g; and/or

- wherein the polymer, copolymer or oligomer comprises 2 to 2000 repeating units, in particular 3 to 200 repeating units; and/or

- wherein the polymer, copolymer or oligomer is in the form of a homopolymer or a copolymer, preferably in the form of a statistical copolymer; and/or

- wherein the polymer, copolymer or oligomer is cross-linkable or cross-linked;

Another preferred embodiment of the present invention relates to polymers, copolymers or oligomers having an intrinsic viscosity of preferably 0.05 to 10 dL/g, more preferably 0.05 to 5 dL/g. The intrinsic viscosity (ηinh = Inηrel/C) is determined by measuring a solution containing the polymer or oligomer at a concentration of 0.5 g/100 ml of solution using N-methyl-2-pyrrolidone as a solvent to assess its viscosity at 30°C.

Furthermore, a preferred embodiment of the present invention relates to polymers, copolymers or oligomers comprising 2 to 2000 repeating units, in particular 3 to 200 repeating units.

The side chain polymers or oligomers according to the present invention can exist in the form of homopolymers as well as copolymers. The term "copolymer" should be understood to refer in particular to statistical copolymers.

In addition, the present invention relates to compositions, in particular blends, comprising

- a polymer, copolymer or oligomer according to the definition and preference of the present invention, which comprises at least a diamine (I) as an essential building block, or

- a polymer, copolymer or oligomer according to the definition and preference of the present invention, obtainable by the process of the present invention, and

Preferably, it further comprises a further diamine different from diamine (I), preferably diamine (L).

The alternative polymers, copolymers or oligomers comprising a diamine (L) as a basic building block have the same preferences as given above.

Preferably, the present invention relates to a composition, in particular a blend, comprising

- a polymer, copolymer or oligomer according to the definition and preference of the present invention, which comprises at least a diamine (I) as an essential building block, or

- polymers, copolymers or oligomers according to the definitions and preferences of the present invention, obtainable by the process of the present invention,

- and/or another polymer, copolymer or oligomer comprising as a basic building block another diamine different from diamine (I), preferably diamine (L), or another polymer, copolymer or oligomer different from polyamic acid, polyamic ester or polyimide, more preferably another polymer, copolymer or oligomer selected from the group consisting of polyacrylates, polystyrenes, polyesters, polyurethanes, polyethylenes, polypropylenes, polyvinyl chlorides, polytetrafluoroethylenes, polycarbonates, polyterephthalates and dendrimers.

Further preferably, the present invention relates to a composition, in particular a blend, comprising

- a polymer, copolymer or oligomer according to the definition and preference of the present invention, which comprises at least a diamine (I) as an essential building block, or

- polymers, copolymers or oligomers according to the definitions and preferences of the present invention, obtainable by the process of the present invention,

- and optionally, another diamine different from diamine (I), preferably diamine (L),

- and additives, preferably silane-containing compounds,

- and/or another polymer, copolymer or oligomer comprising as an essential building block another diamine different from the diamine (I), preferably at least one diamine (L),

- and/or another polymer, copolymer or oligomer different from polyamic acid, polyamic acid ester or polyimide, more preferably another polymer, copolymer or oligomer selected from the group consisting of polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyvinyl ethers and polyvinyl esters, polyallyl ethers and esters, polystyrenes, polysiloxanes, polyimides, polyamic acids and their esters, polyamideimides, polymaleic acid, polyfumaric acid, polyurethanes and their derivatives.

- and/or photoactive polymers, photoactive oligomers and/or photoactive monomers,

- and/or a cross-linking agent, preferably an epoxy-containing cross-linking agent, most preferably selected from: 4,4'-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N'-diglycidyl diimide, polyethylene glycol diglycidyl ether, N,N-diglycidylcyclohexylamine.

The polymers or oligomers according to the present invention can be used as a single polymer or oligomer layer or in combination with other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers, and/or photoactive monomers, depending on the application to which the polymer or oligomer layer is to be added. It will be appreciated that by varying the composition of the polymer or oligomer layer, it is possible to control specific and desired properties, such as induced pretilt angle, good surface wetting, high voltage retention, specific binding energy, and the like.

Polymer or oligomer layers can be readily prepared from the polymers or oligomers of the present invention, and another embodiment of the present invention relates to polymer or oligomer layers comprising the polymers or oligomers of the present invention, preferably prepared by treatment with collimated light. Preferably, the present invention relates to polymer or oligomer layers comprising the polymers or oligomers of the present invention in crosslinked and/or isomerized form.

The polymer or oligomer layer is preferably produced by applying one or more polymers or oligomers according to the invention to a support and, after or without imidization, treating the polymer or oligomer or polymer mixture or oligomer mixture, preferably crosslinking and/or isomerizing, by irradiation with collimated light.

Generally, a transparent support is used, such as a glass or plastic substrate, which is optionally coated with indium tin oxide (ITO).

Furthermore, it is possible to alter the orientation and tilt angle within a polymer or oligomer layer by controlling the direction of the collimated light. It will be appreciated that by selectively irradiating specific regions of a polymer or oligomer layer, it is possible to align very specific regions of the layer. This allows for the provision of a layer with a defined tilt angle. The induced orientation and tilt angle in the polymer or oligomer layer can be maintained by methods, particularly crosslinking.

A process for preparing polymers, copolymers or oligomers according to the invention, wherein a diamine (I) is reacted with one or more tetracarboxylic anhydrides of the general formula (V), optionally in the presence of one or more further diamines, in a polycondensation reaction.

Furthermore, the present invention preferably relates to a process in which the polycondensation reaction for preparing the polyamic acid is carried out in solution in a polar aprotic organic solvent selected from the group consisting of gamma-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethylformamide.

Preferably, the invention relates to a process in which the polycondensation ring formation is carried out thermally with removal of water in the formation of the polyimide.

More preferably, the present invention relates to a process wherein the imidization is carried out before or after coating the polymer, copolymer or oligomer onto the support. Other preferred processes of the present invention relate to

- a method for preparing a vertically aligned polymer or oligomer layer;

- Method for preparing multi-domain vertical alignment of polymer or oligomer layers;

- A method for producing a polymer layer or oligomer layer having a tilted optical axis.

Another embodiment of the present invention relates to a polymer, copolymer or oligomer layer, especially an orientation layer, comprising at least one polymer, copolymer or oligomer according to the present invention.

It should be understood that the polymer or oligomer layer of the present invention (in the form of a polymer gel, polymer network, polymer film, etc.) can also be used as an alignment layer for liquid crystals. Another preferred embodiment of the present invention relates to an alignment layer comprising one or more polymers or oligomers according to the present invention, preferably in crosslinked form. Such an alignment layer can be used to produce unstructured or structured optical or electro-optical elements, preferably hybrid layer elements.

Furthermore, the present invention relates to a process for producing a polymer or oligomer layer, wherein one or more polymers, copolymers or oligomers according to the invention are applied to a support, preferably from a solution of the polymeric or oligomeric material, followed by evaporation of the solvent, and wherein, after any imidization step which may be necessary, the polymer or oligomer or polymer mixture or oligomer mixture is treated with collimated light, preferably by irradiation with collimated light, to effect isomerization and/or crosslinking.

A preferred method of the present invention relates to a method wherein the orientation and tilt angle within a polymer or oligomer layer is changed by controlling the direction of irradiation using collimated light and/or wherein specific areas of the polymer or oligomer layer are aligned by selectively irradiating specific areas of the layer.

The alignment layer is suitably prepared from a solution of a polymer or oligomer material. The polymer or oligomer solution is applied to a support, optionally coated with an electrode, such as a glass plate coated with indium tin oxide (ITO), to obtain a homogeneous layer 0.05 to 50 μm thick. In this process, various coating techniques can be used, such as spin coating, meniscus coating, line coating, slot coating, offset printing, flexographic printing, and gravure printing. Subsequently, or optionally after a prior imidization step, the area to be aligned is irradiated, for example, with a high-pressure mercury vapor lamp, a xenon lamp, or a pulsed UV laser, using a polarizer and, optionally, a mask for generating a structured image.

Furthermore, the present invention relates to the use of a polymer layer, copolymer or oligomer layer according to the invention, preferably in crosslinked form, as an orientation layer for liquid crystals.

Furthermore, the present invention preferably relates to the use of a polymer layer, copolymer or oligomer layer for inducing homeotropic alignment of an adjacent liquid crystal layer, in particular for operating the cell in MVA mode.

The irradiation time depends on the output of the individual lamps and can be from a few seconds to a few hours. However, the photoreactions (dimerization, polymerization, crosslinking) can also be carried out by irradiating the homogeneous layer using, for example, a filter that only allows the radiation suitable for the crosslinking reaction to pass.

It will be appreciated that the polymer or oligomer layers of the invention can be used to prepare optical or electro-optical devices having at least one orientation layer and to prepare unstructured and structured optical elements and multilayer systems. The invention relates to the use of polymer, copolymer or oligomer layers as orientation layers for liquid crystals.

It is preferably used to induce vertical alignment of adjacent liquid crystal layers.

Another embodiment of the present invention relates to an optical or electro-optical device comprising one or more polymers or oligomers according to the present invention in cross-linked form. The electro-optical device may comprise more than one layer. The layer, or each layer, may comprise one or more regions having different spatial orientations.

Preferably, the invention relates to optical and electrooptical unstructured or structured elements, preferably liquid crystal display cells, multilayer and hybrid layer elements, which comprise at least one polymer layer, copolymer or oligomer layer according to the invention.

More preferably, the present invention relates to an orientation layer comprising at least one polymer layer, copolymer layer or oligomer layer according to the present invention.

The advantages of the present invention could not have been anticipated by a skilled artisan. Surprisingly, it was discovered that the introduction of organic fluorine groups into the peripheral positions of the side groups of polymers with a specific molecular structure, in addition to the polyamic acid/polyimide backbone, plays a significant role in obtaining MVA materials with optimized properties, such as the required high voltage holding ratio, the adjustable pretilt angle required for MVA mode, and their stability to light and heat.

The present invention also specifically relates to the following embodiments:

1. Diamine compound of general formula (I):

in,

A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring containing 5 or 6 atoms, two adjacent monocyclic rings containing 5 or 6 atoms, a bicyclic ring system containing 8, 9 or 10 atoms or a tricyclic ring system containing 13 or 14 atoms; and

The following compound residues of general formula (I), namely compounds of general formula (Ia)

represents a linear or branched C ₁ -C ₁₆ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 15,

B represents a straight-chain or branched C ₁ -C ₁₆ alkyl group which, apart from its fluorine substituent, is unsubstituted or substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may independently be replaced by a linking group;

D represents an unsubstituted or substituted aliphatic, aromatic and/or alicyclic diamine radical containing 1 to 40 carbon atoms,

E represents an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N(C ₁ -C ₆ alkyl)-, -CR ² R ³ , wherein R ² and R ³ are independently hydrogen or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl group, wherein one or more -CH ₂ - groups may be replaced independently by a linking group, and with the proviso that at least one of R ² and R ³ is not hydrogen;

S ¹ and S ² each independently represent a spacer unit;

X and Y each independently represent hydrogen, fluorine, chlorine, cyano, unsubstituted or fluorine-substituted C ₁ -C ₁₂ alkyl, wherein one or more -CH ₂ - groups may be replaced by a linking group;

n and n1 each independently represent 1, 2, 3 or 4, provided that if n is 2, 3 or 4, each A, B, _x1 , D, E, ^S1 , ^S2 , X, Y is the same or different; if n1 is 2, 3 or 4, each B, _x1 is the same or different.

2. The diamine compound according to embodiment 1, wherein the linking group is selected from -O-, -CO, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ -, -CH=CH-, -C≡C-, -O-CO-O-, and -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms of the linking group are not directly connected to each other.

3. The diamine compound according to embodiment 1, wherein the spacer unit is a single bond, a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ - groups can be replaced independently of each other by the linking group described in embodiment 2 and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via a bridging group.

4. The diamine compound according to embodiment 3, wherein the bridging group is selected from -CH(OH)-, -CO-, -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -OCO-, -COCF ₂ -, -CF ₂ CO, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -O-CO-O, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH＝CH-, -C≡C-, -CH＝CH-COO-, -OCO-CH＝CH-, -CH＝N-, -C(CH ₃ )＝N-, -N＝N- or a single bond; or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ The - groups can be replaced independently of one another by the linking groups described in embodiment 2 independently of one another.

5. The diamine compound according to any one of the above embodiments, wherein

D is preferably selected from the general formula (III):

H(R ⁵ )N-(Sp ¹ ) _k1 -(X ¹ ) _tt -(Z ³ -C ³ ) _a3 -(Z ⁴ -C ⁴ ) _a4 -(X ² ) _t2 -(Sp ² ) _k2 -N(R ⁶ )H (III)

in:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

Sp ¹ and Sp ² each independently represent an unsubstituted or substituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be replaced by a linking group independently of each other, and

k ¹ , k ² are each independently an integer having a value of 0 or 1; and

X ¹ and X ² each independently represent a linking spacer, and

t ¹ , t ² are each independently an integer having a value of 0 or 1; and

C ³ and C ⁴ each independently represent a non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group, which may have a side chain T, and

Z ³ represents a bridging group; and

Z ⁴ represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups; and/or heteroatoms and/or bridging groups; and

a3 and a4 are independently integers from 0 to 3, satisfying a3+a4≤4; and

wherein D is connected at least once to at least one group S ¹ in the general formula (I) via a group Sp ¹ and/or a group Sp ² ; and/or is connected via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of C ³ and/or a group C ⁴ , and/or is connected via at least one side chain T of a group C ⁴ and/or a group C ³ ; and/or is connected via a group Z ⁴ ; and at least one of k ¹ , k ² , a ³ and a ⁴ is not equal to zero; and wherein

The linking group is as defined in embodiment 2, and the bridging group is as defined in embodiment 4.

6. The diamine compound according to embodiment 5, wherein the side chain T represents a substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be replaced independently of one another by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, or heteroatoms and/or bridging groups, which are connected at least once to at least one group S ¹ in the general formula (I) described in embodiment 1.

7. The diamine compound according to embodiments 5 and 6, wherein

C ³ and C ⁴ are independently selected from the group G ² , wherein G ² is:

in:

"-" represents the bond connecting C ³ and C ⁴ to the adjacent groups of the compound of general formula (III) described in Embodiment 5; and

L is -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, -NR ⁵ R ⁶ , CH ₂ ═C(CH ₃ )-(CO)O-, CH ₂ ═C(CH ₃ )-O-, wherein:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

T represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups may be replaced independently of one another by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or a bridging group;

m is an integer from 0 to 2;

u1 is an integer from 0 to 4, provided that m+u1≤4; and

u2 is an integer from 0 to 3, provided that m+u2≤3; and

u3 is an integer from 0 to 2; the condition is m+u3≤2.

8. The diamine compound according to any one of the above embodiments, wherein D is selected from the following compounds:

in

L, L ₁ , L ₂ and L ₃ are independently -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, -NR ⁵ R ⁶ , CH ₂ ═C(CH ₃ )-(CO)O- or CH ₂ ═C(CH ₃ )-O-,

T, T ₁ , T ₂ and T ₃ are independently substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkylene groups, wherein one or more -CH ₂ - groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, and/or heteroatoms and/or bridging groups;

"-" is a single bond,

q is an integer of 1 or 2; and

q1, q2 and q3 are independently integers from 0 to 2;

m is an integer of 1 or 2;

m1, m2 and m3 are independently integers from 0 to 2;

u3, u3' and u3" are independently integers from 0 to 2;

R ⁵ , R ⁶ and Z ⁴ are as described above; wherein

D is connected at least once to at least one group S ¹ in the general formula (I) described in embodiment 1 via a single bond "-"; or via a side chain T, T ₁ , T ₂ or T ₃ ; or via a group Z ⁴ ;

The condition is

u3+q or u3+m≤4;

u3+q1 and/or u3'+q2 or/and u3+ml, or/and u3'+m2, or/and u3"+q3, or/and u3"+m3≤4; q1+q2 and ml+m2 and q1+q2+q3 and ml+m2+m3≥1.

9. The diamine compound according to any one of the above embodiments, wherein the following compound residue of the compound of formula (I) described in embodiment 1 is

represents a linear or branched C ₁ -C ₁₆ fluoroalkyl group having a terminal unit selected from -CF ₂ H and -CF ₃ .

10. The diamine compound according to any one of the above embodiments, wherein

S ¹ and S ² each independently represent a single bond or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ - groups may be independently replaced by a linker, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of the general formula (IV):

-(Z ¹ -C ¹ ) _a1 -(Z ² -C ² ) _a2 -(Z ^1a ) _a3 - (IV)

in:

C ¹ and C ² each independently represent a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and

Z ¹ , Z ² , and Z ^1a each independently represent a bridging group, and

a1, a2, and a3 each independently represent an integer of 0-3, a1+a2+a3≤6, wherein the bridging groups Z ¹ , Z ^1a , and Z ² are as described in the fourth embodiment.

11. The diamine compound according to any one of the above embodiments, which is a compound of the general formula (VI), (VII), (VIII), (IX), (X), (XI), (XIa) and (XIb)

in

A, B, x ₁ , n, n1, D, E, S ² , S ¹ , X and Y have the meanings given above in embodiment 1, R ⁵ , R ⁶ and Z ⁴ have the same meanings as in embodiment 5;

L is -CH ₃ , -OCH ₃ , -COCH ₃ , nitro, cyano, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, CH ₂ ═C(CH ₃ )-(CO)O- or CH ₂ ═C(CH ₃ )-O-,

u3 is an integer from 0 to 2.

12. The diamine compound according to any one of the above embodiments, which is a compound of formula (XII)

wherein x ₁ , B, n, n1, D, E, S ¹ , X and Y have the meanings given above in embodiment 1,

and ^Z1 have the same meanings as in Embodiment 10, and L, u1 and u2 have the same meanings as in Embodiment 7.

13. The diamine compound according to any one of the above embodiments, selected from

wherein S ¹ has the meaning given in the above embodiment, wherein the following compound residue

represents a linear or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine, and

_x1 is an integer from 1 to 9,

B represents a straight-chain or branched C ₁ -C ₈ alkyl group, which is unsubstituted or, except for its fluorine substituent, is substituted by di-(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₆ alkoxy, nitro, cyano and/or chlorine; and wherein one or more -CH ₂ - groups may be independently replaced by a linker selected from the group consisting of: -O-, -CO-, -CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ - and -CH=CH-, wherein:

R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group; provided that the oxygen atoms are not directly bonded to each other; and wherein the C ₁ -C ₈ fluoroalkyl group has a terminal unit selected from -CF ₂ H, -CF ₃ .

14. A polymer, copolymer or oligomer comprising a diamine (I) according to any one of the above embodiments as an essential building block.

15. The polymer, copolymer or oligomer according to embodiment 14, which is a polyamic acid, a polyamic acid ester, a polyimide or a mixture of a polyamic acid and a polyamic acid ester and/or a polyimide.

16. A method for preparing the diamine compound (XII) as defined in embodiment 12, comprising:

Contact with a dinitro compound of formula (XVI)

The obtained dinitro compound of general formula (XVIa) is then converted into the corresponding diamino compound of general formula (XII)

wherein F, _x1 , n1, n, B, D, X, Y, ^Z1 , L, u1, u2 and ^S1 have the same meanings as in embodiment 11, wherein D1 has the same meaning as D in embodiment 7, with the proviso that the two amino groups of D are replaced by two nitro groups.

17. The compound of formula (XIV) and the compound of formula (XVIa) as defined in embodiment 16.

18. Composition comprising at least one diamine (I) and optionally at least one further diamine different from (I) and/or additives.

19. A process for the preparation of a polymer, copolymer or oligomer comprising the polymerization of a diamine (I).

20. A polymer, copolymer or oligomer obtainable by the reaction according to embodiment 19, comprising the diamine compound (I) according to any one of the above embodiments.

21. A polymer, copolymer or oligomer according to embodiment 20 or prepared according to embodiment 19 which is a polymer gel or a polymer network, a copolymer gel or a copolymer network or an oligomer gel or an oligomer network.

22. A polymer, copolymer or oligomer according to any one of embodiments 20 or 21 or prepared according to embodiment 19, which is capable of photocyclization.

23. A composition, in particular a blend, comprising:

a polymer, copolymer or oligomer comprising at least the diamine (I) according to embodiment 1 as an essential building block, or

- a polymer, copolymer or oligomer obtainable according to embodiment 20.

24. A process for the preparation of a polymer, copolymer or oligomer according to any one of embodiments 20 or 22 or prepared according to embodiment 19, wherein in a polycondensation reaction, the diamine (I) according to embodiment 1 is reacted with one or more tetracarboxylic anhydrides, optionally in the presence of one or more additional diamines.

25. A polymer, copolymer or oligomer layer comprising at least one polymer, copolymer or oligomer according to any one of embodiments 20 or 22 or prepared according to embodiment 19.

26. A method for producing a polymer or oligomer layer, wherein one or more polymers, copolymers or oligomers according to any one of embodiments 20 or 22 or produced according to embodiment 19 are applied to a support, and wherein the polymer or oligomer or polymer mixture or oligomer mixture is treated with collimated light.

27. A polymer, copolymer or oligomer layer obtainable by a process according to embodiment 26.

28. Optical and electro-optical unstructured or structured components, preferably liquid crystal display cells, multilayer and mixed layer components, comprising at least one polymer layer, copolymer or oligomer layer according to embodiment 27.

29. An orientation layer comprising at least one polymer layer, copolymer or oligomer layer according to embodiment 27.

Example 1

synthesis

Preparation of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid

1. Preparation of 14-(4,4,4-trifluorobutoxy)benzoic acid

55.00 g (0.408 mol) of 4,4,4-trifluorobutan-1-ol was dissolved in 550 ml of tetrahydrofuran, and 142 ml (0.102 mol) of triethylamine was added at room temperature. 38 ml (0.490 mol) of methanesulfonyl chloride was added dropwise under nitrogen. The mixture was stirred at 0-5°C for 1 hour. The beige suspension was Hyflo-filtered and washed with tetrahydrofuran. The filtrate was concentrated. The residue was dissolved in 1.4 liters of 1-methyl-2-pyrrolidone, and 62.70 g (0.408 mol) of methyl 4-hydroxybenzoate and 226.00 g (1.43 mol) of potassium carbonate were added to the light brown solution. The reaction suspension was allowed to react at 80°C for 14 hours. 1 liter (1.0 mol) of 1N NaOH solution was added to the above mixture. The suspension was heated at reflux for 30 minutes until the reaction was complete. The reaction mixture was allowed to cool at room temperature and poured into cold water. The solution was carefully acidified with 25% hydrochloride solution and stirred for 15 minutes. The product was filtered, washed with water, and dried under vacuum at room temperature overnight to yield 99.00 g (98%) of 4-(4,4,4-trifluorobutoxy)benzoic acid as a white solid.

1. Preparation of 2-4-formylphenyl-4-(4,4,4-trifluorobutoxy)benzoate

6.89 g (56.4 mmol) of 4-hydroxybenzaldehyde, 14.0 g (56.4 mmol) of 4-(4,4,4-trifluorobutoxy)benzoic acid, and 0.69 g (5.6 mmol) of 4-dimethylaminopyridine were dissolved in 100 ml of dichloromethane. 11.89 g (62.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 hour and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Crystallization from 2-propanol at 0°C yielded 17.1 g of 4-formylphenyl-4-(4,4,4-trifluorobutoxy)benzoate as colorless crystals.

1. Preparation of 3-(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid

5.00 g (14.2 mMol) of 4-formylphenyl 4-(4,4,4-trifluorobutoxy)benzoate and 3.00 g (28.4 mMol) of malonic acid were dissolved in 18 ml (227.1 mMol) of pyridine. 1.21 g (14.2 mMol) of piperidine was added to the suspension, which was allowed to react at 100°C under argon for 1.5 hours. The yellow solution was then poured onto ice. The solution was carefully acidified to a pH of 1-2 with 25% hydrochloride solution and stirred for 15 minutes. The product was filtered off and dried under vacuum at room temperature for 10 hours to obtain 5.2 g of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid as a white powder.

(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylic acid was prepared similarly to Example 1 using 4,4,5,5,5-pentafluoropentan-1-ol instead of 4,4,4-trifluorobutan-1-ol.

The following acrylic acid was synthesized similarly:

(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(2,2,2-trifluoropropoxy)benzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylic acid

(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylic acid

Example 2

synthesis

Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

2.1 Preparation of (2E)-3-{4-[(ethoxycarbonyl)oxy]phenyl}acrylic acid

67 g (0.41 mol) of p-coumaric acid was added to a mixture of 50.4 g (0.90 mol) of potassium hydroxide and 600 ml of water. 53.1 g (0.50 mol) of ethyl chloroformate was added dropwise at 0°C. The reaction temperature was raised to 10°C. The reaction mixture was then allowed to react at 25°C for 2 hours and acidified to pH 1 with 200 ml of 7N hydrochloric acid. The product was filtered off, washed with water, and dried in vacuo to obtain 95.3 g of (2E)-3-{4-[(ethoxycarbonyl)oxy]phenyl}acrylic acid as a white powder.

2.2 Preparation of 6-hydroxyhexyl 3,5-dinitrobenzoate

357.70 g (1.686 mol) of 3,5-dinitrobenzoic acid was suspended in 750 ml of 1-methyl-2-pyrrolidone. The suspension was stirred until 50°C. 386.36 g (4.599 mol) of sodium bicarbonate was added, and the mixture was heated to 90°C. 22.50 g (0.150 mol) of sodium iodide and 204.0 ml (1.533 mol) of 6-chlorohexanol were added to the reaction mixture, which was heated to 100°C for 1 hour. After 1 hour of reaction, the reaction was complete, and the orange suspension was poured onto 2 liters of ice and 1 liter of water. The product was filtered, washed with water, and dried under vacuum at 50°C for 24 hours to obtain 425.0 g (91%) of 6-hydroxyhexyl 3,5-dinitrobenzoate as a rose powder.

2.3 Preparation of 6-[(((2E)-{4-[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl diaminobenzoate

Dissolve 4.53 g (0.0145 mol) of 6-hydroxyhexyl 3,5-dinitrobenzoate, 3.44 g (0.0145 mol) of 4-ethyl carbonate cinnamic acid, and 0.177 g (0.0015 mol) of 4-dimethylaminopyridine in 40 ml of dichloromethane. Add 3.04 g (0.0159 mol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) at 0°C. Stir the solution at 0°C for 1 hour and allow it to stir overnight at room temperature. After 22 hours at room temperature, partition the reaction mixture between dichloromethane and water; wash the organic phase repeatedly with water, dry over sodium sulfate, filter, and concentrate by rotary evaporation. Dissolve the residue in ethyl acetate. Precipitate the product with hexane at 0°C. The precipitate was filtered and dried under vacuum overnight to give 4.2 g (55%) of 6-[((2E)-{4[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate as a light yellow powder.

2.4 Preparation of 6-[(((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

43.20 g (0.081 mol) of 6-[((2E)-{4[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate were dissolved in 66 ml (0.815 mol) of pyridine and 400 ml of acetone at room temperature. 61 ml (0.815 mol) of 25% ammonium hydroxide solution were added dropwise to the solution at room temperature. After a reaction time of 12 h, the mixture was poured onto water and acidified by adding 25% hydrochloride (to pH = 3-4). A paste was obtained, which was filtered, dissolved in ethyl acetate and extracted with water. The organic phase was dried over sodium sulfate, filtered and concentrated by rotary evaporation. The residue was filtered on silica gel using tert-butyl methyl ether as eluent and crystallized from 200 ml of ethyl acetate and 1200 ml of hexane at 0°C to obtain 15.84 g of 6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate as yellow crystals.

2.5 Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

8.61 g (0.0347 mol) of 4-(4,4,4-trifluorobutoxy)benzoic acid was suspended in 100 ml of dichloromethane. 0.42 g (0.0035 mol) of 4-dimethylaminopyridine was added at room temperature. 7.98 g (0.04163 mol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) was added at 0°C. The solution was stirred at 0°C for 1 hour. 15.90 g (0.0347 mol) of 6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate dissolved in 50 ml of dichloromethane was added dropwise at 0°C and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The mixture was acidified with 25% hydrochloride. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 600 g of silica gel using toluene:ethyl acetate (99:1) as eluent and crystallized from ethyl acetate/hexane (1:2) to give 18.82 g (79%) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate as white crystals.

2.6 Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

18.80 g (0.027 mol) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate was dissolved in a mixture of 350 ml of N,N-dimethylformamide and 25 ml of water. 44.28 g (0.164 mol) of ferric chloride hexahydrate were added. 17.85 g (0.273 mol) of zinc powder were added portionwise over 40 min. The mixture was allowed to react for 2 h. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 400 g of silica gel using toluene:ethyl acetate (2:1) as eluent to give 15.39 g (91%) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate as pale yellow crystals.

The following diamines were synthesized similarly:

2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate.

3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate.

4-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.

5-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate.

8-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate.

11-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate.

2-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate.

3-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate.

4-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.

5-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate.

8-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate.

2-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate.

3-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate.

4-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.

5-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.

6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate.

4-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.

5-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate.

8-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate.

11-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate.

2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

5-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

5-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(3-methoxy-4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(3-methoxy-4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate

8-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

2-{2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate

2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

2-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

3-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

4-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

5-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

7-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate.

8-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

11-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-{[(4,4,4-trifluorobutoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-{[(4,4,5,5,5-pentafluoropentyloxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

6-{[((2E)-3-{4-[(4-({[(4,4,5,5,6,6,6-heptafluorohexyloxy)carbonyl]amino})benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Example 3

synthesis

Preparation of 3,5-diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

3.1 Preparation of 3,5-dinitrobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

1.00 g (51.0 mmol) of 3,5-dinitrobenzyl alcohol, 2.00 g (51.0 mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid, and 62 mg (0.51 mmol) of 4-dimethylaminopyridine were dissolved in 10 ml of dichloromethane. 1.07 g (56.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) was added at 0°C. The solution was stirred at 0°C for 1 hour and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation to give 2.1 g of 3,5-dinitrobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate as colorless crystals.

3.2 Preparation of 3,5-diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

5.30 g (9.22 mmol) of (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate was dissolved in a mixture of 55 ml of N,N-dimethylformamide and 6 ml of water. 14.98 g (55.3 mmol) of ferric chloride hexahydrate was added. 6.03 g (91.8 mmol mol) of zinc powder was added portionwise over 40 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 200 g of silica gel using toluene:ethyl acetate (1:1) as eluent and crystallized from an ethyl acetate:hexane mixture to give 3.8 g of 3,5-diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate as pale yellow crystals.

The following diamines were synthesized similarly:

3,5-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,3,3,3-pentafluoropropoxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyloxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5-pentafluorobenzoyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyl)oxy]phenyl}acrylate

3,5-Diaminobenzyl (2E) 3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyloxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5-pentafluorobenzoyloxy)benzoyl)oxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyloxy]phenyl}acrylate

2,5-Diaminobenzyl (2E) 3-{4-[(2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl]oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5-pentafluorobenzoyloxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyl)oxy]phenyl}acrylate

2,4-Diaminobenzyl (2E) 3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Example 4

synthesis

Preparation of 2-(2,4-aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

4.1 Preparation of 2-(2,4-dinitrophenyl)ethanol

22.6 g (100 mmol) of 2,4-dinitrophenylacetic acid was dissolved in 150 ml of tetrahydrofuran and added dropwise over 2 hours to 300 ml (300 mmol) of a 1.0 M solution of borane-tetrahydrofuran complex in tetrahydrofuran. After 3 hours at 25°C, 200 ml of water was carefully added. The reaction mixture was then partitioned between ethyl acetate and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 400 g of silica gel using a 1:1 toluene:ethyl acetate mixture as the eluent and crystallized from an ethyl acetate:hexane mixture to yield 20.7 g (98%) of 2-(2,4-dinitrophenyl)ethanol as pale yellow crystals.

4.2 Preparation of 2-(2,4-dinitrophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 5.24 g (11.8 mmol) of (2E)-3-(4-{[4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl]oxy}phenyl)acrylic acid and 144 mg (1.2 mmol) of 4-dimethylaminopyridine were dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 h and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. The residue was chromatographed on 200 g of silica gel using toluene:ethyl acetate 95:5 as eluent and crystallized from an ethyl acetate:hexane mixture to give 5.35 g (71%) of 2-(2,4-dinitrophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate as colorless crystals.

4.3 Preparation of 2-(2,4-aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

5.35 g (8.38 mmol) of (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate was dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml of water. 13.9 g (51.4 mmol) of iron chloride hexahydrate was added. 5.60 g (85.7 mmol) of zinc powder was added portionwise over 60 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was filtered on 200 g of silica gel using toluene:ethyl acetate (1:3) as eluent and crystallized from an ethyl acetate:hexane mixture to obtain 3.30 g of 2-(2,4-aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate as pale yellow crystals.

2-(2,4-Aminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate was prepared analogously to Example 4 using (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid.

The following diamines were synthesized similarly:

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2-(3,5-aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-aminophenyl)ethyl (2E) 3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-aminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-aminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate

2-(3,5-Aminophenyl)ethyl (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate

2-(3,5-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,5-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,3,3-pentafluoropropyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,55,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,6,6,6-pentafluorohexyl)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3,4-bis(4,4,4-trifluorobutyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxycarbonyl)phenoxy)carbonyl]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate.

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-[(4,4,5,5,5-pentafluoropentyloxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-aminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl}acrylate

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

3-(3,5-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate

3-(2,4-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

3-(2,4-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

3-(2,4-Aminophenyl)propyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

3-(2,4-Aminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate

6-(2,4-Aminophenyl)hexyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

6-(2,4-Aminophenyl)hexyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

6-(2,4-Aminophenyl)hexyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

Example 5

synthesis

Preparation of 2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

5.1 Preparation of 2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione

15.0 g (69.4 mmol) of 4-nitrobenzyl bromide and 5.00 g (34.7 mmol) of Meldrum's acid were dissolved in 100 ml of 2-butanone. 4.40 g (104.1 mmol) of potassium carbonate were added, and the resulting suspension was heated to 50°C and allowed to react for 2.5 hours. After cooling to room temperature, 100 ml of water was added. The product was collected by filtration and washed with plenty of water. 12.3 g (85%) of 2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione was used as a light yellow powder without further purification.

5.2 Preparation of 2,2-bis(4-nitrobenzyl)malonic acid

2.185 g (52.07 mmol) of lithium hydroxide was added to a suspension of 10.79 g (26.04 mmol) of 2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione and 110 ml of a 9:1 mixture of tetrahydrofuran and water. The reaction mixture was then allowed to react at 25°C for 21.5 hours, added to 500 ml of water, and acidified to pH 1 with 20 ml of 3N hydrochloric acid. The mixture was partitioned between ethyl acetate and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue, 9.54 g (98%) of 2,2-bis(4-nitrobenzyl)malonic acid, was used as a white powder without further purification.

5.3 Preparation of 2,2-bis(4-nitrobenzyl)-1,3-propanediol

4.00 g (10.69 mmol) of 2,2-bis(4-nitrobenzyl)malonic acid was dissolved in 40 ml of tetrahydrofuran and added dropwise over 2 hours to 64.1 ml (64.1 mmol) of a 1.0 M solution of the borane-tetrahydrofuran complex in tetrahydrofuran. After 19 hours at 25°C, 50 ml of water were carefully added. The reaction mixture was then partitioned between ethyl acetate and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue, 3.77 g (97%) of 2,2-bis(4-nitrobenzyl)-1,3-propanediol, was used as a white powder without further purification.

5.4 Preparation of 2,2-bis(4-nitrobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

1.76 g (5.07 mmol) of 2,2-bis(4-nitrobenzyl)-1,3-propanediol, 4.00 g (10.14 mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid, and 124 mg (1.01 mmol) of 4-dimethylaminopyridine were dissolved in 100 ml of dichloromethane. 2.14 g (11.16 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 h and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 150 g of silica gel using toluene:ethyl acetate 9:1 as eluent to give 2.20 g of 2,2-bis(4-nitrobenzyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol as white crystals.

5.5 Preparation of 2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2.20 g (2.00 mol) of 2,2-bis(4-nitrobenzyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol were dissolved in a mixture of 25 ml of N,N-dimethylformamide and 3 ml of water. 3.25 g (12.01 mmol) of iron chloride hexahydrate were added. 1.31 g (20.02 mmol) of zinc powder were added portionwise over 40 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 100 g of silica gel using toluene:ethyl acetate 1:1 as eluent and crystallized from an ethyl acetate:hexane mixture to give 1.20 g of 2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

The following diamines were synthesized similarly:

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2,2-bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

Example 6

synthesis

Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl]benzoate

6.1 Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate

6.50 g (11.67 mmol) of 6-hydroxyhexyl 4-(6-hydroxyhexyloxy)-3,5-dinitrobenzoate, 9.67 g (24.53 mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid, and 0.290 mg (2.34 mmol) of 4-dimethylaminopyridine were dissolved in 100 ml of dichloromethane. 5.14 g (26.87 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 h and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 500 g of silica gel using toluene:ethyl acetate 95:5 as eluent and crystallized from an ethyl acetate:hexane mixture to give 7.70 g of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitro-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate as yellow crystals.

6.2 Preparation of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate

7.70 g (6.5 mol) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitro-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate are dissolved in a mixture of 90 ml of N,N-dimethylformamide and 7 ml of water. 10.6 g (39.2 mmol) of iron chloride hexahydrate are added. 4.27 g (65.36 mmol) of zinc powder are added portionwise over 40 minutes. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. The residue was chromatographed on 200 g of silica gel using toluene:ethyl acetate 2:1 as eluent and crystallized from a methanol:ethyl acetate mixture to give 4.92 g of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate as colorless crystals.

Example 7

synthesis

7.1 Preparation of 4,4'-dinitro-1,1'-biphenyl-2,2'-dicarboxylic acid

30.0 g (120.13 mmol) of biphenylcarboxylic acid was dissolved in 469 g (4.59 mol) of concentrated sulfuric acid (96%) at room temperature. The solution was cooled to -15°C, and a mixture of 92.4 g (1.011 mol) of concentrated nitric acid (69%) and 12.0 g (0.117 mol) of concentrated sulfuric acid (96%) was slowly added to maintain the mixture temperature below 0°C. After the addition, the solution was allowed to react at room temperature for 24 hours. After pouring the mixture onto crushed ice, the resulting precipitate was collected by filtration, washed with water, and dried under vacuum at room temperature for 10 hours.

7.2 Preparation of 2,2'-bis(hydroxymethyl-4,4'-dinitro-1,1'-biphenyl

3.6 g (10.83 mmol) of 4,4'-dinitro-1,1'-biphenyl-2,2'-dicarboxylic acid was dissolved in 25 ml of tetrahydrofuran, and 65 ml (65.02 mmol) of a 1.0 M solution of borane-tetrahydrofuran complex in tetrahydrofuran was added dropwise over the course of 1 hour. After 19 hours at 25°C, 50 ml of water was carefully added. After 1 hour, the solution was acidified to a pH of 1-2 with 10 ml of 1N hydrochloride solution and allowed to stir for 30 minutes. The reaction mixture was then partitioned between ethyl acetate and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue, 4.2 g of 2,2'-bis(hydroxymethyl)-4,4'-dinitro-1,1'-biphenyl, was used as a white powder without further purification.

7.3 Preparation of 2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-dinitro-1,1'-biphenyl

3.92 g (12.8 mmol) of 2,2'-bis(hydroxymethyl-4,4'-dinitro-1,1'-biphenyl, 13.20 g (33.5 mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid prepared according to Example 1 and 0.630 mg (5.15 mmol) of 4-dimethylaminopyridine were dissolved in 200 ml of dichloromethane. 6.91 g (11.16 mmol) of N,N'-dicyclohexylcarbodiimide were added at 0°C. The solution was stirred at 0°C for 2 h and allowed to stir overnight at room temperature. After 22 h at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. The mixture was then dried over 150 g of silica gel using toluene:ethyl acetate 9:1 as eluent. The residue was precipitated to obtain 12.0 g of 2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-dinitro-1,1'-biphenyl as white crystals.

7.4 Preparation of 2,2'-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2.27 g (2.14 mol) of 2,2'-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4'-dinitro-1,1'-biphenyl was dissolved in a mixture of 40 ml of N,N-dimethylformamide and 3 ml of water. 3.48 g (12.8 mmol) of iron chloride hexahydrate was added. 1.40 g (21.4 mmol) of zinc powder was added portionwise over 40 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 100 g of silica gel using toluene:ethyl acetate 7:3 as eluent to obtain 1.74 g of 2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl as pale yellow crystals.

2,2′-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4′-diamino1,1′-biphenyl was prepared using (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylic acid in analogy to Example 7.

The following diamines were synthesized similarly:

2,2'-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}propenoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl]prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl]prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

2,2'-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

Example 8

synthesis

Preparation of 2-(2,4-aminophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

8.1 Preparation of 2-(2,4-dinitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2.90 g (12.0 mmol) of 2-(4-nitrophenyl)-1,3-propanediol, 9.54 g (24.2 mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid. 296 mg (2.42 mmol) of 4-dimethylaminopyridine were dissolved in 100 ml of dichloromethane. 9.20 g (49.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 hour and allowed to stir overnight at room temperature. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 600 g of silica gel using toluene:ethyl acetate 9:1 as eluent to obtain 7.60 g of 2-(4-nitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol as white crystals.

8.2 Preparation of 2-(2,4-aminophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

7.60 g (7.64 mmol) of 2-(4-nitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol was dissolved in a mixture of 45 ml of N,N-dimethylformamide and 5 ml of water. 12.39 g (45.84 mmol) of iron chloride hexahydrate was added. 4.99 g (76.4 mmol) of zinc powder was added portionwise over 40 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 1000 g of silica gel using toluene:ethyl acetate 1:1 as eluent and crystallized from an ethyl acetate:hexane mixture to give 4.30 g of 2-(2,4-aminophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol.

The following diamines were synthesized similarly:

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-Aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2-(2,4-Aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(2,4-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(2,4-Aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(2,4-Aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

2-(3,5-aminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol

Example 9

Polymerization step A (formation of polyamic acid)

2.25 g (11.47 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added to a solution of 8.030 g (12.77 mmol) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate in 56.0 ml of tetrahydrofuran. The mixture was then stirred at 0°C for 2 hours. An additional 0.255 g (1.30 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was then added. The mixture was then allowed to react at room temperature for 21 hours. The polymer mixture was diluted with 56 ml of THF, precipitated into 2000 ml of diethyl ether, and collected by filtration. The polymer was reprecipitated from THF (160 ml) into 3500 ml of water and dried under vacuum at room temperature to obtain 9.42 g of polyamic acid 1 as a white powder; [η] = 0.50 dL/g

Similar to Example 9, polyamic acid was prepared using the following diamine and 1,2,3,4-cyclobutanetetracarboxylic dianhydride:

6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced polyamic acid 2 as white powder; [η] = 0.24 dL/g

6-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 3; [η] = 0.25 dL / g.

8-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 4; [η] = 1.09 dL / g.

4-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 5; [η] = 0.21dL / g.

2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 6; [η] = 0.87 dL / g.

2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 7; [η] = 0.48 dL / g.

3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 8; [η] = 0.63 dL / g.

6-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced as a white powder polyamic acid 9; [η] = 0.26 dL / g.

6-{[((2E)-3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced as white powder polyamic acid 10; [η] = 0.71 dL/g

6-{[((2E)-3-{4-[(4-trifluoromethylbenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Polyamic acid 11 was produced as a white powder; [η] = 1.21 dL/g

6-{[((2E)-3-{4-[(4-(2,2,3,3-tetrafluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced polyamic acid 12 as a white powder; [η] = 0.48 dL/g

6-{[((2E)-3-{4-[(4-(2,2,3,3-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate

Produced polyamic acid 13 as white powder; [η] = 0.48 dL/g

3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 14 as a white powder; [η] = 0.59 dL/g

3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 15 as white powder; [η] = 0.20 dL/g

3,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 16 as white powder; [η] = 0.38 dL/g

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 17 as a white powder; [η] = 0.50 dL/g

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 18 as a white powder; [η] = 0.27 dL/g

2-(2,4-Aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 19 as white powder; [η] = 0.19 dL/g

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,3-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

Produces polyamic acid 20 as a white powder; [η] = 0.28 dL/g

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

Produced as white powder polyamic acid 21; [η] = 0.54 dL/g

2-(2,4-Dinitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

Produces polyamic acid 22 as a white powder; [η] = 0.17 dL/g

2-(2,4-Dinitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

Produced polyamic acid 23 as a white powder; [η] = 0.16 dL/g

2,2'-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

Produced polyamic acid 24 as a white powder; [η] = 0.55 dL/g

Example 10

Similar to Example 9, polyamic acid was prepared using the following diamine and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride:

3,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Produced as white powder polyamic acid 25; [η] = 0.40 dL/g

2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

Produced polyamic acid 26 as a white powder; [η] = 0.47 dL/g

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Produced polyamic acid 27 as a white powder; [η] = 0.23 dL/g

2-(2,4-Aminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

Produces polyamic acid 28 as a white powder; [η] = 0.14 dL/g

3,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

Produces polyamic acid 29 as a white powder; [η] = 0.45 dL/g

2,2'-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

Produces polyamic acid 30 as white powder; [η] = 0.30 dL/g

2,2'-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-diamino-1,1'-biphenyl

Produced polyamic acid 31 as white powder; [η] = 0.17 dL/g

2-(2,4-Dinitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

2-(2,4-Dinitrophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol

Example 11

Similarly to Example 9, polyamic acid was prepared using the following tetracarboxylic dianhydride and 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate.

4-(2,5-Dioxatetrahydrofuran-3-yl)tetralinalene-1,2-dicarboxylic dianhydride diaminobenzoate yielded polyamic acid 32 as a white powder; [η] = 0.15 dL/g.

Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride produces polyamic acid 33 as a white powder; [η] = 0.11 dL/g

2,3,5-Tricarboxycyclopentyl acetic dianhydride produces polyamic acid 34 as a white powder; [η] = 0.43 dL/g

5-(2,5-Dioxatetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride produces polyamic acid 35 as a white powder; [η] = 0.16 dL/g

4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride produces polyamic acid 36 as a white powder; [η] = 0.51 dL/g

Example 12

Similar to Example 9, polyamic acid was prepared using the following tetracarboxylic dianhydride mixture and 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate.

A 25:75 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride yielded polyamic acid 37 as a white powder; [η] = 0.16 dL/g

A 1:1 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride yielded polyamic acid 38 as a white powder; [η] = 0.20 dL/g

A 75:25 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride yielded polyamic acid 39 as a white powder; [η] = 0.20 dL/g

A 90:10 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride yielded polyamic acid 40 as a white powder; [η] = 0.17 dL/g

A 25:75 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 5-(2,5-dioxatetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride yielded polyamic acid 41 as a white powder; [η] = 0.16 dL/g

A 1:1 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 5-(2,5-dioxatetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride yielded polyamic acid 42 as a white powder; [η] = 0.16 dL/g

A 75:25 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 5-(2,5-dioxatetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride yielded polyamic acid 43 as a white powder; [η] = 0.16 dL/g

Example 13

Similar to Example 9, a 75:25 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride and 3,5-diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate was used to prepare polyamic acid 44 as a white powder; [η] = 0.17 dL/g

Example 14

Similar to Example 9, a 75:25 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride and 3,5-diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate was used to prepare polyamic acid 45 as a white powder; [η] = 0.24 dL/g

Example 15

Similar to Example 9, a 75:25 (molar ratio) mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4-(2,5-dioxatetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic dianhydride and 2-(2,4-aminophenyl)ethyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate was used to prepare polyamic acid 46 as a white powder; [η] = 0.11 dL/g

Example 16

Similar to Example 9, a 1:1 (molar ratio) mixture of 2,2-bis(4-aminobenzyl)-1,3-di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol and 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]hexane-3,5-diaminobenzoate and 1,2,3,4-cyclobutanetetracarboxylic dianhydride were used to prepare polyamidic acid 47 as a white powder; [η] = 0.98 dL/g

Example 17

Similar to Example 9, an 80:20 (molar ratio) mixture of 2,2-bis(4-aminobenzyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol and 4,4′-diaminodiphenylmethane and 1,2,3,4-cyclobutanetetracarboxylic dianhydride were used to prepare polyamic acid 48 as a white powder; [η] = 1.00 dL/g

Example 18

Polymerization step B (formation of polyimide)

0.50 g of polyamic acid No. 1 obtained in Example 9 above was dissolved in 3 ml of 1-methyl-2-pyrrolidone (NMP). 0.28 g (3.57 mmol, 4 equivalents) of pyridine and 364 mg (3.57 mmol, 4 equivalents) of acetic anhydride were added, and dehydration and ring closure were carried out at 80°C for 2 hours. The polymer mixture was diluted with 1.5 ml of NMP, precipitated into 100 ml of diethyl ether, and collected by filtration. The polymer was reprecipitated from THF (10 ml) into 200 ml of water and dried under vacuum at room temperature to produce 0.55 g of polyimide No. 1; [η] = 0.50 dL/g, imidization degree ID = 100%

The following polyamic acid was used to prepare a partially imidized polyimide similar to the polymerization procedure of Example 18. The ratio of acetic anhydride to pyridine was used to adjust the degree of imidization.

Polyamic acid 1 was reacted with 1.2 equivalents of acetic anhydride and pyridine to produce polyimide 1 as a white powder; [η] = 0.23 dL/g, ID = 40%.

Polyamic acid 1 reacts with 0.8 equivalents of acetic anhydride and pyridine to produce polyimide 1 as a white powder; [η] = 0.26 dL/g, ID = 30%.

Polyamic acid 1 was reacted with 0.4 equivalents of acetic anhydride and pyridine to produce polyimide 1 as a white powder; [η] = 0.27 dL/g, ID = 14%.

Polyamic acid 2 produces polyimide 2 as a white powder; [η] = 0.24 dL/g, ID = 100%

Polyamic acid 5 produces polyimide 5 as a white powder; [η] = 0.36 dL/g, ID = 100%

Polyamic acid 13 produces polyimide 14 as a white powder; [η] = 0.88 dL/g, ID = 100%

Polyamic acid 14 produces polyimide 13 as a white powder; [η] = 0.48 dL/g, ID = 100%

Polyamic acid 15 produces polyimide 15 as a white powder; [η] = 0.20 dL/g, ID = 100%

Polyamic acid 16 produces polyimide 16 as a white powder; [η] = 0.27 dL/g, ID = 100%

Polyamic acid 17 produces polyimide 17 as a white powder; [η] = 0.29 dL/g, ID = 100%

Polyamic acid 18 produces polyimide 18 as a white powder; [η] = 0.28 dL/g, ID = 100%

Polyamic acid 19 produces polyimide 19 as a white powder; [η] = 0.19 dL/g, ID = 100%

Polyamic acid 20 produces polyimide 20 as a white powder; [η] = 0.28 dL/g, ID = 100%

Polyamic acid 21 produces polyimide 21 as a white powder; [η] = 0.63 dL/g, ID = 100%

Polyamic acid 25 produces polyimide 25 as a white powder; [η] = 0.43 dL/g, ID = 100%

Polyamic acid 27 produces polyimide 27 as a white powder; [η] = 0.20 dL/g, ID = 100%

Polyamic acid 28 produces polyimide 28 as a white powder; [η] = 0.14 dL/g, ID = 60%

Polyamic acid 28 reacted with 1.0 equivalent of acetic anhydride and pyridine to produce polyimide 28 as a white powder; [η] = 0.23 dL/g, ID = 25%.

Polyamic acid 34 produces polyimide 34 as a white powder; [η] = 0.40 dL/g, ID = 100%

Polyamic acid 39 produces polyimide 39 as a white powder; [η] = 0.21 dL/g, ID = 100%

Polyamic acid 44 produces polyimide 44 as a white powder; [η] = 0.14 dL/g, ID = 100%

Polyamic acid 45 produces polyimide 45 as a white powder; [η] = 0.12 dL/g, ID = 100%

Example 19

Preparation of an alignment layer for vertical alignment using unpolarized UV light

A 4% solution of LPP (see the molecular structure in Formula 1) was prepared in a solvent mixture of N-methyl-2-pyrrolidone (NMP) and butyl glycol (BC) in a 1:9 weight ratio. This LPP solution was filtered through a 0.2 μm Teflon filter and applied to two rectangular glass plates coated with indium tin oxide (ITO) by spin coating at 1350 rpm for 30 seconds. The resulting film was then pre-dried at 130°C for 5 minutes and post-baked at 200°C for 40 minutes. The two ITO-coated glass plates were irradiated with unpolarized UV light at a dose of 48 mJ/ ^cm² . The light was incident (10° tilted relative to the plate normal and the incident plane) parallel to the short side of the substrate. A cell with a 20 μm pitch was constructed using these two irradiating plates in an anti-parallel arrangement, with the irradiated surfaces facing each other. The cell was then filled with the isotropic liquid crystal mixture MLC6610 (available from Merck) at 105°C. The cell was then gradually cooled from T = 105°C to T = 85°C at a rate of 0.1°C/min and from T = 85°C to room temperature at a rate of 2°C/min. When aligned between crossed polarizers, the cell appeared uniformly black at every angle between the short edge of the cell and the transmission axis of the polarizer, as long as it was viewed perpendicularly. In short, the liquid crystal mixture was in homeotropic alignment.

When the short edge of the cell was positioned at 45° to the polarizer axis and an AC voltage of 7V and 90Hz was applied, the liquid crystal switched, causing the cell to appear green (high-order birefringence). No defects or tilt domains were observed. When viewed in reverse, the brightness and color of the switched cell changed asymmetrically, but at equal tilt angles along a plane parallel to the cell's short edges. Conversely, when viewed at a reverse angle within a plane parallel to the cell's long edges, no asymmetry was observed. When the short edge of the switched cell was aligned parallel or perpendicular to one of the polarizer transmission axes, the cell again appeared dark. These observations indicate that irradiation with obliquely incident unpolarized light induced the LC alignment ability in the thin film on the substrate. The azimuthal alignment direction was parallel to the plane of incidence of the unpolarized UV light. Tilt angle evaluation using the crystal rotation method yielded a tilt angle value of 89.2° relative to the substrate surface. The orientation of the LC molecules was midway between the surface normal and the direction of incident light.

Example 20

Using non-polarized UV light to prepare an alignment layer with a defined tilt angle

The same experiment was conducted using the same LPP, except that the incident light was tilted 40° relative to the plate normal. The azimuthal alignment direction was parallel to the plane of incidence for the unpolarized UV light. Tilt angle evaluation using the crystal rotation method yielded a tilt angle of 88.65° relative to the substrate surface. The LC molecules were oriented midway between the surface normal and the incident light direction.

Formula 1: Molecular structure of LPP

Comparative Synthesis Example 1

Similarly to Example 21, 6-{[((2E)-3-{4-[(4-butoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate was synthesized.

Contrast aggregation 1

Using 920.2 mg (1.683 mmol) of 6-{[((2E)-3-{4-[(4-butoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate and 330.1 mg (1.683 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, a comparative polyamic acid 1 (1.01 g) was prepared similarly to Synthesis Example 9; [η] = 0.25 dL/g

Comparative Synthesis Example 2

Similarly to Example 3, 3,5-diaminobenzyl (2E) 3-{4-[(4-pentyloxy)benzoyl]oxy}phenyl}acrylate was synthesized.

Contrast Aggregation 2

A reaction mixture was prepared similarly to Synthesis Example 9 using 1.0390 g (2.15 mmol) of 3,5-diaminobenzyl (2E) 3-{4-[(4-pentyloxy)benzoyl]oxy}phenyl}acrylate and 422.2 mg (2.15 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride to produce 1.349 g of comparative polyamic acid 2; [η] = 0.87 dL/g

Example of preparing an alignment layer with a certain tilt angle

A 2% solution of polyamic acid 1 in cyclopentanone was filtered through a 0.2 μm Teflon filter and applied to an indium tin oxide (ITO)-coated glass plate in a spin coating apparatus at 3000 rev/min over 60 seconds. The resulting film was then pre-dried at 130°C for 15 minutes and imidized at 200°C for 1 hour to form a polyimide film. The resulting LPP film was irradiated with linearly polarized UV light (30 mJ/ ^cm² ), with the incident direction tilted 20°-40° relative to the plate normal. The polarization direction of the light was maintained in the plane defined by the incident direction and the plate normal. A cell with a 20 μm spacing was formed from the two plates, with the irradiated surfaces facing each other and the initial irradiation polarization directions parallel. The cell was then filled with the isotropic liquid crystal mixture MLC6609 (Merck) at 100°C. The cell was then gradually cooled to room temperature at a rate of 0.1°C/min to 2°C/min. A uniformly oriented liquid crystal layer was observed between the crossed polarizers. The tilt angle of this parallel cell was determined to be 88.7° by the crystal rotation method.

Example of measuring voltage holding ratio (VHR)

Two glass plates coated according to the above-described example were irradiated perpendicularly with linearly polarized UV light within 4 minutes. From these two plates, a cell with a spacing of 10 μm was obtained, so that the irradiated surfaces faced each other and the previous irradiation polarization directions were parallel. The cell was then kept at 120° C. for 14 hours under high vacuum and thereafter filled with the TFT liquid crystal mixture MLC6610 (from Merck) under vacuum at room temperature. A uniformly oriented liquid crystal layer was observed between the crossed polarizers. Before testing the voltage holding ratio (VHR), the cell was first aged at 120° C. for 50 hours. The voltage decay V(T=20 ms) was then measured over a period of T=20 ms for a voltage surge of 64 μs at V ₀ (V at t=0)=0.2 V. The voltage holding ratio was then determined, given by VHR=V _rms (t=T)/V ₀ ,

result

Claims (28)

1. Diamine compounds of general formula (I): in, A represents 1,4-phenylene, which is unsubstituted or monosubstituted with a halogen atom and/or acryloyloxy or methacryloyloxy and/or an alkoxy, alkylcarbonyloxy or alkoxycarbonyl group containing 1-10 carbon atoms, and Among them, the compound residues (Ia) of the compounds of the above general formula (I) Indicates a straight-chain or branched _C1 - _C8 fluoroalkyl group, wherein F is fluorine, and x ₁ is an integer from 1 to 9. B represents a straight-chain or branched _C1 - _C8 alkyl group that is unsubstituted or one or more of the _-CH2- groups may be independently replaced by a linker selected from the following: -O-, -CO-, -CO-O-, -O-CO- and -CH=CH-; The condition is that the oxygen atoms are not directly bonded to each other; and The _C1 - _C8 fluoroalkyl group has a terminal unit selected from _-CF₂H , -CF₃, _-CF₂CF₃ , _{-CF₂CHF₂ ,} - _{( CF₂} ) _₂CF₃ , -( _CF₂ ) _₂CHF₂ , -( _CF₂ ) _₃CHF₂ , -( _CF₂ ) _₃CF₃ , _-CF ( _CF₃ ) _{₂ , and -CF₂} ( _CHF ) _{CF₃ .} D is selected from the following compounds: "-" indicates the linking bond between D and ^S1 in compound (I) and also represents a single bond; and _L represents _-CH3 , -COCH3, _-OCH3 , nitro, cyano, halogen, _CH2 =CH-, _CH2 =C( _CH3 )-, _CH2 =CH-(CO)O-, _CH2 =CH _- O-, ^-NR5R6 , ^CH2 =C( _CH3 )-(CO)O- or _CH2 =C( _CH3 )-O-; ^R5 and ^R6 each independently represent a hydrogen atom or a _C1 - _C6 alkyl group; u3 is an integer between 0 and 2; E represents an oxygen atom; ^S1 represents a single bond or a straight-chain _C1 - _C8 alkylene group, one of which can be replaced by -O-, -OCO-, -COO-, _-NR1CO- , or _-CONR1- , where _R1 is hydrogen or a _C1 - _{C6 alkyl} group; ^S2 is replaced by a group of general formula (IVa). -(Z ¹ -C ¹ ) _a1 -(Z ^1a ) _a3 - (IVa) in: ^C1 represents 1,4-phenylene, which is unsubstituted or substituted with a halogen atom and/or an alkoxy, alkyl carbonyl or alkoxy carbonyl group containing 1-10 carbon atoms, or is monosubstituted or polysubstituted. ^Z1 and ^Z1a represent -COO-, -OCO-, -CH2- _CH2- , _-OCH2- , _-CH2O- , -CH＝ _CH- , -C≡C-, -CH＝CH-COO-, -OCO-CH＝CH-, or single bonds; X and Y are hydrogen atoms; a1 represents 1, and a3 represents 0 or 1; and n is 1 or 2, and n1 is 1 or 2; The condition is that if n or n1 is 2, then each A, B, _x1 , D, E, ^S1 , and ^S2 can be the same or different; if n1 is 2, then each B and _x1 can be the same or different. 2. The diamine compound according to claim 1, selected from... Wherein ^S1 , B, _x1 are as defined in claim 1. 3. Diamine compounds, selected from: 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate, 2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate, 3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate, 4-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate, 5-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate, 8-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate, 11-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate, 2-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate, 3-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate, 4-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate, 5-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate, 8-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate, 2-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate, 3-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate, 4-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate, 5-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate, 6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate, 4-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate, 5-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate, 8-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate, 11-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate, 2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate 5-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate 5-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 8-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(3-methoxy-4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 8-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(3-methoxy-4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl-3,5-diaminobenzoate 6-{[((2E)-3-{4-[(3-methoxy-4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(3-methoxy-4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl-3,5-diaminobenzoate 6-{[((2E)-3-{4-[(3-methoxy-4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate 2{2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate 2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 2-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate 4-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate 5-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 7-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl3,5-diaminobenzoate 8-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate 11-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-{[(4,4,4-trifluorobutoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-{[(4,4,5,5,5-pentafluoropentoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 6-{[((2E)-3-{4-[(4-({[(4,4,5,5,6,6,6-heptafluorohexyloxy)carbonyl]amino})benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate 3,5-Diaminobenzyl (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(2,2,3,3,3-pentafluoropropoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-(4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentoxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl(2E)3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyloxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl(2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[4-(4,4,5,5,5,-pentafluoropentanoyloxy)benzoyloxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyloxy]phenyl}acrylate 3,5-Diaminobenzyl (2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyloxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl(2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate 2,5-Diaminobenzyl (2E)3-{4-[4-(4,4,5,5,5,-pentafluoropentanoyloxy)benzoyloxy]phenyl}acrylate 2,5-Diaminobenzyl (2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyloxy]phenyl}acrylate 2,5-Diaminobenzyl (2E)3-{4-[(2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexanoyl)oxy)benzoyloxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate 2,4-Diaminobenzyl (2E)3-{4-[4-(4,4,5,5,5,-pentafluoropentanoyloxy)benzoyloxy]phenyl}acrylate 2,4-Diaminobenzyl(2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexanoyloxy)benzoyloxy]phenyl}acrylate 2,4-Diaminobenzyl (2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate; 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,3,3-pentafluoropropoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,6,6,6-pentafluorohexyl)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3,4-di(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxycarbonyl)phenoxy)carbonyl]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate, 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-[(4,4,5,5,5-pentafluoropentoxy)carbonyl]amino)benzoyl]oxy}phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 3-(3,5-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 3-(2,4-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 3-(2,4-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 3-(2,4-Diaminophenyl)propyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 3-(2,4-Diaminophenyl)propyl(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}acrylate 6-(2,4-Diaminophenyl)hexyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 6-(2,4-Diaminophenyl)hexyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate 6-(2,4-Diaminophenyl)hexyl(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol; 2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2,2-Bis(4-aminobenzyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]hexyloxy]benzoate 2,2'-Bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4'-diamino1,1'-biphenyl; and 2,2'-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4'-diamino1,1'-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]phenyl]prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]phenyl]prop-2-enoyl]methyl-4,4’-diamino-1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl]prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoylmethyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2,2’-Bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl4,4’-diamino1,1’-biphenyl 2-(2,4-Diaminophenyl)-1,3-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(2,4-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(3-methoxy-4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutyryl)oxy)benzoyl]oxy]-3-methoxyphenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol 2-(3,5-Diaminophenyl)-1,3-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]propanediol. 4. A polymer comprising, as a basic building unit, the diamine (I) according to claim 1 or the diamine according to any one of claims 2-3. 5. The polymer according to claim 4, wherein it is a copolymer or oligomer. 6. Preparation method of diamine compound (XII) Including compounds of general formula (XIV) Contact with dinitro compounds of general formula (XVI) The obtained dinitro compounds of general formula (XVIa) are then converted into diamino compounds of the corresponding general formula (XII). Wherein F, _x1 , _n1 , n, B, D, E, X, Y and ^S1 have the same meaning as in claim 1, and ^Z1 represents a bridging group; _{L represents -CH3, -COCH3, -OCH3 , nitro} , cyano, halogen, _CH2 ＝CH-, _CH2 ＝C( _CH3 )-, _CH2 ＝CH-(CO)O-, _CH2 ＝CH _- O-, ^-NR5R6 , ^CH2 ＝C( _CH3 )-(CO)O-, _CH2 ＝C( _CH3 )-O-; in: ^R5 and ^R6 each independently represent a hydrogen atom or a _C1 - _C6 alkyl group; u1 is an integer between 0 and 4; and u2 is an integer between 0 and 3; D1 has the same meaning as D, provided that the two amino groups of D are replaced by two nitro groups. 7. A composition comprising at least one diamine (I) according to claim 1, or a diamine according to any one of claims 2-3, or a polymer according to claim 4, and optionally, at least one other diamine and/or additive different from (I). 8. The composition according to claim 7, wherein the polymer is a copolymer or an oligomer. 9. A method for preparing a polymer, comprising the polymerization of the diamine (I) according to claim 1 or the diamine according to any one of claims 2-3. 10. The method of claim 9, wherein the polymer is a copolymer or an oligomer. 11. Polymers obtainable by the reaction according to claim 9, wherein they comprise a diamine compound according to any one of claims 1-3. 12. The polymer according to claim 11, wherein it is a copolymer or oligomer. 13. The polymers according to claim 11 or prepared according to claim 9 are capable of photocycloidization. 14. The polymer according to claim 13, wherein it is a copolymer or oligomer. 15. A composition comprising: -A polymer comprising at least the diamine (I) according to claim 1 as a basic building block or the diamine according to any one of claims 2-3, or - A polymer that can be obtained according to claim 9. 16. The composition of claim 15, wherein the polymer is a copolymer or an oligomer. 17. The composition according to claim 15, wherein it is a blend. 18. A method for preparing a polymer according to claim 11 or according to claim 9, wherein in the polycondensation reaction, the diamine (I) according to claim 1 or the diamine according to any one of claims 2-3 is reacted with one or more tetracarboxylic anhydrides, optionally in the presence of one or more other diamines. 19. The method of claim 18, wherein the polymer is a copolymer or an oligomer. 20. A method for preparing a polymer layer, wherein one or more polymers according to claim 11, or prepared according to claim 9, or prepared according to claim 4 are coated onto a carrier, and wherein the polymer or polymer mixture is treated with calibrated light. 21. The method of claim 20, wherein the polymer is a copolymer or an oligomer. 22. A polymer layer that can be obtained by the method according to claim 20. 23. The polymer layer according to claim 22, wherein it is a copolymer or oligomer layer. 24. Optical and electro-optical unstructured or structured structural elements comprising at least one polymer layer according to claim 22. 25. The optical and electro-optic unstructured or structured structural element of claim 24, wherein the polymer is a copolymer or oligomer. 26. The optical and electro-optic unstructured or structured element according to claim 24, wherein it is a liquid crystal display unit, a multilayer or hybrid layer element. 27. An orientation layer comprising at least one polymer layer according to claim 22. 28. The orientation layer of claim 25, wherein the polymer is a copolymer or an oligomer.