LU85103A1 - LIQUID CRYSTALINE SUBSTANCES SUITABLE FOR PRODUCING POLYMER FILMS - Google Patents

Description

Brevet Ν ° .8 5 1 () ^ AND ~ DUCHÉ DE LUXEMBOURG BL-3517 / EM / EG

du 25 novembre 1963 WÊ Monsieur le Ministre,, _ de l'Économie et des Classes Moyennes î re e vre ........................... .............. Service de la Propriété Intellectuelle

LUXEMBOURG

Demande de Brevet d'invention I. Requête ..lA ^ üciSti ..- dijÄ..J ^ m.tx! Rtg .. ^ Cödl.IMmt.riej ... In.c ... * Libe.rt: y .... Ä .... Cb.arXoittft ...................... (1) -Streets, LaaeasÎ € r> iefinsylvsni-a - l -76-ô4iÎJSA, · repré »eatêe - par-lfi £ EilEYLUîSER .............. ··· - • £ riifiat ... T ....... &. ... ïiSY £ SS .... Err, e £ ..t., ..., ing * ..... co.as. «..... et .... i'rDi> rl ind *. *. 46. *. rue ... du .... Ciiae.tier.e, (2)

Ltatembour. £ ris; .tr. t en qualité ce r ..ne! st ^ i re __.................................

dépose (nt) ce ..... gin.gt:._ein% .rLQy & nhge cent quatre vingt trois (3) à ......... heures, au Ministère de l'Économie et des Classes Moyennes, à Luxembourg: 1. la présente requête pour l'obtention d'un brevet d'invention concernant: 8ipfee "........... <4) 2. la délégation de pouvoir, datée de ..... .......................... le £. __________________ 3. la description en langue .............. ... ..... ............ de l'invention en deux exemplaires; 4. ........., .......... ............ planches de dessin, en deux exemplaires; 5th la quittance des taxes versées au Bureau de l'Enregistrement à Luxembourg, le ............. .................................................. .................................................. ............, ............. · V ...;: T. ............... .................................................. ................

v ~~~~ décïare (nt) en assumant la responsabilité de cette déclàraîionrque l '(es) inventeur (s) est (sont): -Feuî-Asiu, .. p, ... ........ ....................., ....... ivr-ü, - !? «- 47551, -USA- (5) revendique (nt) pour la susdite demande de brevet la priorité d'une (des) demande (s) de (6) ...... * - -................... .................. déposée (s) en (7) · —-.-................... .................................................. ................

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le ............ çuirrr "ÎÊs ™ rr; r- · τ ±; τ x ^ ur-cerr - q astre '· vixrrr ceux ............ .................................................. ................ W

au nom de ....... "arë _______..................................... ..........................-....................... ...... ............................................ ............. (9) élit (élisent) pour lui (elle) et, si désigné, pour son mandataire, à Luxembourg .............. .....................

, ..... 4-5 y - ~ ”& ·· 4 · ................................ .................................................. ............ ...................................... ................................................. ( 10) sollicite (nt) la délivrance d'un brevet d'invention pour l'objet décrit et représenté dans les annexes susmentionnées, - avec ajournement de cette délivrance a .......... /. .......... mois. (11)

Le- ____________________________ "" '_ XI. Procès-verbal de Dépôt

La susdite demande de brevet d'invention a été déposée au Ministère de l'Économie et des Classes Moyennes, Service de la Propriété Intellectuelle à Luxembourg, en date du: 25-t.orfp · - / A "j \ / ^ _. / ·? '' "V" · - v- \ Pr. Le Ministre iiûn — ce i S. ·· e ·: - 1 de l'Économie et des Glasses Moyennes, 0 ~ 15ï05 ........ ..heures ô; - t, · / \% -: ~ i / ·· / V 1 '«...... / /

I BL-3517 / EM / EG

Claiming the priority of a patent application # filed in the United States under No. 450,088 on December 15, 1982: t / /

I PATENT APPLICATION

LIQUID AND CRYSTALLINE SUBSTANCES SUITABLE FOR THE PRODUCTION OF POLYMER FILMS.

Il ----! j $ r \ i i: i * j £! | \ t. Armstrong World Industries Inc.

1 'Liberty & Charlotte Streets l5 Lancaster, Pennsylvania 17604 \ r usa || il fl: "i il.

I ** j - 1 -

FOR THE PRODUCTION OF POLYMER FILMS FILLED- LIQUID CRYSTALLINE SUBSTANCES

A

. The invention relates to liquid crystals, in particular monomeric liquid crystals, which are suitable for producing polymeric liquid crystal materials.

The existence of liquid crystalline substances has been known since the 1990s. The terms "liquid crystals" or "mesophases" refer to a number of material states that move between liquid crystals and randomly oriented isotropic liquids. Liquid crystalline substances have structural features of crystals on the one hand, but on the other hand can also be viscous to slightly fluid.

j j With liquid crystals, one can differentiate between three different structures (mesophases) due to their different degree of order. In the crystalline state, the liquid crystals have a uniform three-dimensional structure with an orientation and positioning order. If the crystals are then heated, they can initially change one dimension of their positioning order. lieren. In this state, the so-called smectic

State, the liquid crystals retain the • orientation order of the crystalline state as well as the two-dimensional positioning order.

jl · p | 25 With further heating, the liquid crystals in | to pass the nematic state. In this phase f the last positioning order is also lost and! the liquid crystalline substance only remains the one! , dimensional orientation order of the crystalline state.

$ X

i - 2 - «j *

The molecular arrangement of nematic states is characterized in that the molecules are arranged along an axis that coincides with the longitudinal axis of the molecules. The centers of gravity of the molecules show a random arrangement, so that there is no longitudinal arrangement.

In the cholesteric mesophase, the molecular arrangement is characterized in that the molecules are arranged along an axis which, as in the nematic phase 10, coincides with the longitudinal axis of the molecules. However, this axis continuously changes its direction along a second axis which is perpendicular to the first. The cholesteric mesophases are therefore often referred to as helical and twisted nematic mesophases (twist structure). The prerequisite for the cholesteric mesophase is the optical activity of the liquid crystals in question.

I The term "cholesteric" is primarily historical. The first discovered cholesteric structure! The liquid crystal substance exhibiting was namely | 20 cholesteryl benzoate. However, it has been around for a long time! knows that the presence of the cholesterol fragment I is not necessary and that non-cholesterol derivatives 1 can also have a cholesteric structure.

'1 .

Liquid crystalline substances are of particular interest. 25 with cholesteric structure, since such substances have unique optical properties, such as selective reflection

Ixion of visible light to produce iridescent

Show colors as well as circular dichroism. So e.g. are described in US Pat. No. 3,720,623 mixtures of cholesteric and 30 nematic liquid crystals which are suitable for temperature-sensitive visual displays. Films for decorative purposes are described in US Pat. No. 3,766,061 (S ......

* * .V

- 3 - contain the solids in such a ratio that the composition shows cholesteric properties. US Pat. No. 3,923,685 relates to cholesteric substances which change into the nematic state under the action of an electric field. US Pat. No. 3,931,041 describes combinations of nematic and optionally cholesteric substances which are suitable for imaging and display devices, l

Although colored images made using cholesteri-10 see fabrics in this way are quite useful, they are usually not permanent.

There is therefore a lively interest in the production of cholesteric substances whose color can be fixed. For example, in the above-mentioned US-PS 15 3 766 061 films for decorative purposes described in which the color is fixed by cooling. In addition, US Pat. No. 4,293,435 also describes polymeric liquid crystals in which the color is fixed by lowering the polymer temperature below the glass transition temperature, which in turn fixes the polymer in the solid state.

The use of temperature changes to fix the dye is not always appropriate. There has therefore been an interest in the development of cholesteric substances whose color is different, e.g. can be fixed by photopolymerization, the resulting fixed color being insensitive to temperature. This side! However, it is only a single such polymer known. A group of Japanese researchers reports on such a polymer. It is | 30 poly {gamma-butyl-L-glutamate) which is converted to triethylene glycol

Ij dimethacrylate can be photopolymerized, whereby; I the color is fixed so that it is insensitive to temperature «Is borrowed.

J

\ £ - - h -

One object of the invention is therefore to provide monomeric cholesteric liquid-crystalline substances which are suitable for the production of polymer films with fixed, essentially temperature-insensitive colors 5.

Another object of the invention is the provision of monomeric compounds which, in combination with other liquid-crystalline substances can be used to prepare compositions which show different optical behavior within a wide temperature range.

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These and other objects of the invention will be apparent from the following detailed description of the preferred 'j' embodiments.

% 15 The invention relates to new cholesteric liquid crystal; line monomers that are suitable for the preparation of polymers with J unique optical properties.

One embodiment of the invention relates to photopoly; merizable monomers that are used to make polymer '! 20 films are suitable and have the following structure "R.o 0

1! 1Ü I! I I

CHo = C-C-G ~ R "-C-0" <. J

* 2 2 \ "| \ i '• 1 H j

i y I

îj - H

I y where Rj is H or CH ^, an alkylene chain with 3 to 14 Ü methylene or lower alkyl] substituted methylene groups! J, ÿ% s: (\ ____ j - 5 - and y mean 0 or 1, provided that y is 1 if CH means ^.

The second embodiment of the invention relates to photo-polymerizable monomers which are suitable for the production of polymer films and have the following structure: '"Γ' - 'Υ

R, ° 0 S

I 1II II H

iCH ^ C-C-O-A-C-O-y ^ v J

! Hy

ί H

Î * y | where Rj is H or CH ^, A -R ^ O- or -R O-, R ^ is an alkylene- f | . chain with 2 to 14 methylene or lower alkyl substituents! ten methylene groups, R. an alkylene or lower alkyl 10 substituted alkylene ether, diether or triether with, .A total of 3 to 14. Carbon atoms in the alkylene units mean: • under the condition that the final | s! ge, adjacent to the carbonate unit alkylene unit | I has at least 2 carbon atoms and y is 0 or 1 * 15.

il | . A third embodiment of the invention relates to compounds which are suitable as intermediates for the production of photopolymerizable monomers and have the following structure: f Î! il 9 f ’] I% 4 i» v— "j p

/ V

ïi / - 6 - wherein Br, J or a sulfonic acid ester, R2 is an alkylene chain with 3 to 14 methylene- or lower alkyl-substituted methylene groups and y is 0 or 1.

Cholesterol derivatives which can be used according to the invention are Cho-5 lesterin (with y = 0) and 5,6-dihydrocholesterol (y = 1). There are also a number of substitution options in the 3-position side chain. So e.g. For example, the polymerizable portion of the side chain can contain an acrylate or methacrylate fragment that is connected via a bridge to (10) an ester or carbonate unit

If an ester unit is present, the bridge can contain an alkyl chain of 3 to 14 methylene or lower alkyl-substituted methylene groups, lower alkyl being understood to mean 1 to 4 carbon atoms. 15 of the Soviet literature describes methacrylate esters with Rj = CH ^ and n = 5, 10 and 14. However, these were used for the purpose of their use in solvent poly. merization reactions produced. However, there is no question of their usability for producing photopolymerized films.

On the other hand, if there is a carbonate bond, the bridge can be more complex. So e.g. it can contain 2 to 14 methylene or lower alkyl substituted methylene groups or an alkylene or lower alkyl substituted alkylene ether, 25 diether or triether with a total of 3 to 14 carbon atoms in the alkylene units. contain, wherein the terminal, adjacent to the carbonate fragment alkylene unit has at least two C-Atoir.e. The reason for this limitation is described below. Examples for . 30 ether residues, as can be used in the practice of the invention, are analogs of ethylene glycol,, diethylene glycol, triethylene glycol, tetramethylene glycol, 3,3'-oxybis-l-propanol, 4,4'-oxybis-l-butanol, l, l'-Oxy-i i bis-2-propanol and others

1 £ t,, t -Τ ι: ‘In the pure state, the compounds according to the invention are somewhat difficult to treat, since they show the tendency to crystallize out at unfavorable moments. In addition, it is difficult to colored polymers from the pure polymers.

| 5, since most of them either show no colored cholesteric mesophase at all or only; a very narrow one. The pure compounds according to the invention are therefore limited in their ability to produce polymer films with desired properties.

(10 Surprisingly, it has now been found that these restrictions can be eliminated and that colored and uncolored films can be prepared on the basis of the compounds according to the invention and photopolymerized in the presence of a suitable photoinitiator, 15 which gives films with fixed optical properties. When the film is colored, the fixed color is preferably substantially the same as that of the unpolymerized film, but in certain circumstances it may be desirable to obtain a polymerized film having a fixed color that is different from that of the unpolymerized film Films differs.

! (- I The cholesterol ester derivatives according to the invention can be obtained in a surprisingly high yield by reacting w-sub-! -Stated alkyl acid halide (I), which is preferably an i 25 w-bromoalkyl acid chloride, with the desired; cholesterol derivative (II) to give a cholesterol Substituted alkyl ester (III) The reaction of this compound with an alkali metal acrylate or methacrylate (IV) in the presence of a radical inhibitor and I 30, a suitable catalyst then gives the desired

Acrylate or methacrylate ester (V). The sequence of the individual 2-8 individual reactions can be represented by the following reaction scheme

VvK + L 11

HyJ

JV i y

(? [KT

111

H

y 1! R, 0 y

j I 1 II

5 CH2 = C-C-0-M + III-^

IV

R, 0 O v

* 1 il «H

I CH2 = C-C-0-R2 "C-0

! H

! yhyi (j In these and other reactions shown here, K or CH ^, F> 2 mean an alkylene chain with 3 to 14 methylene- or lower alkyl-substituted methylene groups,. [10 y 0 or 1, Br, I or a sulfonic acid ester, X2 Br or Cl and M Na or K. Examples of suitable sulfonic acid esters are CH-SO.-, p-CH-, CrR .SO--, C ^ H.SO, -, * jjw * h 4 J bbb p-BrC ^ H .SO ,, - including X, preferably means Br and X_ Cl. Jb 4 3 1 - 2 j In the case of the intermediates of type III, R2 preferably has 4 to 14 C atoms in the 15 alkylene chain.

The cholesterol carbonate derivatives IX can

JL

_____.

; /

B

- 9 - loot can be produced in a slightly different way. In this reaction sequence, a haloalcohol VI is reacted with a suitable cholesterol haloformate VII to give a w-haloalkylcarbonate derivative VIII, which in turn is reacted with an alka-5 limetallacrylate or methacrylate IV, as described above, to give a carbonate monomer IX. However, the compounds IX can also be prepared by reacting a compound VII with a hydroxyalkyl acrylate or methacrylate X. Compounds IX can thus be prepared according to the following reaction scheme, which illustrates the two ç alternatives listed: ro, s C "? T ___

Xj ^ -A-H + X2-C-0Jx ^ Jv 1 ^

V

Hy ^

VI

! (

i "l ^ T

! - '? nvi ......

i Χ ,, - Δ-C-O — L ..! -J VIII

ί I ^ ^ *. ' Hi *! / 1 y i i y I Ψ I .cL- b 4 ii - 10 - R, ο o ix f1 «Il Η IV + VIII ^ C ^ C-C-O-Ä-C-oA ^^ J.? ^! y! C r, o f I 1 ii CH2 = è-C-O-A-H + VII-

; X

! => wherein, X ^, X2 and y have the meanings given; and A is -R ^ O- or R ^ O-, where R ^ is an alkylene chain j 5 with 2 to 14 methylene- or lower alkyl-substituted i methylene groups and R ^ is an alkylene- or lower alkyl-substituted alkylene ether, -diether or -triether j is a total of 3 to 14 carbon atoms in the alkylene units, provided that the alkylene unit adjoining the carbonate part contains at least 2 carbon atoms: Examples of suitable ether fractions are given above, but the restrictions regarding the length of the one terminal unit must be pointed out.

This is the alkylene group adjacent to the carbonate portion I 15 in compound IX. None of the synthesis options described here is for the Ver. Turn of an ether with a single carbonate

! proportion of adjacent C atom. The compounds VI

|! and X must therefore not contain a -0-CH2-0H group. The 20 terminal alkylene unit adjacent to the carbonate portion must therefore contain at least two carbon atoms.

The advantages and features of the invention are illustrated in more detail by the examples below. However, this does not limit the scope of the invention.

example 1

Production of cholesterol-w-subst. Type 5 III alkyl esters.

0.1 mol of cholesterol or 5,6-dihydro-cheolesterol, 0.12 mol of pyridine and 0.12 mol of w-b'romalkanoyl chloride are dissolved in 200 to 300 ml of a suitable solvent, such as ethanol-free! . · (Chloroform or ether / dichloromethane dissolved. The mixture obtained in this way is then stirred for 2 hours at 0 ° C. and then for 16 hours at room temperature and then diluted with 300 ml of solvent. The organic phase is then mixed with two portions 200 ml of 1N HCl and then washed with water and dried over magnesium 15 sulfate, and the dried solution is obtained by evaporating the esters III, which are then recrystallized from a suitable solvent, such as e.g.

Purified ether-ethanol (1: 1). Representative compounds according to the invention are illustrated in the following table: i (“I Ύ;". '^! I j__i i o

· Er- (CH2) n-c-0-l ^ _ ,. j III

ί H

i n YJ

f i! t- ~ I / j I.

"I" - 12- * /

Compound n y Yield (%) Sp (° C) _

Ilia 10 0 89 99-100 IHb 5 0 86 120-121 IIIc 30 86 87- 90 5 Illd 31 91 92-93

Ille 10 1 87 65- 67 I Example 2

Preparation of Type V Cholesterol Ester Monomers

In a mixture of water (30 ml) and chloroform (15 ml) 10, a two-phase solution of 0.15 mol of Acrylate-K or Methacrylate-K, 0.05 mol of Ester III, 0.01 mol of Ν, Ν, Ν, Ν-tetra-1 n-butylammonium bromide and 0.0034 mol 2,6-di-t-butylcresol | as a radical inhibitor. This is then heated and stirred with a magnetic stirrer in an i 15 oil bath at 110 to 115 ° C. for 40 hours. After cooling, the mixture is diluted with 500 ml of a solution of ether and dichloromethane (4: 1) and the organic phase is separated off and washed twice with water. After drying over magnesium sulfate, the organic phase is concentrated to give the acrylate or methacrylate monomer V, which is recrystallized from a suitable solvent, such as ether-ethanol or acetone-ethanol. The table below shows representative ones Monomers according to the invention illustrated: * '"j

Sr t * ί - 13 - v

Ich2 = c-c-o- (ch2) ^ I V

HY

/· H

(y | Yield melting or meso; compound Rx n y (%) phase range (° C)

Va H 10 0 83 * 54.5 - 71.5 ij 5 Vb CH 10 0 88 * 58 - 64

I J

ji Vc H 5 0 87 * 45.5 - 68.5 ji Vd CH3 5 0 90 * 48 - 57.5 I Ve H 3 0 83 68.5 - 70.5 (67.5) jj Vf CH3 3 0 75 73-74 (56.0) I 10 Vg H 3 1 58 41 43 (35.5} vh CH 3 1 71 43 - 45 (under Rt) îi ij Ç Vi H 10 1 70 62.5 - 64.5 ( 58.0) | vj CH3 10 1 56 * 33.7 - 49.0 j ------------------------------- -

Il * | i In these examples and in the following examples | . 15 means the temperature ranges, unless otherwise stated, melting ranges. These are identified by an asterisk | i - | j chen *) or by brackets. An asterisk | means that the range is a mesophase range, whereas the brackets indicate that the range is a mono-20 troper mesophase range, the latter being measured at a reduced temperature. For compounds with precisely determinable melting points, the monotropic j; Mesaphase range often below the melting range.

I T5 B, i m - 14 - *

Example 3 ‘According to this example, cholesterol ester monomers from

Type V made using a polar aprotic solvent system and not under phase transfer catalyzed conditions as * in Example%. A mixture containing 0.05 mol of bromine-substituted ester III, 0.10 mol of Acrylate-K and 0.0034 mol of 2,6-di-t-butylcresol as radical inhibitor is prepared in dimethylformamide (50 ml)! posed. The mixture thus obtained is heated in an oil bath at 70 to 80 ° C for 3 hours.

After cooling, the mixture is diluted with water (250 ml) and extracted with ether (4 x 150 ml). The organic phase is washed with brine, dried over magnesium sulfate and concentrated to give the acrylate monomer il V, which is recrystallized from ether-ethanol.

1 - Iodine-substituted esters III also give useful results under these conditions.

Î,) <Example 4 5 Production of cholesterol-w-haloalkylcarbonates from! Type VIII.

A solution of 6-bromohexanol (0.075 mol) and pyridine | ((0.055 mol) in dichloromethane (50 ml) is mixed with ii. * "Of a commercially available solution of cholesterol chloroformate (0.05 mol) in 50 ml dichloromethane. The addition is carried out at room temperature The mixture is stirred for 18 hours, after which it is diluted with 200 ml of dichloro-1; "^^, -: · methane and then washed twice with 75 ml portions of I" 1 n.HCl and then with water organic

The phase is dried over magnesium sulfate and concentrated to give solid w-bromoalkyl carbonate of type S VIII, which is obtained by recrystallization from Sther- | Ethanol is cleaned. The compound (villa) I obtained (yield 78%) has an S of 87 to 88.5 ° C.

2 il p * t 1 «k * * - 15 -

Example 5

Preparation of cholesterol acryloyl or methacryloyl oxyalkyl carbonates from carbonates of type VIII.

A solution of 0f02 mol of the product from Example 4 (Villa) 5 and 0.06 mol of methacrylate-K is heated for 40 hours as described in Example 2. After recrystallization j of the solid product from a solution (1: 1: 5) of acetone! Ethanol gives a methacrylate monomer (yield 68%) with a temperature of 58.5 to 60 ° C.

i 10 Example 6 i This example illustrates the alternative method to t

Preparation of Type IX Compounds by Reaction of a Type X Hydroxyalkyl Acrylate or Methacrylate

} j with a cholesterol haloformate of type VII. A solution of hydroxyalkyl acrylate or methacrylate (0.06 mol) i and pyridine (0.044 mol) in 40 ml dichloromethane is added dropwise to a solution of cholesterol haloformate (0.05 Mol) in 40 ml of dichloromethane. The addition takes place at 0 ° C. Thereafter, the mixture 20 thus obtained is warmed to room temperature and stirred for 6 hours stirs. The product mixture obtained is diluted with 250 ml of dillchloromethane, washed with 60 ml of 1N.HCl and then with water. The organic phase is dried over magnesium sulfate and concentrated to give a solid which is recrystallized from a suitable solvent, such as j-acetone-ethanol. The representative products are summarized in the following table: j Î y i: i I * - 16 - * r, o o 11 II II I ®

CH ^ C-C-O-A-C-O-k ^^ / IX

yT

c j compound R, A y yield melting or! (%) Mesophase range ___________________________________ (° C) ____ 5 IXa CH0 (CH_) cO 0 68 58.5 - 60 (51.0) j Z b IXb CH3 (CH2) 20 0 82 80 - 81 (40.1) IXe H (CH2) 20 0 81 85.5 - 87 (56.0) IXd H (CH2) 60 0 48 ** * 52 - 62 ** Prepared by treating compound Villa, ί · 10 as described in Example 2.

(

Example 7

This example illustrates the production of alkylene! Type IX ethers and diethers, in which A = - (CH2CH20) 2 ~ and - (CH2CH20) The starting compounds X are prepared by 15 methods known from the chemical literature; and, as in Example 6, implemented, whereby the * following products are obtained:

Compound R ^ A y From enamel or prey mesophase range 20 ___________________________ ___ (_% _) range (° C) ______ IXe CH3 (CH2CH20) 2 0 60 48.5-52.9 (33.1) | IXf CH3 (CH2CH20) 3 0 62 no S (6.5)

P

: <? - 17 - I Λ rn * **

Example 8

This example illustrates the color ranges of the various monomeric esters V according to the invention, measured with the aid of a Leitz light microscope with light passing through cross-polarizers at 250-fold magnification.

A temperature controller of type Mettler FP5 and a heating table of type Mettler FP52 are used for the temperature setting, the cooling taking place by passing a nitrogen stream through a copper coil-cooler cooled with dry ice and then through the heating table.

(| Connection_________________Color range (° C) _

Va 57.8 - 59.2 j: Vb (55.8 - 55.3) 15 Vc (48.5 - 33.0) | Vd (51.0 - 26.5) * Ve no color | Vf no color ---------------------- 1' ....

1 The invention is not solely based on the above description ç 20 and the examples given are limited, but also apply to all modes covered by the claims fications.

| V

ji s / 1%>! / I a [* j! L if i * i tl IJ- 'li

'S

Claims (5)

3. Compounds according to claim 2, characterized g e k e η n - that R4 is lower alkyl substituted. 4. Connections of structure Ï: rX ^ i 5 IM yHT. ! 'where X. Br, J or a Su] f onSäurestcr, R_ an alkyl chain with 3 to 14 methylene or n i ederal kyl subst i -! Mutated methylene groups and y mean 0 or 1. : λ I - 20 -! - "* 5. Compounds according to claim 4, characterized in that 1 * 2 is 4 to 14 methylene or lower alkyl-substituted methylene groups. » 6. Compounds according to claim 4, characterized g e k e η n - * \ - that Xj means Br. 7. Compounds according to claim 5, characterized g e k e η n that Br means. ^ .j / f. Ï | [3; - i a i i; * i · * V1 I * - i il