DE4109262A1 - New di:alkynyl malonate cpds. and polymers for photochromic materials - prepd. by reacting malonyl di:chloride with unsatd. alcohol pref. prop-2-yn-ol and knoevenagel condensation - Google Patents

Abstract

New dialkynyl malonate derivs (I); and new unsatd polymers (II) are claimed. A = organic gp contg aromatic ring(s), which intrinsically (A1) cannot form liq crystalline (LC) phases and/or (A1) has nonlinear optical properties and/or (A3) has photochromic properties or which (A4) can form calamitic LC and/or (A5) discotic LC phase(s) or which (A6) can form calamitic LC and/or discotic LC phase(s) and also has nonlinear optical and/or photochromic properties; n = an integer from 1 to 6; B = a bifunctional -X-(Y)m-X- gp; X = -MRR1- or -M1-R- with M = Si, Ge or Sn, M1 = B, Al or P and R and R1 independently = alkyl(aryl) or (alkyl)-cycloalkyl; Y = a bifunctional organic or organometallic, low mol, oligomeric or polymeric linking gp, 0 or S, which has a metal-metal bond if m = 0 and M = Si, Ge or Sn or a polycentred bond if m = 0 and M1 = B or Al; m = 0 or 1. (I) are prepd by reacting malonyl dichloride with the relevant unsatd alcohol, esp prop-2-yn-l-ol, and Knoevenagel condensation with suitable low mol cpds, using piperidine acetate as catalyst. (II) are prepd (claimed) by reacting (I) and cpd(s) having negatively polarised H atoms of formula H-X-(Y)m-X-H (III). USE/ADVANTAGE - (I) are claimed for use as starting materials for (II); and both (I) and (II) are claimed for producing materials and equipment with photochromic, LC and/or nonlinear optical properties, which are claimed for use in holography, laser optical data recording, reprography, nonlinear optics and information displays. (I) and (II) can be prepd easily.

Description

The present invention relates to new dialkinmalonate derivatives general formula I.

where the index n and the variable A have the following meaning:

• A organic residue that contains at least one aromatic nucleus and which on its own
  • A1) is unable to form a liquid-crystalline phase and / or
  • A2) nonlinear optical properties and / or
  • A3) has photochromic properties or which
  • A4) at least one calamitic liquid crystalline and / or
  • A5) is capable of forming at least one discotic liquid crystalline phase or which one
  • A6) is able to form at least one calamitic liquid-crystalline and / or at least one discotic liquid-crystalline phase and moreover has nonlinear optical and / or photochromic properties;
• n integer from 1 to 6.

The present invention further relates to polymers of general Formula II

wherein the index n and the variable A are those given in claim 1, respectively Have meaning and in which the variable B has the following meaning:

• B bifunctional radical of the general formula III where the variables X and Y and the index m have the following meaning:
  • X -MRR¹-, wherein M denotes a silicon, germanium or tin atom and the radicals R and R¹ can be identical or different from one another and represent alkyl, cycloalkyl, alkylcycloalkyl and alkylaryl groups;
  • X -M¹R-, wherein M¹ denotes a boron, aluminum or a phosphorus atom and the radical R has the above meaning;
  • Y bifunctional organic or organometallic, low molecular weight, oligomeric or polymeric linking radical and oxygen or sulfur atom;
  • Y for m = 0 and M = silicon, germanium or tin atom is a metal-metal bond;
  • Y for m = 0 and M¹ = boron or aluminum atom is a multicenter bond;
  • m 0 or 1.

Low molecular weight liquid crystalline compounds which are dovetail-shaped, d. H. long chain and branched, substituents on their linear or bear approximately linear aromatic ring systems are from the Articles from

- D. Demus in Liquid Crystals, Volume 5, pages 75 and following,
- J. Malthete et al. in Tetrahedron, volume 37 (1981), pages 2823 and following, and from
- W. Weissflog et al. in Crystal Research and Technology, Volume 19, pages 583 and following,

known. These low molecular weight compounds have broad liquid crystalline Phases on, however, they are not suitable for production of polymers.

The use of low molecular weight liquid crystalline compounds for laser optical data recording and for displaying information is for example from the patents DE-A 36 14 113, DE-A 36 04 757, EP-A 02 35 748, EP-A 02 05 187, EP-A 01 53 729, WO 87/07 890, WO 86/02 937, US-A 47 52 820 and US-A 47 33 370 are known. Also those described here low molecular weight liquid crystalline compounds are not suitable for the production of liquid crystalline polymers.

Low molecular weight photochromic compounds with a pronounced photochromic Behaviors are from US-A 42 20 708, DE-A 25 32 224, the DE-A 26 47 850, the article by Akira Kaneko et al., "Photochemical Fatigue Resistances and Thermal Stabilities of Heterocyclic Fulgides in PMMA Film ", in Bulletin of the Chemical Society of Japan, Volume 61, Pages 3569 to 3573, 1988, and the article by Veerle Deblauwe et al., "Quantum yields of the photochromic reactions of heterocyclic fulgides and fulgimides ", in Macromolecular Chemistry, volume 189, pages 2503 to 2512, 1988, known.

The use of these low molecular weight photochromic compounds in devices for storing information, for holographic Recording, for making fax copies or for displaying Information is also from US-A 42 20 708, DE-A 25 32 224 and DE-A 26 47 850.

Furthermore, JP-A 01/26 846 is an N-stearyl-substituted one known photochromic compound, which is suitable for the production of Langmuir-Blodgett films are suitable.

In addition, the stabilization of EP-A 00 70 631 photochromic compounds through their storage in clay minerals such as Bentonite or montmorillonite. These stabilized compositions can be used as a paper coating agent or as a filler for Plastics are used.

Furthermore, from the article by Yukaei Hattori et al., "Photochromism in anisotropic matrices ", in the conference proceedings of the International Symposium on  Chemistry of Functional Dyestuffs, Osaka, Japan, June 1988, P-84, Devices such as a photosensitive recording element or a known laser optical data plate, wherein fulgides in anisotropic matrices such as nematic liquid crystalline phases, stretched polyvinyl alcohol films or stretched polyethylene films. With the help of this photosensitive Recording elements or laser optical data disks should prevent the written information from being read again is deleted, which is often the case with recording elements and laser-optical Data plates based on photochromic substances is the case.

The previously known low molecular weight photochromic compounds have when used in holography, laser optical data recording, reprography, non-linear optics and the display of Information disadvantages. So meet the devices for the Holography, the laser-optical data plates, the light-sensitive ones Recording elements for reprography, devices for the nonlinear optics and the elements used to display information far from all the demands and expectations of these today Devices are put into practice. Often they can only very low molecular weight photochromic compounds known so far poorly orientate in thin layers. If you orient yourself allow, the layers concerned are often unstable, which ultimately leads to a loss of the information written into these layers. Often these layers also show a rapid "fatigue" of the photochromism, which is caused by the increased occurrence of side reactions in the repeated conversion of the photochromic compounds. Furthermore are layers of the well-known low molecular weight photochromic compounds not mechanically stable, and those inscribed in these layers Information may U. also by diffusion processes again be destroyed.

It is also highly desirable to add new photochromic materials find which not only thermally and photochemically, but also are mechanically stable and in which diffusion processes no longer matter play.

Low molecular weight liquid crystalline compounds and manufactured therefrom Polymers with at least one mesogenic side group, which a is able to form nematic or smectic liquid-crystalline phase, and the use of these polymers in holography, laser-optical Data recording and the display of information are examples from the patents EP-A 01 88 785, DE-A 27 22 589, EP-A 02 31 858 (DE-A 36 03 267), DE-A 36 23 395 (GB-A 21 93 338) or EP-A 02 31 857  (DE-A 36 03 268) known. As from the patent specification EP-A 01 71 045 (DE-A 34 29 438), these polymers can also pleiochroic side groups included.

Low molecular weight liquid crystalline compounds and manufactured therefrom Polymers with at least one mesogenic side group, which a cholesteric liquid crystalline phase can form, as well as the Use of the polymers in laser optical data recording known from EP-A 00 07 574 or DE-A 36 04 757.

Low molecular weight liquid crystalline compounds and manufactured therefrom Polymers with at least one mesogenic side group, which a ferroelectric smectic liquid crystalline phase is able to form, as well the use of the polymers in laser-optical data recording, The holography and the display of information are from the Patents DE-A 38 23 153, DE-A 38 23 154, EP-A 01 84 482, EP-A 02 28 703, EP-A 02 58 898, EP-A 02 71 900 or EP-A 02 74 128 known.

Small molecular compounds with nonlinear optical properties and polymers prepared therefrom with at least one side group, which is non-centrosymmetric and an easily polarizable conjugate π electron system and at least one terminal electron acceptor group has, and their use in non-linear optics go from the patents US-A 47 55 574, WO-A 88/04 305, EP-A 02 71 730, EP-A 02 35 506, US-A 46 94 066 or US-A 47 57 130.

Polymers with at least one straight-chain C₁₀ to C₂₀ alkyl radical as Side groups are known from EP-A 02 32 113. These polymers can be used for laser optical data recording.

From the article by Michael M. Carpenter et al., "The characterization of Langmuir-Blodgett films of a non-linear optical, side-chain liquid crystalline polymer ", in Thin Solid Films, volume 161 (1988), pages 315 to 324, polymers are known which both

• i) at least one mesogenic group, which is a ferroelectric smectic liquid crystalline phase is able to form, as well
• ii) at least one non-centrosymmetric, one easily polarizable conjugated π electron system and at least one terminal Group containing electron acceptor group

have as page groups. These polymers are used for the production of Langmuir-Blodgett layers are used.

The preparation of polymers of the type mentioned above by (Co) polymerization of ethylenically unsaturated groups Monomers is described, for example, in the patents DE-A 38 23 153, DE-A 38 23 154, EP-A 01 84 482, EP-A 02 28 703, EP-A 02 71 900, DE-A 36 04 757, EP-A 01 88 785, EP-A 02 31 858, DE-A 36 23 395 (GB-A 21 93 338), EP-A 02 31 857 (DE-A 36 03 268), EP-A 01 71 045 (DE-A 34 29 438), US-A 47 55 574, WO-A 88/04 305 and EP-A 02 71 730 as well the article by Michael M. Carpenter in Thin Solid listed above Films, volume 161 (1988), pages 315 to 324.

The production of polymers of the type mentioned above by polycondensation is for example in the patent addresses EP-A 02 58 898 and EP-A 02 74 128 described.

In addition, from the patent addresses DE-A 33 34 056, DE-A 01 41 512, US-A 47 62 912, US-A 43 58 391, US-A 43 88 453 and US-A 44 10 570 polymers known, which by adding a ethylenically unsaturated group-containing monomers on organopolysiloxanes can be produced with at least one SIH group. These well-known too Polymers can be used for laser optical data recording, in holography or be used in nonlinear optics.

As is known, these polymers and polymers have theirs Side groups corresponding to low molecular weight compounds advantages. These are in particular that the application properties of devices for holography, laser-optical data plates, photosensitive recording elements for reprography, devices for nonlinear optics and elements for displaying information not based on these known polymers and polymers more deteriorated by diffusion and / or crystallization processes will. In addition, there are thin layers of these known polymers and polymers are generally mechanically more stable than layers from the low molecular weight compounds, which the side groups of correspond to known polymers and polymers.

However, the known polymers and polymers have the most serious Disadvantage that compared to the low molecular weight compounds, that correspond to their side groups, are very highly viscous. This is clear especially due to the sometimes drastically extended response times of the Polymers and polymers in their application in holography, in the  laser optical data recording and for displaying information noticeable.

The object of the present invention is to develop new low molecular weight To provide connections that are easily available and which on its own do not form a liquid crystalline phase ability and / or nonlinear optical properties and / or photochromic Have properties or which have at least one calamitic liquid crystalline and / or at least one discotic liquid crystalline phase able to form and also nonlinear optical and / or have photochromic properties. In addition, the new low molecular weight compounds for the production of new polymers suitable, which have the property profile listed above and no longer have the disadvantages of the prior art. These new substances, i.e. H. the new low molecular weight compounds and the new polymers are also said to be advantageous in holography, in laser optical data recording, in reprography, in the not linear optics and can be used for displaying information.

Surprisingly, this task could be accomplished by the ones defined at the beginning new dialkinmalonate derivatives of the general formula I can be solved. It was surprising with regard to the prior art and could therefore not be provided by the specialist that these new low molecular weight compounds such an extremely variable property profile and would have such broad applicability. Completely It was surprising that it was these new low molecular weight ones Connections particularly well for the production of the initially defined would be suitable new polymers of the general formula II, which the Disadvantages of the prior art no longer have.

Accordingly, the subject matter of the present invention is the dialkinmalonate derivatives of the general defined at the beginning Formula I, which in the following for the sake of brevity as "invention Dialkinmalonatderivate I "are called.

Accordingly, the new polymers of the general formula II in hereinafter referred to as "inventive polymer II".

The dialkinmalonate derivatives I according to the invention are characterized by the general Formula I described.

In the general formula I, the index n denotes an integer of 1 to 6. The index n can also be a larger number, such as 7, 8, 9 or  10, but it has been found to be advantageous according to the invention, if the index n is not greater than 6. Within this In an advantageous range, the index n can be chosen arbitrarily. According to the invention, it is particularly advantageous if the index n is the Numbers 1, 2 and 4 denotes, where it is of particular advantage if the index n is 1.

In the general formula I, the variable A denotes an organic one Rest, which contains at least one aromatic nucleus. This organic residue A has by itself, i.e. H. either as residue A in one any chemical environment or as the compound A 'from which it is derived derives the following property profile:

• A1) The organic radical A is unable to form a liquid-crystalline phase and also has no non-linear optical or photochromic properties on.
• A1) + A2) The organic radical A is not capable of a liquid-crystalline phase form, but has non-linear optical properties.
• A1) + A3) The organic radical A is not capable of a liquid-crystalline phase form, but has photochromic properties.
• A1) + A2) + A3) The organic radical A is unable to form a liquid-crystalline phase, but he has both nonlinear optical and photochromic Properties.
• A4) The organic radical A is capable of at least one calamitic liquid crystalline Form phase, taking a calamitic liquid crystalline Phase nematic, smectic, cholesteric or ferroelectric smectic liquid-crystalline phases are to be understood.  
• A5) The organic radical A is able to form at least one discotic liquid-crystalline phase, which, for example
  • (i) a position and a long-range order of columns whose molecules are stacked at regular or irregular intervals (eg "discotic hexagonal ordered", D _ho );
  • (ii) only a distant orientation order of columns, the molecules of which are stacked at regular or irregular intervals (eg "nematic columnar", N _C ); or
  • (iii) exclusively a long-range orientation of individual disc-shaped compounds or residues of so-called "discoids"("discoticnematic", N _D );
• exhibit.
• A4) + A2) The organic radical A is capable of at least one calamitic liquid crystalline Phase and also has non-linear optical Properties.
• A4) + A3) The organic radical A is capable of at least one calamitic liquid crystalline Phase and also has photochromic properties.
• A4) + A2) + A3) The organic radical A is capable of at least one calamitic liquid crystalline Phase and also has nonlinear optical and photochromic properties.
• A4) + A5) The organic radical A is capable of at least one calamitic liquid crystalline and to form at least one discotically liquid-crystalline phase.  
• A4) + A5) + A2) The organic radical A is capable of at least one calamitic liquid crystalline and to form at least one discotic liquid crystalline phase and also has nonlinear optical properties.
• A4) + A5) + A3) The organic radical A is capable of at least one calamitic liquid crystalline Phase and at least one discotically liquid crystalline phase form and also has photochromic properties.
• A4) + A5) + A2) + A3) The organic radical A is capable of at least one calamitic liquid crystalline Phase and at least one discotically liquid crystalline phase form and also has both nonlinear optical as well photochromic properties.
• A5) + A2) The organic radical A is capable of at least one discotically liquid crystalline Phase and also has non-linear optical Properties.
• A5) + A3) The organic radical A is capable of at least one discotically liquid crystalline Phase and also has photochromic properties.
• A5) + A2) + A3) The organic radical A is capable of at least one discotically liquid crystalline Phase and also has both nonlinear optical and also photochromic properties.

Accordingly, organic radicals A are the dialkinmalonate derivatives according to the invention I suitable all organic residues, which one of the above have listed property profiles. Examples according to the invention Suitable organic radicals A of this type are from the above State of the art known.  

According to the invention, it is advantageous if the radicals A are the radicals general formula IV can be used

In the general formula IV, the indices p and q are independent from each other for 0 or 1, d. that is, both indices p and q are both both can stand for 0 or for 1 or that they are different from one another. Regardless of the indices p and q, the index r denotes an integer from 1 to 12, preferably 2 to 11 and in particular 3 to 10, or it is is 0. Independent of the indices p, q and r, the index denotes s an integer from 1 to 3, advantageously 1 and 2 and in particular 1, or it is equal to 0.

The choice of indices depends primarily on which of the have the property profiles listed above of the organic radical A. should. Indices p, q, r and s suitable according to the invention are capable of the person skilled in the art in a simple manner from the prior art cited at the beginning to derive.

In the general formula IV, the variable C denotes a residue, which contains at least one aromatic nucleus. Examples according to the invention suitable radicals C are the phenylene, biphenyldiyl, terphenyldiyl and the naphthylene residue. Of these, the p-phenylene-, biphenylene-4,4'- diyl-, terphenyl-4,4 ′ ′ - diyl and the naphth-2,6-ylene radical very particularly advantageous.

In the general formula IV, the variable D denotes either Oxygen or a sulfur atom. However, it can also be a bifunctional linking residue D. Come as bifunctional linking residues D. all divalent linking functional groups of the organic or organometallic chemistry, where those of organic chemistry are advantageous according to the invention.  

Examples of particularly advantageous bifunctional linking radicals D are

- Imino group

in which the radical R² denotes a hydrogen atom or a C₁- to C₄-alkyl radical such as methyl, ethyl, n-propyl and n-butyl,
- methyleneimino group -C = N- and -N = C-,
- ester group

- thiolester group

- amide group

where R² has the meaning given above,
- urethane group

where R² has the meaning given above,
- diazo group -N = N-,
- azoxy group

such as
- Sulfonic ester group -SO₂-O- and -O-SO₂-.

Of these, the ester group, the methyleneimino group, the diazo group and the azoxy group is particularly advantageous, the ester groups being whole is particularly preferably used.

In the general formula IV, the variable E denotes a linear, approximately linear or disk-shaped organic or organometallic Rest.

Examples of linear or approximately linear that are suitable according to the invention Radicals E are the phenylene, biphenyldiyl, terphenyldiyl, naphthylene, Cycloalkylene, phenylene-cycloalkylene, bicycloalkylene and linear linked cycloalkylene radicals. Of these, the p-phenylene, Biphenyl-4,4'-diyl-, terphenyl-4,4'-diyl-, naphth-2,6-ylene-, cyclohex- 1,4-ylene, 4- (cyclohex-1 ', 4'-ylene) phen-1-ylene, decalin-2,6-ylene and 1,1'-Bicyclohexan-4,4'-ylene is particularly advantageous.

Examples of other radicals E which are suitable according to the invention are those mentioned above radicals E mentioned, which have the bifunctional linking residues D are linked to one another.

Linear or approximately linear organic radicals E of those listed above Kind are known from the prior art cited at the beginning.  

Examples of disk-shaped organic or suitable according to the invention organometallic residues are all those that stand for themselves seen form a discotic liquid crystalline phase.

Examples of organic or particularly suitable according to the invention Organometallic residues E of the type mentioned are residues E1 to E8:

In the general structures E1 to E8 listed by way of example, the variable Z explained in detail below stands for a long-chain radical, as is usually used in the field of discotic liquid-crystalline compounds. The variable Q in the general structures E1 to E8 stands for a bifunctional linking radical which is customary and known in this field and which is usually an alkanediyl group. The variable D of the general structures E1 to E8 listed by way of example is the radicals D explained above in detail. The variable S of the general structure E7 denotes an oxygen or a sulfur atom or an imino, methylene or carbonyl group, and the Variable T of the general structure E8 stands for a transition metal cation such as Cu ²⁺ , Ni ²⁺ or Fe ²⁺ , a main group metal cation such as Al ³⁺ or titanyl, vanadinyl, Al (OH) ²⁺ or SiO ²⁺ cation.

Examples of such disk-shaped organic or organometallic Residues E are also from the prior art cited at the beginning known.  

In the general formula IV, the variable Z denotes a reactive one organic functional group, a long chain residue, an optical active chiral residue, an electron acceptor group, a pleiochroic Dye residue or a photochromic residue.

Examples of suitable reactive organic functional ones according to the invention Z groups are the hydroxyl, amino, mercapto, methoxy, methanthio, Diazo, formyl, carboxyl, haloformyl, alkoxy and aryloxycarbonyl, Sulfonic acid and the sulfochloride group. Of these, the hydroxy ones are the Formyl and the carboxyl group are particularly advantageous.

Examples of long-chain radicals Z which are suitable according to the invention are n-pentan-1-oxy-, 1,4,7-trioxa-oct-1-yl-, 1,4-dioxa-3-oxo hexan-1-yl, the 2- (4′-n-hexylphen-1-yl) -ethin-1-yl- and the 2- (4′-n- Octylphen-1'-yl) -ethin-1-yl radical.

Examples of optically active chiral Z radicals which are suitable according to the invention are the following residues Z1 to Z5:

Examples of pleiochroic dye residues Z which are suitable according to the invention are the residues Z6 and Z7:

An example of a photochromic residue Z is residue Z8:

Examples of electron acceptor groups suitable according to the invention are Nitro, cyano, trifluoromethyl, triazinyl, pyridin-4-yl and the Fulven-6-yl group.

All of the above Z radicals are common and known and go for example from the prior art cited at the beginning.

The selection of the variables C, D, E and Z of the general formula IV judges as well as the selection of the indices p, q, r and s in the main according to which property profile the organic residue A and ultimately the dialkinmalonate derivative I according to the invention is said to have:

Should z. B. the dialkinmalonate derivative I of the invention nematic have liquid crystalline properties, one is called variable A of general formula I choose a mesogenic residue known per se, which is able to form a nematic liquid crystalline phase.

Should the dialkinmalonate derivative I according to the invention smectically liquid crystalline Have properties, one is called variable A of the general Formula I use a mesogenic residue known per se, which is a smectic liquid-crystalline phase is able to form.  

Should the dialkinmalonate derivative I according to the invention be ferroelectric smectic liquid crystalline properties, is used as variable A in the general formula I choose a mesogenic residue, which one ferroelectric smectic liquid crystalline phase is able to form.

In contrast, the dialkinmalonate derivative I according to the invention is intended to be nonlinear have optical properties, one is called variable A in general Formula I choose a residue that is a non-centrosymmetric one easily polarizable conjugated π electron systems and at least contains a terminal electron acceptor group Z, choose.

On the other hand, the dialkinmalonate derivative I according to the invention is discotic have liquid crystalline properties, one is called variable A of general formula I choose a mesogenic residue, which is a discotic able to form liquid crystalline phase.

The dialkinmalonate derivative I according to the invention is intended to be cholesteric liquid-crystalline Have properties, one is called variable A of the general Formula I choose a mesogenic residue, which is a cholesteric liquid crystalline Phase.

In contrast, the dialkinmalonate derivative I according to the invention is not intended to be liquid-crystalline Form phase, you will as variable A of the general formula I choose a residue that has no mesogenic properties.

Should the dialkinmalonate derivative I according to the invention have photochromic properties have, as variable A of the general formula I one Choose the rest that has photochromic properties.

In a corresponding manner, the person skilled in the art can use radicals A of the general formula I select if the relevant dialkinmalonate derivative according to the invention for example the property profile (A4) + (A2) listed above should have.

Examples of particularly suitable dialkinmalonate derivatives I are described in Scheme I listed below.  

Scheme 1

Examples of advantageous dialkinmalonate derivatives I according to the invention

Of these, the dialkylmalonate derivatives I-2, I-9, I-11, 1-15 and I-16 are particularly advantageous.

The preparation of the dialkinmalonate derivatives according to the invention is methodical I no peculiarities, but is done with the help of procedures performed as usual in preparative organic chemistry and are known. The manufacturing process is advantageously based on Synthesis of a dialkinmalonate, advantageously of dipropine malonate, by reaction of malonic acid dichloride with the unsaturated in question Alcohol, especially prop-2-in-1-ol. The dialkinmalonate in question can then under the conditions of the piperidine acetate-catalyzed Knoevenagel- Condensation with suitable low molecular weight compounds, which the Precursors of the radicals A of the general formula I are to those according to the invention Dialkinmalonatderivaten I be implemented. Suitable low molecular weight organic compounds which act as precursors for the residues A the general formula I are suitable, are common and known and Part commercially available, or they can in the usual and be made in a known manner.

The dialkinmalonate derivatives I according to the invention have excellent application properties Properties and can therefore be used in all areas of application the materials known so far in all applications nonlinear optical, photochromic, calamitic liquid crystalline and / or discotic liquid crystalline properties in full replace. So you can in holography, laser optical data recording, reprography, non-linear optics or display  of information used and the devices for holography, the laser-optical data plates, the light-sensitive recording elements or devices for reprography, the devices for non-linear optics and elements or devices for display of information based on the dialkinmalonate derivatives according to the invention I have numerous application technology advantages over the State of the art. Above all, however, the inventive ones are suitable Dialkinmalonate derivatives I for the preparation of those defined in the introduction polymers II according to the invention.

In the general formula II, the index n and the variable A have the at of the general formula I and in the description of the invention Dialin malonate derivatives I meaning explained in more detail.

In the general formula II, the variable B stands for a bifunctional one Rest of the general formula III.

In the general formula III, the index m stands for 0 or 1.

The variable X of the general formula I stands for an -MRR¹ group, in which the variable M denotes a silicon, germanium or tin atom. M advantageously represents a silicon atom. In this group you can the radicals R and R¹ are the same or different from one another and are for Alkyl, cycloalkyl, alkylcycloalkyl and alkylaryl radicals are. A Example of a very particularly advantageous variable X in question standing type is the -Si (CH₃) ₂ group.

The variable X of the general formula III can also be used for a -M¹R group, wherein M¹ is a boron, aluminum or a phosphorus atom designated and the radical R has the meaning given above.

According to the invention, the variables X with M = silicon atom are special advantageous and are therefore very particularly preferred for the construction of the inventive polymers II used.

In the general formula III, the variable Y denotes a bifunctional one organic or organometallic, low molecular weight, oligomers or polymeric linking residue or an oxygen or a sulfur atom. In addition, the variable Y of the general formula III for the Case that the index m = 0 and the variable M for a silicon, Germanium or tin atom is a metal-metal bond. About that  In addition, the variable Y can be used if the index is m = 0 and the Variable M¹ represents a boron or an aluminum atom, a multi-center bond be.

According to the invention, it is advantageous if the variable Y is a silicon-silicon bond, an oxygen atom, a low molecular weight oligomeric or polymeric bifunctional siloxane residue general formula IIIa

wherein the radicals R and R¹ have the meaning given above, or is a phenylene, in particular a p-phenylene radical.

The polymers II according to the invention can by any method of Polymer chemistry can be produced. According to the invention, however, it is from Advantage to synthesize them according to the inventive method.

The method according to the invention is based on the implementation known per se of terminally acetylenically unsaturated compounds with compounds, which negatively polarized hydrogen atoms, i. H. Hydride atoms, contain. As is known, this implementation is advantageously in the Presence of heavy metal catalysts, especially platinum (II) complexes such as dicyclopentadienylplatin (II) chloride.

Accordingly, in the inventive method for producing the inventive polymers II at least one according to the invention Dialkinmalonate derivative I with at least one compound of the general Formula IIIb

implemented.

In the general formula IIIb, the index has m and the variables X and Y the meaning given above.

Examples of particularly advantageous polymers II according to the invention are in Scheme 2 below.  

Scheme 2

Examples of advantageous polymers II according to the invention

These advantageous polymers II according to the invention can also be used in particularly advantageously by the method according to the invention getting produced.

The method according to the invention for producing the invention Polymer II is not only linear to those listed above Polymers II of the invention limited, but it can with the help of inventive method also inventive polymers II in the form of rings and three-dimensional networks. To this Purpose is only necessary instead of a bifunctional connection of the general formula IIIb to choose a compound which has more than two Contains residues H-X with a negatively polarized hydrogen atom.

The polymers according to the invention have particularly unexpected advantageous ones Properties on.  

So they are particularly easy to manufacture, whereby set your desired property profiles in a targeted and safe manner can be. This makes it possible to use the polymers II according to the invention tailored for a specific purpose, what a This is an advantage that cannot be overestimated. This Another advantage is the inventive method for producing the Polymers II according to the invention further reinforced because the inventive The process is extremely variable and the manufacture of the allows a wide variety of polymers II according to the invention. In addition to the liquid crystalline, non-linear optical and / or photochromic Properties that differ over the type of variables A and B of the general Have Formula II particularly simple and elegant the new polymers II also have a particularly low viscosity, which is why they respond particularly quickly to the effects of energy. The polymers II according to the invention are therefore particularly suitable for Holography, being especially with the holographic methods can be used as described by Christoph Bräuchle and Donald M. Burland in Angewandte Chemie, Volume 95 (1983), pages 612-629 are described. In addition, the new polymers II can be used if appropriate Selection of the radicals A and / or B of the general formula II which so far replace known polymers in all the applications as they are Donald R. Ulrich in the article "Non linear optical polymer systems and devices "in Molecular Crystals and Liquid Crystals, Volume 160 (1988), Pages 1 to 31 are described. In addition, the invention Polymers II with a suitable choice of the radicals A and / or B of the general Formula II for the manufacture of devices for laser optical Data recording, how laser optical data plates are used, how for example in GB-A 21 81 263, US-A 47 52 820, the EP-A 02 05 187 or EP-A 01 71 045 can be described. Here you can the relevant laser-optical data plates based on the new Polymers II with the help of the particularly advantageous laser-optical Writing and reading methods of EP-A 02 78 446 described and read will. In addition, the polymers II according to the invention can suitable choice of the radicals A of the general formula II photochromic properties have what they for the manufacture of devices such photosensitive recording elements suitable for reprography do.

Last but not least, the polymers II according to the invention are suitable for the Display of information on large screens. Because of her polymeric construction they are downright for this purpose predestined.  

Because of the special advantages of the invention described above Polymers II are the devices for holography that laser optical data plates, the light-sensitive recording elements for reprography, devices for nonlinear optics and the elements for displaying information on the basis of the invention Polymers II superior to previously known devices.

Example 1 Production and properties of the dialkinmalonate derivative according to the invention I-2 (Dipropin-4-hydroxybenzylidene malonate)

The dialkinmalonate derivative I-2 according to the invention was catalyzed by the piperidine acetate Knoevenagel condensation (cf. B. Kübel, Liebigs Ann. der Chemie, Volume 9 [1980], pages 1392 and ff.) of Dipropinmalonat and 4-Hydroxybenzaldehyde prepared in a toluene / tetrahydrofuran mixture. The chromatographically purified dialkinmalonate derivative I-2 fell into 83% yield and had a melting point of 101 to 103 ° C. The elemental composition determined by chemical analysis was correct agrees very well with the theoretically calculated values.

The dialkinmalonate derivative I-2 according to the invention did not have any liquid-crystalline ones Properties, however, it could be beneficial for manufacturing further dialkinmalonate derivatives I according to the invention are used will.

Examples 2 to 5 The preparation of the dialkinmalonate derivatives I-9, I-11, I-15 and I-16

The dialkinmalonate derivative I-9 according to the invention was known per se Way by reacting the hydroxyl group of the invention Dialkinmalonate derivative I-2 prepared with p- (n-pentoxy) benzoic acid chloride.

The dialkinmalonate derivatives I-11, I-15 and I-16 according to the invention were on the other hand in a manner known per se by esterification of the hydroxyl group of the dialkinmalonate derivative I-2 according to the invention with the following acids made in the presence of dicyclohexylcarbodiimide:

in Example 3 (dialkinmalonate I-11 according to the invention)  

in Example 4 (dialkinmalonate I-15 according to the invention)

in Example 5 (dialkinmalonate I-16 according to the invention)

The resulting dialkinmalonate derivatives I-9, I-11, I-15 and I-16 were determined by elemental analysis and proton nuclear magnetic resonance spectroscopy identified. Here they voted through chemical analysis determined elementary compositions of the invention Dialkinmalonate derivatives I very well with the theoretically calculated Values match. The relevant proton nuclear magnetic resonance spectra also corresponded the theoretical expectations.

Further test results as well as properties relevant to application technology are summarized in Table 1.

The phase transition behavior of the dialkinmalonate derivatives according to the invention I using differential thermal analysis (DSC) with a Perkin-Elmer DSC-2 calorimeter examined. In addition, polarization microscopic Investigations using a Leitz Ortholux Pol-BK-II polarizing microscope, which is equipped with a Mettler FP-52 heating table was equipped.  

Table 1

Further test results and application properties of the dialkinmalonate derivatives I according to the invention

The dialkinmalonate derivatives according to the invention of Examples 2 to 5 were excellent for the production of the polymers II according to the invention suitable.

Examples 6 to 14 The preparation and the properties of polymers II according to the invention General manufacturing instructions

The polymers II were prepared by reacting equimolar amounts of a dialkinmalonate derivative I according to the invention and a compound of the general formula IIIb in the presence of dicyclopentadienylplatinum (II) chloride in dry and freshly distilled toluene under argon. The reaction time was 3 days and the reaction temperature was 80 ° C. The course of the reaction was monitored by means of the absorption band of the Si-H group at 2140 cm ^{-1 by} IR spectroscopy. The polymers II according to the invention were purified by precipitation in methanol or methanol-acetonitrile mixtures and by preparative gel permeation chromatography (GPC) with 10³-10⁴-Å columns from the Polymer Laboratories using CHCl₃ as the eluent. The polymers II according to the invention were then dissolved in benzene, filtered through a microfilter and freeze-dried. After further drying under vacuum for at least 24 hours, the polymers II were obtained in a yield of 50 to 80%. Both the IR spectra and the proton nuclear magnetic resonance spectra and the chemically determined elementary compositions of the polymers II according to the invention corresponded to the theoretical predictions.

The number average molecular weight _{n of} some of the polymers II according to the invention was measured in a customary and known manner.

The phase transition behavior of the polymers II according to the invention was as described in Examples 2 to 5.

Table 2 gives an overview of the polymers II according to the invention produced, the starting compounds used for this, the phase transition behavior of the polymers II according to the invention and the number-average molecular weight _{n of} three polymers II according to the invention.

The values for the phase transition behavior summarized in Table 2 show that with the help of the method and the invention Polymers II the phase transition behavior extremely wide can be varied.  

Table 2

Starting compounds for the preparation of the polymers II according to the invention and some properties of the polymers II according to the invention which are relevant in terms of application technology

Claims (16)

1. Dialkinmalonate derivatives of the general formula I where the index n and the variable A have the following meaning:

• A organic residue that contains at least one aromatic nucleus and which on its own
  • A1) is unable to form a liquid-crystalline phase and / or
  • A2) nonlinear optical properties and / or
  • A3) has photochromic properties or which
  • A4) at least one calamitic liquid crystalline and / or
  • A5) is capable of forming at least one discotic liquid crystalline phase or which one
  • A6) is able to form at least one calamitic liquid-crystalline and / or at least one discotic liquid-crystalline phase and moreover has nonlinear optical and / or photochromic properties.
• n integer from 1 to 6.

2. Polymers of the general formula II wherein the index n and the variable A each have the meaning given in claim 1 and wherein the variable B has the following meaning:

• B bifunctional radical of the general formula III where the variables X and Y and the index m have the following meaning:
  • X -MRR¹-, wherein M denotes a silicon, germanium or tin atom and the radicals R and R¹ can be identical or different from one another and represent alkyl, cycloalkyl, alkylcycloalkyl and alkylaryl radicals;
  • X -M¹R-, wherein M¹ denotes a boron, aluminum or phosphorus atom and the radical R has the meaning indicated above;
  • Y bifunctional organic or organometallic, low molecular weight, oligomeric or polymeric linking radical and oxygen or sulfur atom;
  • Y for m = 0 and M = silicon, germanium or tin atom is a metal-metal bond;
  • Y for m = 0 and M¹ = boron or aluminum atom is a multicenter bond;
  • m 0 or 1.

3. The substances according to claim 1 or 2, characterized in that at least one radical of the general formula IV is used as variable A here where the indices p, q, r and s and the variables C, D, E and Z have the following meaning:

• C radical containing at least one aromatic nucleus;
• D oxygen and sulfur atom and bifunctional linking radical;
• E linear, approximately linear or disk-shaped organic or organometallic residue;
• Z reactive organic functional group, long-chain residue, optically active chiral residue, electron acceptor group, pleiochroic dye residue and photochromic residue;
• p 0 and 1;
• q 0 and 1;
• r 0 and an integer from 1 to 12;
• s 0 and an integer from 1 to 3.

4. The substances according to claim 3, characterized in that the index s and the variable C have the following meaning:

• C phenylene, diphenyldiyl, terphenyldiyl and naphthylene;
• s 0 and 1.

5. The substances according to claim 3 or 4, characterized in that the variable D has the following meaning:

• D oxygen and sulfur atom as well as the bifunctional linking residues wherein R² denotes a hydrogen atom or a C₁ to C₄ alkyl group

6. The substances according to one of claims 3 to 5, characterized in that the variable E has the following meaning:

• E phenylene, biphenyldiyl, terphenyldiyl, naphthylene, cycloalkylene, phenylene-cycloalkylene, bicycloalkylene and linearly linked cycloalkylene radicals;
• E phenylene, biphenyldiyl, terphenyldiyl, naphthylene, cycloalkylene, phenylene-cycloalkylene, bicycloalkylene and linearly linked cycloalkylene radicals which are linked to one another via oxygen or sulfur atoms or via bifunctional linking radicals D;
• E disk-shaped organic or organometallic residue which, seen in itself, is able to form a discotic liquid-crystalline phase, the variable Z designating a long-chain residue.

7. The polymers according to any one of claims 2 to 6, characterized in that that the variable M denotes a silicon atom. 8. The polymers according to claim 7, characterized in that the variable Y is a silicon-silicon bond, an oxygen atom, a low molecular weight, oligomeric or polymeric bifunctional siloxane radical of the general formula IIIa wherein the radicals R and R¹ have the meaning given above, or denotes a phenyl radical. 9. Use of the dialkinmalonate derivatives I according to one of claims 1 to 6 for the manufacture of materials and devices with photochromic, liquid crystalline and / or nonlinear optical Properties. 10. Materials and devices with photochromic, liquid crystalline and / or nonlinear optical properties, characterized in that that they have at least one dialkinmalonate derivative I according to one of the Claims 1 to 6 contain or consist thereof.   11. Use of the dialkinmalonate derivatives I according to one of claims 1 to 6 and the materials and devices according to claim 10 in the Holography, laser optical data recording, reprography, the non-linear optics and the display of information. 12. Use of the dialkinmalonate derivatives I according to one of claims 1 to 6 for the preparation of the polymers II according to one of claims 2 till 8. 13. A process for the preparation of the polymers II according to one of claims 2 to 8 by reacting terminally acetylenically unsaturated compounds with compounds which contain negatively polarized hydrogen atoms, characterized in that at least one dialkinmalonate derivative I according to one of claims 1 to 6 with at least a compound of general formula IIIb where the index m and the variables X and Y have the meaning given above. 14. Use of the polymers II according to one of claims 2 to 8 and Polymers II prepared according to claim 13 for the production of Materials and devices with photochromic, liquid crystalline and / or non-linear optical properties. 15. Materials and devices with photochromic, liquid crystalline and / or nonlinear optical properties, characterized in that that they contain at least one polymer II according to one of claims 2 to 8 and / or at least one polymer II prepared according to claim 13 contain or consist of. 16. Use of the polymers II according to any one of claims 2 to 8, the polymers II and materials and Devices according to claim 15 in holography, laser-optical Data recording, reprography, non-linear optics and Display of information.