DE2346935A1 - POLYCARBONATES CONTAINING S-TRIAZINE RINGS WITH FUNCTIONAL GROUPS, THEIR PRODUCTION AND USE - Google Patents

Description

Bayer Aktiengesellschaft 2346935

Central Patents Department. Trademarks and licenses

L / GW 509 Leverkusen. Bayerwerk

17th Sept 1973

Polycarbonates containing s-triazine rings with functional groups, their production and use

The present invention relates to polycarbonates based on aromatic bishydroxy compounds, in particular based on of bis (hydroxyphenyl) alkanes, the s-triazine compounds as links between each 2 moles of the aromatic bishydroxy compounds via one oxygen atom each on the one hand and via carbon atoms of the s-triazine rings on the other Contained bonded, the s-triazine rings on at least one other carbon atom via oxygen, nitrogen or carry sulfur-bonded organic radicals with functional groups.

Functional groups here are acid groups, modified Acid groups, such as esters or amide groups, and aliphatic groups Understood hydroxyl groups, in particular carboxyl groups, esterified or amidated carboxyl groups, sulfonic acid groups, amidated sulfonic acid groups and aliphatically bonded hydroxyl groups. Preference is given to those bound via nitrogen organic residues with carboxyl groups or with aliphatically bonded hydroxyl groups.

The s-triazine compounds can contain one or two e-triazine rings; In the s-triazine compounds with two 8-triazine rings, these are linked by organic radicals that carry functional groups, these being organic

Le A 15 223 '- 1 -

5 0 9 8 U Π 1 8 9 bad original

Best via oxygen or sulfur, but preferably via nitrogen on one carbon atom each of two s-triazine rings can be bound.

The invention also relates to a process for the production of said polycarbonates, according to which said polycarbonates aromatic bishydroxy compounds modified with s-triazine compounds containing functional groups, by themselves or with the use of correspondingly unmodified aromatic bishydroxy compounds according to known ones Process with the help of phosgene or other polycarbonate-forming Derivatives of carbonic acid are converted into polycarbonate.

The invention also relates to the use of the new polycarbonates mentioned as absorbents.

The polycarbonates according to the invention can e-triazine rings the following general formula 1,

(R -> - 4Q) _a

in the

Z stands for -0-, -S-, -NH- or -NR-,

R alkylene groups with 1-20 carbon atoms, cycloalkylene groups with 5-12 carbon atoms, mononuclear or polynuclear Arylenes or carbon-bonded heteroaryls = res te with up to 14 carbon atoms, mono- or polysubstituted mono- or polynuclear arylene or over

Ie A If 2 23 - 2 -

509814/1189

Carbon-bonded heteroarylene radicals with "up to 14 ring carbon atoms, where possible substituents include, for example, alkyl, alkoxy or alkylmercapto groups with 1-4 carbon atoms, halogen atoms such as chlorine or bromine, -NO ₂ or -CN, alkylarylene radicals with a total of up to to 30 carbon atoms, or aralkylene radicals with a total of up to 30 carbon atoms,

R ¹ alkyl radicals with 1 to 20 carbon atoms, cycloalkyl radicals with 5 to 12 carbon atoms, mono- or polynuclear, unsubstituted or substituted aryl or carbon- bonded heteroaryl radicals with up to 14 ring carbon atoms, where the substituents Z ₀ B ₀ ADcyl- , Alkoxy or alkyl mercapto groups with 1 to 4 carbon atoms, halogenators such as ζ _β ΰ. Chlorine or bromine * -TTO _? or -OTT in embossing can mean alkylaryl radicals with a total of "up to 30 carbon atoms, Ai-alkyl radicals with a total of bie zv 30 carbon atoms or Hyclroxyelkylreute with 1 to 10 carbon atoms,

Q is a -COOH-, -COOR ² -, -CONR ³ R ⁴ -, -SO ₃ H-, -SO ₂ NR ³ R ⁴ - or aliphatically bonded -OH group,

R ^{2 represents} alkyl groups with 1-4 carbon atoms,

R'u. R * independently of one another for hydrogen, for straight-chain or branched alkyl groups with 1-4 carbon atoms or for an unsubstituted, single or polysubstituted phenyl radical or together with the N atom a 5- or 6-membered ring system form and

a.,. ^ lne ^ whole ^ ahl ^ of. ,, 1 ^ -. | ^ be (|| ^ tet »ala

-dem ny & c rfoslnis

a ^ mIS

Le A 15 223 - 3 -

^{5 r} " ¹ feil · V \ A Γ 8β 03 ^BAD original

The polycarbonates according to the invention can be used instead of the thatch or in addition to the radicals of the general formula 1, festivals of the general! Formula 2,. _

(2)

in the

R ⁵ and R ⁶ independently represent H or alkyl, hydroxyalkyl, carboxyalkyl, alkoxycarbonylalkyl groups, C 1 -C 4 cycloalkyl, substituted and unsubstituted C 6 -C 4 aryl groups containing 1-5 carbon atoms

like-j ne air. r ^ l Rin £ systoir-, vie -I

· 1ρτπ ll-.M ~ rr, - ^

I- ζ ^ R

χτ :> · -] i. ^ i r. ~, Ti: er ^; -71

as a link between the aromatic bishydroxy compounds contain bound via their oxygen atoms.

Preferred substituents of the formulas 1 and 2 mentioned are: Z = -NH-, -NR ¹ -, R = alkylene with 1-10 carbon atoms or phenylene, Q = -COOH, -SO, H or aliphatically bonded hydroxyl groups, R ₁ = alkyl with 1-6 carbon atoms or hydroxyalkyl with 1-6 carbon atoms, R ₁ - and Rg - independently of one another hydrogen, hydroxyalkyl with ί-λ π, 4 "l> yT ¹ ^ ⁺ 1-1 C ₁ phenyl and sulfoxyphnnyl .

The new polycarbonates containing s-triazine rings can consist essentially of identical or non-identical structural units the following general formula 3 and / or 4 be built up,

BAD ORJGJNAL

Le A 15 223

8u7iN ~ 8

JS *

-0-XOO) ₅ - (4)

in those
X

one ο-, m- or p-phenylene radical, one single or multiple substituted ο-, m- or p-phenylene radical, where as Substituents e.g. lower alkyl groups with 1-4 carbon atoms or halogen atoms, such as chlorine or bromine, are possible or preferred one by the formula 5

R ⁷ R '

(5)

marked remainder means in which

and R for hydrogen atoms, alkyl radicals with 1-4 carbon atoms or halogen atoms, of the latter preferably chlorine or bromine atoms, are and are identical or different Have meaning

a single bond, an alkylene or alkylidene radical with 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -0-, -S-, -CO-, -SO-, -SOp- or a radical of the formula 6a or 6b,

(6a)

(6b)

11

Xe A 15 223

5098U / 1 189

r9 to R ¹¹ denote alkyl radicals with 1-4 carbon atoms, R ¹¹ also denote hydrogen or halogen atoms, such as chlorine or

Bromine, can stand,

Z, R, Q, a, R ⁵ and R ^{6 have} the same meaning as given under the formulas 1 and 2 and η is a number between 1 and 200, preferably between 3 and

100 is.

Preferred Y radicals are the isopropylidene and the cyclohexylidene radical.

The weight average molecular weight (M), determined by the light scattering method, is generally above 10,000, preferably between 20,000 and 200,000. Of course, it can polycarbonates containing s-triazine rings with lower molecular weights can also be produced.

pie end groups of the new polycarbonates have on the properties of the products does not have a decisive influence. For the sake of completeness, the end groups A for the left side of the Structural formulas 3 and 4 and the following as end groups B for the right-hand side:

A in 3 and 4 represents H or -CO-OR ¹² , where 12

R denotes a phenyl radical or a mono- or polysubstituted phenylreand, in 3 also denotes a radical of the general formula 7,

<HQ _a (7)

Ie A 15 22?

5098U / 1 189

where Z, R, Q and a herenτ the meaning given above

B stands for -OR, where R has the aforementioned meaning.

Polycarbonates containing s-triazine rings with functional groups were not previously known

The new polycarbonates according to the invention are distinguished in particular by the fact that, through the incorporation of the s-triazine structural units of the formulas 1 or 2 via the substituent Q in formula 1 or via the sulfo group and / or via the radicals R ⁵ and R ⁶ in Formula 2 are suitable for polymer-analogous reactions.

Polycarbonates «it structural units of formula 3» in the Q for -COOH or -SO, H show surprisingly strongly lipophilic properties when in common polycarbonate solvents are insoluble. The lipophilic character of these modified polycarbonates can be influenced to a large extent The type and proportion of triazine segments on the one hand or by changing the molecular weight on the other hand can be varied. Ia generally suffice to achieve the desired effect, triazelines of the formula 1 of less than 15 mol Ji, preferably 10 mol-jC or less than 10 mol-jG, possessed. on the Structural unit of the formula 3. The solubility of these polycarbonates can be controlled, among other things, by installing Terzweigern or Verneteern. With such products you can e.g. from mixtures or solutions of aliphatic or aromatic hydrocarbons such as methylene chloride, chlorobenzene, Benzene or xylene with or in water remove the hydrocarbons almost quantitatively by absorption, which is great Is important for the purification of industrial wastewater.

The invention therefore also relates to the use of polycarbonates of the formula 3 containing α-iriazine rings, in the

Q is -COOH or -SO, H and Z, R, a, I and η have the meaning given above,

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5098U / 1 1 89

for the absorptive removal of aliphatic, cyoloäliphatic, aromatic and halogenated hydrocarbons from mixtures or solutions of these hydrocarbons with or in aqueous solutions containing water or inorganic salts.

A particular object of the invention is the use of s-triazine rings-containing polycarbonates of the formula 3 in the

Z for NH,

Q for -COOH,
a stands for 1,

χ _ // Vc - // ^N > - means and

R has the meaning given above,

for the absorptive separation of aliphatic, oycloaliphatic, aromatic and halogenated hydrocarbons from mixtures or solutions of these hydrocarbons with or in aqueous solutions containing water or inorganic salts Solutions.

High molecular weight polycarbonates containing s-triazine rings according to the invention can be prepared by initially Dihalo-s-triazines of formula 8,

(8th)

(RffQ)

Le A 15 225 - 8 -

5098U / 1189 ¹ ^ ⁰ OBlGlNAL

Hal F, Cl, Br and J, but preferably Cl, denotes and Z, R, Q and a have the abovementioned meaning, or dichlorobistriazinyl compounds formula 9,

SO, H
j ο

Cl-r ^ V ^ -Z ^ -OH-CH - / ^ "^^^ - ^ O)

wherein R "R" B / V

R ft

R ι '* - ¹ v ⁱ have orgenannte importance, m 11 -> bit "201 jn equivalent of an aromatic dihydroxy compound of the formula Vin'iiir ^ 10.

HO-X-OH (10)

woi'.i .ι λ d'u ^{1 has the} abovementioned meaning, either in the presence of a proton acceptor or preferably with 2 to 201 equivalents of the alkali metal salts of an aromatic dihydroxy compound of the formula 10 by conventional processes for the preparation of trisubstituted s-triazines

a) i: i a rain over the reactin components 8, 9 and 10 indifferent organic solvent or

b) in an aqueous alkaline medium or

c) in a one- or two-phase mixture of one opposite organic solvent indifferent to the reactants and an aqueous alkaline phase

at temperatures between 0 and 300 ° C., preferably between 30 and 150 ° C., and reaction times between 0.2 and 20 hours converts and then the intermediately formed s-triazine rings containing aromatic dihydroxy compounds of. 11 and 12 or their alkali salts

Le A 15 2? 3 - 9 -

BATH

5098U / 1 189

23A6935

ο-χ-οκ

(H)

SO ₃ H

HO-XO -, * ¹ K-NH-Z ^ V CH = CH- ^ ^> - NH-r ^ ^N -jpO-Σ-ΟΗ (1?) NN / Υ /

depending on the choice of the Mo 1 ratio used in the implementation of 8 or 9 with 10 either on its own or in the Mixture with further 10 with phosgene and / or bischlorocarbonic acid esters of the aromatic dihydroxy compounds 10 and / or from 10 obtainable oligomeric carbonates containing chlorocarbonic acid ester end groups, the sum of the equivalents the dihydroxy compound 10, used as such and / or as their allcalis salts and / or all their bischlorocarbonic acid esters and / or as oligomers containing chlorocarbonic acid ester end groups prepared from the dihydroxy compound 10. Carbonates, not exceeding 201 equivalents per equivalent of the compounds or 9, and wherein per phenolic OH equivalent at least 1.05 chlorine equivalents bound via -CO- are used, according to known polycarbonate production processes, preferably the process of interfacial polycondensation.

Both different dihalo-s-triazines 8 and different bistriazinyl dichloro compounds 9 as well as mixtures of 8 and 9 and also different aromatic dihydroxy compounds 10 can be reacted next to one another if a corresponding carbonate copolymer is desired. In addition, it is easily possible to react the reaction products of 8 and 9 with an aromatic dihydroxy compound with other aromatic dihydroxy compounds and the abovementioned polycarbonate-forming compounds.

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B098U / 1189

The process according to the invention is characterized in that the production of the s-triazine-containing bishydroxy compounds 11 and / or 12 and the subsequent production of the polycarbonates on the basis of 11 and / or 12 and optionally other dihydroxy compounds in the same reaction medium and in the same reaction vessel can be done without isolating the intermediate stages 11 or 12. Separate production of the s-triazine-containing bisphenols is possible, but not necessary.

A particular advantage of the process for producing the s-triazine-containing polycarbonates of the formula 3 is also that instead of the purified halogen-s-triazines 8 also the Solutions or suspensions of the reaction of trihalogen-s-triazines, preferably cyanuric chloride, with nucleophiles Compounds of formula 13,

(Q ^ - (Rl-Z-H (13)

in the

Z, R, Q and a have the abovementioned meaning, in a known whiteness (see p. 12) obtained unpurified dihalo-s-triazines immediately for the next «? Condensation with aromatic dihydroxy compounds IO can be used.

Another variant of the production of the polycarbonates according to the invention consists in the conversion of the dihalo-s-triazines 8 and / or 9 with the bishydroxy compounds 1Γ in the presence of 0.01 to 5 mol percent of a trihalogen triazine, based on the structural unit of the formulas 3 and / or 4, where Hai has the meaning given for 8 has, but is preferably Cl, so that trifunctional hydroxy compounds of the formula 14

jO-X-OII (14Ί)

0-X- (

OH
Le A 15 223 - 11 -

50981 4/1189

are contained in the reaction mixture toi the following Reaction with polycarbonate-forming compounds such as phosgene and / or, bishlorocarbonic acid esters of bishydroxy compounds cause branching of the polycarbonates via s-triazine rings.

For the production of the homo- or copolycarbonates according to the invention Dihalogen-s-triazines 8 and 9 used are, if not already known, according to in the chemical Process known from the literature.

The dichloro-s-triazines of the formula 8, in which Hal denotes Ol, are obtained, for example, by reacting cyanuric chloride with aliphatic or aromatic amines, alcohols, phenols, mercaptans or Tliiophenolen / see, for example, JR Thurston et al., J. At the. former Soc. 22 »2981 ff. (1951); H. Koopman et al., Rec. Trav. chim. Pays-Bas J [8, 967 (1959}; H. Koopman and J. Daams, Rec. Trav, chira. Pays-Bas 22i 235 (1956), H. Nestler and H. Fürst, J. Prakt. Chen, pj 2g, 173 (1963); S. Horrobin, J. formerly doc. / Londonj 1963 t 4l3Oj DAS 1 176-19; .DOS 1 670 8327

The dichlorobistrjazinylaminostilbene derivatives of the formula 9 are obtained for example, by reacting aminodichlorotriazine compounds with 4,4'-diaminostilbene-2,2'-disulfonic acid or its Salts according to DOS 1 670 832.

As dihalo-s-triazines of the formula 8, which are suitable for the production of s-triazine-containing polycarbonates of the formula 3 are, for example, the compounds that are available when using cyanuric chloride

LeA 15 223 - 12 -

5098U / 1 189

Hydroxyacetic acid, hydroxyacetic acid ~ n-bi? +; / Le3ter, 2-hydroxypropionic acid (Lactic acid), 2-hydroxypropionic acid ethyl ester, 2-hydroxysuccinic acid (malic acid), 2-hydroxypropane tricarboxylic acid (l, 2,3) (Citric acid), mercaptoacetic acid, 2-hydroxyethanesulfonic acid (isethionic acid), 2-aminoethanol, N-methylethanolamine, diethanolamine, 3-amino-lpropanol, l-amino-2-propanol, diisopropanolamine, dihydroxytertiary-tmtylamine, Trihydroxy-tert-butylamine, aminoacetic acid (Glycine), methylaminoacetic acid, 3-aminopropionic acid, 4-aminobutyric acid, 6-aminohexanoic acid, 11-aminoundecanoic acid, Aminosuccinic acid, 2-aminoglutaric acid, methionine, 2-aminoethanesulfonic acid (Taurine), N-methyl-aminoethane-sulfonic acid, 3-hydroxybenzoic acid, 3-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acid, 4-mercaptobenzoic acid, 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid propyl ester, 3-chloro-4-hydroxybenzoic acid, 4-hydroxyphthalic acid, phenol-3-sulfonic acid, Phenol-4-sulfonic acid, 2,6-dichlorophenol-4-sulfonic acid, l-naphthol-4-sulfonic acid, l-naphthol-3,6-disulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-5,7-disulfonic acid, N- (2-hydroxyethyl) cyclohexylamine, arainoacetic acid ethyl ester, 6-aminohexanoic acid ethyl ester, 2-hydroxypropionic acid methyl ester, 6-hydroxyhexanoic acid ethyl ester, mercaptoacetic acid methyl ester, Mercaptosuccinic acid diethyl ester, 2-hydroxyethylaniline, Anilinoraethanesulfonic acid, anilinoacetic acid, hydroxyethyl-mtoluidine, m-toluidino-methanesulfonic acid, 2-aminobenzoic acid, 2-aminobenzamide, 3-aminobenzoic acid, 4-chloro-3-aminobenzoic acid, 4-chloro-3-aminobenzaraid, 6-chloro-3-aminobenzoic acid, 5-nitro-3-aminobenzoic acid, e-Nitro-S-aminobenzoic acid, 4-aminobenzoic acid, 4-aminobenzoic acid ethyl ester, 4-aminobenzamide, 2-nitro-4-aminobenzoic acid, 4-Amino-3-methylbenzoic acid, 3-Atnino-4-methylbenzoic acid, 5-Aminoisophthalic acid, 4-Aminonaphthalinrl, 8-dicarboxylic acid, 3-amino-4-methoxy-benzoic acid, aniline-2-sulfonic acid, Aniline-3-sulfonic acid, aniline-3-sulfonic acid amide, 3-aminobenzenesulfonic acid anilide, 3-aminobenzenesulfonic acid-N-methylanilide,

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5098U / 1 189

e-chloro-aniline-S-sulfonic acid, 4-chloroaniline-3-sulfonic acid. Aniline· 4-sulfonic acid, 4-aminobenzenesulfonic acid amide, diphenylamine-4-sulfonic acid, 4-benzylaminobenzenesulfonic acid, 2,5-dichloro-4-aminobenzenesulfonic acid, 4-aminotoluene-2-sulfonic acid, 4-aminotoluene-2-sulfonic acid anilide, 5-aminotoluene-2-sulfonic acid, 4-aminophenylmethanesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-1,3,5-trisulfonic acid, 2-mercaptobenzothiazole sulfonic acid in a molar ratio of 1: 1 in a known manner.

There are, of course, numerous other dihalo-s-triazines as well as starting materials for the preparation of polycarbonates of the formula 3 containing s-triazine rings.

As aminodichlorotriazine compounds of formula 15,

R ⁵

Cl

which can be ^{reacted with 4,4'-diaminostilbene-2,2 I-} disulfonic acid or its salts to form dichlorobistriazine compounds of the formula 9, which are suitable for the preparation of s-triazine-containing polycarbonates of the formula 4, come, for example the compounds that can be obtained by using cyanuric chloride with ammonia, methyl, ethyl or butylamine. Dimethyl, diethyl or dipropylamine, mono- or diethanolamine, N-methylethanolamine, aminoacetic acid, 4-aminobutyric acid or 6-aminohexanoic acid, aminoacetic acid ethyl ester or ß-aminopropionic acid ethyl ester, aniline, aniline-3-sulfonic acid, aniline-4-cyclobulfylamine or lyrrolidine, piperidine or morpholine in a molar ratio of 1: 1 in “I know what you know” ”? implements.

IeA 15 223 -U-

5098H / 1 189

Suitable aromatic dihydroxy compounds of the formula 10 are, for example: hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, cycloalkanes, sulfides, ethers, ketones, sulfoxides or sulfones. Furthermore ca, a ^f -Bis- (hydroxyphenyl) -dlisopropylbenzenes as / ie the corresponding ring-alkylated or ring-halogenated compounds.

Some preferred aromatic dihydroxy compounds are e.g. B .: 2,2-3is- (4-hydroxyphenyl) propane (bisphenol A), 2,2-BIs- (J, 5-dimethyl-4-hydroxyphenyl) -propane, 2,2-Bls- (5,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (5,5-dibromo-4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane and trinuclear bisphenols, such as », a'-bis (4-hydroxyphenyl) -p-diisopropylbenzene.

These and others for the production of the invention Bisphenols suitable for high molecular weight polycarbonates are described in US Pat. No. 2,970,151, 2,991,275, 2,999,855, 2,999,846, 5 014 891, 5 028 5 ^ 5/5 062 781, 5 148 172, 5 271 567. 5 271 568, 5 280 078 and in DT-OS 1 570 705.

Phenol and mono- or polysubstituted phenols are suitable as molecular weight limiters, but also monohaloene-s-triazines of the general formula 16 in which are suitable

Quay

Z, R, Q _f a and Hai have the meaning already mentioned above. These compounds are obtained as by-products in the preparation of the corresponding dihalogen derivatives.

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5098U / 1189

The production of the polycarbonates according to the invention containing s-tziazine ring alt structural units of tonal 3 can be carried out as follows:

First, the trihalo-s-triazine, for example cyanuric chloride, with a nucleophilic compound of the formula 13 in a molar ratio of 1: 1 in a manner known per se, for example in aqueous Medium in the presence or absence of organic solvents for the cyanuric chloride, such as acetone, methyl ethyl ketone or dioxane, with the addition of that for the elimination of hydrogen chloride from cyanuric chloride and 13 on the one hand, and optionally the acidic groups present in 13 for neutralization on the other hand necessary stoichiometric amount of a proton acceptor such as NaOH or KOH. The resulting dihalo-s-triazine 8 is now either isolated from the reaction mixture and purified or as a solution or suspension ir that used in the implementation

Solvent without further work-up directly into the subsequent reaction with an aromatic dihydroxy compound used.

The aromatic dihydroxy compound is placed in a separate vessel and an alkali hydroxide, preferably sodium or potassium hydroxide, dissolved in a molar ratio of 1: 2 in enough water that about a 10% aq. Alkali salt solution of the bisphenol is present. Water-insoluble or sparingly soluble alkali salts of dihydroxy compounds are called aq. Suspension in the Reaction used. More dilute or concentrated alkali salt solutions or suspensions can also be used without disadvantage will.

A solution or suspension of a bisphenol is then added to this aqueous alkali salt solution or suspension of bisphenol

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509814/1189

isolated and by recrystallization, distillation or Washing out purified or a non-isolated dihalogen triasin, dissolved or suspended in water in the presence or absence of Veit fines organ. Solvent such as acetone, Methyl ethyl ketone or dioxane or one that cannot be detected with water and is indifferent to dihalotriazine organic solvent in a molar ratio of 201: 1 or 2: 1 in portions or in one portion.

As an indifferent organ. Solvents can be used, for example, chlorinated hydrocarbons such as CH ₃ Cl ₂ , CHCl ₃ , CCl ₄ , eth: ylene chloride and trichlorethylene, benzene, toluene, xylenes, chlorobenzene, chlorotoluenes, dichlorobenzene and higher chlorinated aromatics.

The dichlorotriazine solution or suspension can just as easily be submitted and the alkali salt solution or suspension of the bisphenol added.

The well-stirred one- or two-phase Gemisch.wird now held over a period of 0.2 to 20 hrs. At a temperature between 0 and 300 ^e C, preferably between 30 and 150 * C. If necessary, in the course of this reaction stage, those from the reaction of cyanuric chloride with 1? remaining organic «. Solvents such as acetone removed by distillation. As a rule, the condensation of the dichloro-rs-triazine with the dihydroxy compound has ended after 5 hours at the latest. The entire reaction up to this point is carried out under Inex'tgae ^ txioephflre, for example under nitrogen. The alkali salts formed of the bisphenols of the formula '11 containing s-triazine rings are more or less soluble in water, depending on the type of dihalo-s-triazine used and the aromatic dihydroxy compound used, so that either a solution, an emulsion or a suspension is present after condensation has taken place , but this is not of critical importance for the formation of the polycarbonates according to the invention.

Le A 15 225 - 17 -

BAD ORiGtNAL 5 0 9 8 U / 1 1 8 9

If you want to prevent side reactions between the aromatic dihydroxy compound and two molecules of dihalo-s-triazine with formation of intermediates of formula 17

Hai - <^ \ - O-X-0— ^ v. — Hai

A Λ L ¹ N (17)

Z Z

■ ■ (R) - (Q), (RHQK

in which X, Z, R, Q, a and Hai have the meaning given above, occur, it is advantageous to choose a large excess of bisphenol and carry out both the addition of the dihalo-s-triazine as well as condensation at elevated temperatures. However, the formation of the by-products of Formula 17 has an effect not disturbing the overall reaction process, since these too Connections are smoothly built into the polycarbonate framework.

The one- or two-phase ffemisch, in which the im The alkali metal salts of the aromatic dihydroxy compound used in excess and the alkali metal salts of the s-triazine-containing bisphenol of the formula 11 are dissolved or suspended, a solvent suitable for aromatic polycarbonates is optionally added see below, such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane, chlorinated aromatics such as dichlorobenzene, Chlorotoluene or chlorobenzene, and after adding the above-mentioned molecular weight limiter, it sets in the alkaline Environment at a pH between 10 and 14, depending on the type of bisphenol component 10 and the one used s-triazine-containing bisphenol 11, known per se With compounds that form carbonate groups, such as phosgene, bi-chlorocarbonic acid esters, or from dihydroxy compounds Oligomers containing chlorocarbonic acid ester end groups Carbonates around.

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The polycarbonates containing s-triazine rings prepared by the two-phase interface process, which either consist of the reaction mixture precipitate or in the organ. Phase solved are isolated in the usual way, e.g. by acidifying the alkaline reaction mixture and the precipitated The polycarbonate is filtered off and washed neutral with water or the polycarbonate present in solution is removed from the organic Phase precipitates or the neutral washed solution of the polycarbonate evaporates.

The polymers obtained in this way are of low or high molecular weight, depending on the amount of chain limiter added.

When using such dihalo-s-triazines of the formula 8, in which Q is a -CCOH, -SO ₃ H or aliphatic OH group, it is possible, if desired, to use the above-described method via the -COCH, - Polycarbonates containing SO — H or aliphatic —OH group branched or crosslinked s-triazine rings are prepared by carrying out the polycarbonate formation at a high pH, preferably at a pH> 13.

The polycarbonates with structural units of the formula 4 are produced in a manner analogous to that of the polycarbonates with structural units of the formula 3

The novel polycarbonates containing s-triazine rings according to the invention of formula 3 and 4 are due to the incorporation of the s-triazine structural units of formula 1 and 2 via the substituent Q in formula 1 or via the SO, H group or via the radicals R

6 ^x

and R in formula 2 is excellently suited for polymer-analogous reactions. For example, s-triazine-containing polycarbonates, which contain aliphatic OH groups, with aminoplasts or their defined precursors such as melamine, benzoguanamine or urea resins, phenolic resins or di- and polyisocyanates be crosslinked to form hard coatings.

5098U / 1 189

Polycarbonates from Pornieln containing ester and carboxyl groups 3 and 4 can be used, for example, with bisoxazolines or di- and polyepoxide compounds such as glycidic esters to form hard coatings be networked. The paints can optionally contain pigments and the usual paint auxiliaries.

Polycarbonates with structural units of the formula 3, in which Q is a carboxyl or sulfoxyl group, which with a certain molecular weight are insoluble in numerous organic solvents, are ideal for absorptive separation or removal of aliphatic, cycloaliphatic, aromatic and halogen hydrocarbons from aqueous solutions or mixtures with water.

In the following examples, "hours" means hours, "Min" = minutes and "Ex" = example.

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5098U / 1 1 89

sw

Leg game 1

Copolycarbonate from 2,2-ice- (4-hydroxyphenyl) -propane (bisphenol A) and 2-diethanolamino-4,6-dichloro-s-triazine (95: 5 molar parts) with chain breaker.

To a solution of 21.7 g (0.095 mol) of bisphenol A and 7.6 g (0.19 mol) of NaOH in 180 ml of water, 1.27 g (5 mmol) of diethonolamino- ^ ö-dichloro-s-triazine, suspended in 60 ml chlorobenzene, and 0.2 g FaBH. given. The well-stirred two-phase mixture is heated for 4 hrs. At about 90 ⁰ G. It is then allowed to ^{cool to about 20 °} C., an intermediate product precipitating out. After adding 0.43 g (?, 86 mmol) of p-1ert-butylphenol and 120 ml of CHpCIp, 10 percent strength is added. 11 hydrochloric acid to pH - 12 and provided with intensive stirring over a period of about 30 min at 24 -. 27 ⁰ C 13.4 g (0.135 mol) of ₂ GOCl initiated. During the phosgenation, in which the intermediate product dissolves, the pH is kept between 11 and 12 by adding dropwise In-NaOH solution. After the addition of 5.5 ml of 1 ^ strength aqueous triethylamine solution, the mixture is stirred for 10 minutes at pH 11-12, the two-phase mixture becoming highly viscous. After acidification with dilute phosphoric acid, the organic base is separated off, washed with dist. Washed neutral with water and added dropwise to methanol, the polycarbonate precipitating in powdery white form.

After 17 hours of drying at 10O ⁰ C and 15 torr resulted 21.4 g (86 $) s-triazine-containing polycarbonate.

The rel. Viscosity (0.5 g of product in 100 ml of GH ₂ Cl ₂ at 25 ^° C.) is 1.254.

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N content: calc. 1.12 # found. 1.04 ί>

$ aliphatic. OH: calc. 0.68 # found. $ 0.62

The polycarbonate obtained according to Example 1 is dissolved in chlorobenzene and treated with toluylene diisooyanate at the boiling point networked. Hard products result which precipitate from the reaction solution and are insoluble in organic solvents are.

Example 2

Copolycarbonate from bisphenol A and 2-diethanolamino-4,6-dichloro-s-triazine (78:22 molar parts) with chain terminator.

20.1 g (0.088 mol) of bisphenol A and 7.04 g (0.176 mol) of NaOH are dissolved with the addition of 0.2 g NaBH ₄ to ^ atmosphere in 180 ml of water and heated to about 6O-7O ^e C. A suspension of 6.27 g (24.8 nmol) of 2-diethanolamino-4,6-dichloro-s-triazine in 60 ml of chlorobenzene is added dropwise to this solution and allowed to react for 2 hours at 80 ° -90 ° C. with vigorous stirring . After cooling to room temperature, the pH is adjusted to 11 with dilute hydrochloric acid, then 120 ml of CH ₂ Cl ₂ and 1.315 g (8.75 mmol) of p-tert.-butylphenol are added and, according to Example 1, with 9.3 g ( 0.094 mol) COCl ₂ reacted at pH 11-12. After adding 6.3 ml of 1 % aq. Triethylamine solution is stirred for 1 hour at pH 11 and the polycarbonate by evaporation of the neutral washed organ. Phase isolated.

Yield: 24.2 g (93 %) triazine-containing polycarbonate U ^ rel ^{( 0.5 g product in 10} ° ^{ml CH} 2 ^C1 2 ^'25 " ^{C): X} ' ⁰⁷⁸ N content: calc. 5.35 % found 4.97 % OH number calculated 107 found 91

The polycarbonate obtained in Ex. 2 is, for example, with hexamethylolmelamine hexamethyl ether Can be stoved in m-cresol in the presence of p-toluenesulphonic acid at 200 ° C. to form hard coatings.

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Example 3

Cross-linked copolycarbonate made from bisphenol A and 2-diethanolamino-4,6-dichloro-s-triazine (90:10 molar parts) with chain terminator.

According to Example 1, 20.6 g (0.09 mol) of bisphenol A _1, 7.2 g (0.18 mol) of NaOH and 2.53 g (0.01 mol) of 2-diethanolamino-4,6-dichloro Striazine in a solvent mixture of 180 ml of water and 60 ml of chlorobenzene with the addition of 0.09 g of NaBH, 4 hours. Reacted at reflux temperature. After cooling, 0.27 g (1.8 mmol) of p-tert-butylphenol and 140 ml of CH ₂ Cl _{2 are} added, the pH is adjusted to 14 with 2N NaOH solution and 11.9 g are added at pH 14 with vigorous stirring (0.12 mol) COCl ₂ initiated. After the phosgenation is the aq. Phase free from bisphenolate salt. Then 4.9 ml of 1 percent. aq. Triethylamine solution added and condensed. After a further stirring time of about 3 minutes, the batch initially becomes highly viscous and finally clumps together so strongly that further stirring is no longer sensible. The gel-like swollen polycarbonate mass is filtered off with suction, treated several times with dilute phosphoric acid and then washed with water.

After drying for 24 hours in a vacuum drying cabinet at 100 ^° C., about 25 g of a hard, viscous mass are obtained.

The product is insoluble in most organic solvents.
N content: Ber. 2.29% found 2.20%

Example 4

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazin-2-yl) -p-aminobenzoic acid (90:10 parts by mole).

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To a solution of 20.6 g (0.09 mol) of bisphenol A and 7.6 g (0.19 mol) of NaOH in 190 ml of water, with the addition of 0.2 g of NaBH _4, 2.85 g (0.01 Mol) N- (4,6-dichloro-s-triazin-2-yl) -parainobenzoic acid added and heated to about 90-95 ° C. for 5 hrs. The dichloro-s-triazine dissolves during the heating process. A clear solution is obtained after cooling to 20 ° C. After adding 2OO ml of CH ₃ Cl ₂ , a pH of 12 is set and, as described under Example, _{reacted with 11.9 g (0.12 mol) of COCl 2} at pH 12, a milky white, slightly viscous emulsion being formed forms. The pH is then adjusted to 13, 8 ml of 1% strength aqueous triethylamine solution are added and the mixture is stirred at pH 13 for 1 hour.

After acidification with dilute phosphoric acid, shake out twice with distilled water and then the entire two-phase mixture, since the two phases separate very slowly, added dropwise to methanol, the polycarbonate being powdery turns out white.

Yield: 24.7 g (100 %) triazine-containing polycarbonate N content: calc. 2.26 % Found 2.22 % COOH: "1.82 % " 1.7 %

The product is insoluble in common polycarbonate solvents such as CH ₂ Cl ₂ , tetrahydrofuran, dioxane and pyridine.

The N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid used was made as follows:

In a solution of 92.2 g (0.5 mol) of cyanuric chloride in 650 ml of acetone at 0-5 ^e C a suspension of 68.6 g (0.5 mole) of p-aminobenzoic acid and 50.6 g (0, 5 mol) TrietVvlan / registered in ir. L? 50 ml acetone. The reaction temperature is allowed to rise to 20 ° C. within 90 minutes and stirring is continued for a further 90 minutes. The precipitated reaction product is filtered off with suction, washed with dist. Water washed free of chloride, boiled twice with acetone and ^{dried at 50 e} c / 15 Torr.

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Yield: 114 g (80 % of theory ), melting point> 300 ° C. Analysis: Calc. C 42.1 % H 2.11 N 19.65 Cl 24.95 found 41.7 % 2.17 19.2 24.7

Example 5

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s ~ triazin-yl-2) -p-aminobenzoic acid (89.5: 10.5 parts by mole).

According to Example 4, 18.3 g (0.08 mol) of bisphenol A, 7.2 g (0.18 mol) of NaOH and 5.7 g (0.02 mol) of N- (4,6-dichloro-s triazin-2-yl) -p-aminobenzoic acid in 320 ml H ₃ O 5 hrs. reacted at 90-95 C ^e.

After cooling, a solution of 31.8 g (0.09 mol) of bisphenol A-bischlorocarbonic acid ester in 620 ml of CH ₃ Cl _{2 is allowed to run into the yellow solution of the sodium salts of the dihydroxy compounds over the course of 2 minutes while stirring vigorously} 15.2 ml of 1% aq. Triethylamine solution is added and the mixture is then stirred, the pH of the aqueous solution being kept at 12. The two-phase mixture becomes very viscous in a short time. The reaction is terminated after about 20 minutes, as a white black-like gel precipitates and stirring is no longer useful. The reaction mixture is acidified with dilute phosphoric acid and the gel formed is filtered off with suction. The filtrate consists exclusively of an aqueous phase, all of the CH ₃ Cl ₂ is adsorbed ^v om triazine-containing polycarbonate. The polycarbonate is made by slurrying with dist. Water washed largely neutral and dried for 20 hours at 50 ° C./15 torr.

Yield: 46.5 g (99 %) of flaky white triazine-containing polycarbonate

N content: Ber. 2.38% found 2.25%

The product is soluble in dimethylformamide (DMF). % COOH (in DMF): calc. 1.91 % Gef.1.70 %

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Example 6

Removal of hydrocarbons from aq. Solutions duiich Absorption on a copolycarbonate of bisphenol Λ and N- (4, e-dichloro-s-triazin-yl - ^ -) -p-aminobenzoic acid (89.5 i10.5 mol parts).

A 30 cm long column with an internal diameter of 1.5 cm is filled with 10 g of the copolycarbonate prepared in Example 5 (Fill height of the very voluminous material about 20 cm). Then successively solutions of hydrocarbons are allowed in Run water or salt solutions (50 ml each) through the column, and determine before and after your. Pass gaschrctna'ic'rrripr.isch the hydrocarbon content in the aq. Solution (see table 1):

Table 1 (for example 6):

Mixed solvent Hydrocarbon content
before absorption after absorption
sorption [mq / n Separation
stung rmq / 11 30th f% l CH ₂ Cl ₂ / dist. H ₂ O 11000 1 99.7 Chlorobenzene / dist. H ₃ O 120 <s ^a) 99.2 Benzene / dist. H ₃ O 11c <i ^a) > 94.5 Xylene / dist. H ₃ O 30th <i ° ^a) > 96.7 CH-Cl ₂ / CHlorobenzene /
ALRAL SALINE SOLUTION 4500 CH-Cl ₂
50 chlorobenzene 2600 CH-Cl ₉ 10
10 chlorobenzene <1 * ' 98.9
> 98 CH ₃ Cl / chlorobenzene /
acidic saline solution 99.6
> 90

a) Limit of detection

Example 7

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -p-aminobenzoic acid (95: 5 mole parts) with chain terminator.

According to Example 5, first 9.1 g (0.04 mol) of bisphenol A in alkaline solution with 1.5 g (5.26 mmol) of N- (4,6-dichloro-striazin-yl-2) -p-aminobenzoic acid reacted, then 474.3 mg

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(3.16 idl-Io 1) ρ-tert-butylphenyl added, a solution of 21.2 g (0.06 mol) bisphenol-A-bischlorocarbonic acid ester in 180 ml CH _? C1 _{2 is allowed to} run in, 10.1 ml of 1 # aqueous triethylamine solution are added and the mixture is stirred at pH 13. After about 10 minutes, the triazine-containing polycarbonate precipitates like a gel and is worked up as described in Example 5.

Yield: 26.0 g (99 %) of white granular product N content: calc. 1.12 % found 1.02 «6
COOH content: Ber. 0.897 % found . $ 0.899

Example 8

Gopolycarbonate made from bisphenol A and N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid (98: 2 molar parts) with chain terminator.

a) According to Example 5, 9.1 g (0.04 mol) of bisphenol A are mixed with 0.57 g (2 mmol) of N- (4,6-dichloro-s-triazin ~ yl-2) -p-aminobenzoic acid reacted and then in the presence of 383 mg (2.55 mmol) p-tert-butylphenol with 21.2 g (0.06 mol) bisphenol-A-bischlorocarbonic acid ester with the addition of 10.1 ml of liquid water. TiJ-tbylamine solution condensed at pH 12-13. After 10 minutes the copolymer precipitates like a gel and is as above worked up.

Yield: 25 g (97
NGalt B 0

Yield 25 g (97 ^)

N content: Ber. 0.439% Gef. 0.41 %

b) If the reaction described under a) is carried out in the presence of 766 mg (5.11 mmol) of p-tert-butylphenol, that remains Polycarbonate dissolved in methylene chloride. After the addition of triethylamine the mixture is subsequently stirred at pH 12-13 for 1 hour, and the organic phase is evaporated after washing until neutral and dried for 65 hours at 100 ° C./15 torr.

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Yield: 22.2 g (86%) of triazine-containing copolycarbonate "l-rel * ^{0 '5 g of product in l0} ° ^ml CH ₂ Cl _2, 25 * C): 1.267 N content: 0.434% Found Ber 0.. , 41 % COOH content: "0.349%" 0.34%

Example 9

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid (80:20 molar parts).

According to Example 5, 10 g (0.044 mol) of bisphenol A, 8 g (0.2 mol) of NaOH and 5.7 g (0.02 mol) of N- (4,6-dichloro-s-triazin-yl-2 ) -paminobenzoic acid reacted in 250 ml of water and then condensed with 12.7 g (0.036 mol) of bisphenol-A-bischlorkohlensäureejster in 230 ml of CH ₂ Cl ₂ with the addition of 10.1 ml of 1% aqueous triethylamine solution. Already 5 minutes after the addition of triethylamine, the polycarbonate precipitated like a gel. After stirring for 1 hour, the mixture is worked up as described above. The neutral washed gel is dried for 30 hrs. At 8O ^e C / 15 Torr.

Yield: 22 g (92 %) white, fine-grained powder N content ·: Ber. 4.65 %, 4.48 % COOH content: "3.74%" 2.96%

Example 10

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid branched with cyanuric chloride (90:10 parts by mole).

According to Example 4, 20.6 g (0.09 mol) of bisphenol A and 2.85 g (0.01 mol) of N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid in 190 ml of 1N NaOH solution were dissolved and a solution of 40.5 mg (0.22 mmol) of cyanuric chloride in 50 ml of dioxane was added. The mixture is heated to 90 - 95 ° C for 5 hours while stirring and under an N _{2 atmosphere,}

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then cooled to 2O ^e C and the resulting clear solution, after addition of 150 ml CH ₂ Cl at pH 12 reacted with 11.9 g (0.12 mol) COCl. ₂ After dilution with 150 ml of CH ₂ Cl ₃ , 8.3 ml of 1% aq. Triethylamine solution was added and the mixture was subsequently stirred at pH 12-13 for 1 hour. After acidification with dilute phosphoric acid, the triazine-containing polycarbonate precipitates like a gel and is worked up as described in Example 5.

Output: 24 g (97 %) white flaky product N-content: Ber. 2.06 % Found 2.08 %

Example 11

Oopolycarbonate made from bisphenol A and N- (4,6-dichloro-s-triazinyl-2) sulfanilic acid (90: ip molar parts).

According to B; 3--. 4 are? 0.6 g (0.09 KnI) bisphenol A, 1.2 g (0.13 mol) NaOH and 3.43 g (0.01 mol) of the Na salt of the N- (4.6- Dichloro-s-triazin-yl-2) -sulfanilic acid reacted, an-

at r ^u 1? Stirred with 11.9 S (0.12 mol) of COCl _{2 from} P.-alrt-joti and after adding triethylarain for 1 hour at pH 13. When the reaction product is acidified, the polynarbonate precipitates as a white powder, which is filtered off with suction, washed neutral by slurrying with water, then washed with methanol and dried for 65 hours at 80 ° G / 15 Torr. Yield: 23.5 g (93 %) copolycarbonate N content: calc. 2.21% found 2.16 %

Example 12 Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazin-yl-

2) ethyl p-aminobenzoate (85.7: 14.3 parts by mole).

According to Example 1, a solution of 20.6 g (0.09 mol) of bisphenol A and 7.2 g (0.18 mol) of NaOH in 180 ml of H ₃ O is used for 3 hours at 80-90 °

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reacted with a suspension of 4.69 g (15 mmol) of N- (4,6-pichlorostriazin-yl-2) -p-aminobenzoic acid ethyl ester in 60 ml of chlorobenzene. When cooling down to room temp. a semolina-like intermediate product precipitates. After adding 120 ml of CH ₂ Clj, the pH is adjusted to 13 and the mixture is reacted with 11.9 g (0.12 mol) of COCl ₂ at pH 13. After adding 5 ml of 1% aqueous triethylamine solution, stirring is continued until the copolycarbonate precipitates as a gel after about 15 minutes. The precipitated product is worked up as described in Example 5.

Yield: 26 g (100%) triazine-containing copolycarbonate N content: calc. 3.22 % Gef. 3.15 %

The IR spectrum (KBr compact) clearly shows that an ester group-containing Polycarbonate is present. The product is in dimethylformamide soluble.

The used N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid äthy Ie ster was according to one of Thurston et al. (J. Am. Former Soc. _73, 2981 [1951]) described procedure for the preparation of 2-amino-dichloro-s-triazines by reacting 0.5 mol of cyanuric chloride with 0.5 mol of p-aminobenzoic acid ester with the addition of 0 , 25 mol Na ₃ CO ₃ in acetone (2OO ml) / dioxane (50 ml) / water (300 ml) at 0-5'C. The dichlorotriazine which precipitates out of the reaction mixture is purified by boiling with acetone.

Yield: 76 %, m.p. 294-295'C.

Ber. C. 46 , 05 H 3 , 22 N 17th , 9 Cl 22nd , 70 Found 46 , 15 3 , 13 17th ,8th 22nd , 6

Example 13 '

Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazine-

yl-2) glycine.

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According to a procedure for the preparation of 2-amino'4,6-dichloros-triazines (J. Thurston et al., J. Am. Former Soc. 76, 2981 [1951]) 1.84 g (0.01 mol) of cyanuric chloride and 0.79 g (10.5 tnMol) glycine, with the addition of 0.84 g "(2Γ mmol) of NaOH in acetone / H ₂ 0 (7:11 parts by volume) is reacted at about 0 ^# C The mixture is stirred for 1 hour and allowed to warm to room temperature .. A solution of 9.6 g (42 mmol) of bisphenol A and 3.36 g (84 mmol) of NaOH is added to this orange-red colored solution of dichlorotriazine in acetone / water in 42 ml H ₂ O and gradually heated to about 90-95 ⁰ C, the acetone is removed by distillation from the ReaTctionslösung After removal of the acetone 3 hrs bei.95 is -... lOO'C stirred mixture is allowed to cool to room temp , dilute the pale yellow solution with 100 ml of water, let a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonate run in with vigorous stirring, add 10.1 ml of 1% aqueous triethylamine solution and allow at pH Stir 13. After about 15 min If the polycarbonate becomes gelatinous. The reaction is terminated and the polycarbonate is worked up as described in Example.

Yield: 22.3 g (93 %) of flaky white copolycarbonate N content, calculated. 2.32% found 2.28% COOH content: Ber '. 1.87 % found 1.7%

The product can absorb about 38 times its own weight in Cl _2.

Example 14 Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazine-

yl-2) -6-aminohexanoic acid (90:10 parts by mole).

According to Example 13, 1.84 g (0.01 mol) of cyanuric chloride with 1.38 g (10.5 mmol) of 6-amino-hexanoic acid are converted into the N- (4,6-dichloro-s-triazinyl-2) - 6-aminohexanoic acid implemented the resulting white

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Suspension with 9.6 g (42 mmol) of bisphenol A. koi «d« -ri3J, whereby the acetone from the first reaction stage from the mixture is distilled off, and the resulting colorless solution of the dihydroxy compounds at 20-25 ° C with a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester in Methylene chloride at pH 13 after adding 10.1 ml of 1% triethylamine solution 1 hour polycondensed. The organic phase is separated off, acidified with dilute phosphoric acid, Washed neutral and added dropwise to methanol, the triazine-containing polycarbonate precipitating in a flaky white form.

Yield: 21.4 g (87%)

^ rel ⁽⁰ ' ^{5 g product in 10} ° ^{ml CH} 2 ^C1 2' ^{25 # C} > ^: 1 * 535 N-content: Calc. 2.27 % Gef. 2.12%

COOH content: Ber. 1.62 % found 1.59%

Example 15

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -2-aminobenzoic acid.

According to Example 4, 9.6 g (42 mmol) of bisphenol A, 3.76 g (94 mmol) of NaOH and 2.85 g (10 mmol) of N- (4,6-dichloro-s-triazin-yl-2 ) -2-aminobenzoic acid in 180 ml water for 5 hrs. at about 95-lOO ^e C reacted leaves in the resulting milky aqueous solution, a solution of 16.96 g (48 mmol) of bisphenol-a-bischlorocarbonic acid in 170 ml CH ₂ Cl ₂ run in, gives 10.1 ml of 1% aq. Triethylamine solution and condensed for 1 hour at pH 13. The viscous organ. Phase is worked up as described in Example.

Yield: 24.7 g (100%) of flaky white copolycarbonate 1rel ^{( 0.5 g of} product in 100 ml of CH ₂ Cl ₂ , 25 ° C.): 1.372 N content: calc. 2.26 % found 2.08 % COOH content: calc. 1.82% Gef. 1 # 7 %

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The N- (4,6-dichloro-s-triazine "/ l" 2) -2-aninobanzoic acid used was obtained by reacting 36.8 g (0.2 mol) of cyanuric chloride and 27.4 g (0.2 mol) of 2-aminobenzoic acid prepared in 520 ml of acetone at 0-2 C ^e in the presence of 20.3 g (0.2 mol) of triethylamine as an HCl acceptor. The resulting reaction product is washed free of chloride with dilute hydrochloric acid and then with water, boiled with acetone and dried.

Yield: 30.2 g (53 %) ; Melting point> 33O ^e C (decomposition) Analysis: Calc. C 42.1% H 2.11 % Cl 24.95 % Gef. 42.4 % 2.19 % 24.9 %

Example 16

Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -2-aminoethanesulphonic acid (90:10 parts by mole).

According to Example 13, 1.84 g (10 mmol) of cyanuric chloride are added to 1.31 g (10.5 mmol) 2-aminoethane-1-sulfonic acid (taurine) to the corresponding Dichloro-s-triazine reacted, the resulting white suspension at 6O-95 * C with 9.6 g (42 mmol) of bisphenol A reacted with simultaneous distilling off of the acetone in the reaction mixture, a colorless solution arises, and finally with a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester in methylene chloride after adding 10.1 ml of 1% aqueous triethylamine solution polycondensed at pH 13.

After stirring for a further 30 minutes, the triazine-containing copolycarbonate precipitates like a gel and is worked up as described in Example 5.
Yield: 23.8 g (97 %)
N content: Ber. 2.27 % found 2.18 %

The product can absorb approx. 36 times its own weight in CH-C 1_.

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Example 17

Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -5-aminoisophthalic acid (90:10 mole parts) ·.

According to Example 13, first 1.84 g (10 mmol) of cyanuric chloride with 1.9 g (10.5 mmol) of 5-aminoisophthalic acid in the presence of 1.24 g (31 mmol) of NaOH at 0-5 * C in acetone / Reacted water, the resulting light yellow suspension with 9.6 g (42 mmol) of bisphenol A condensed at 60-90'C for 5 hours, - and finally the aqueous solution of the dihydroxy compounds at room temperature by the interfacial process with a solution of 16.96 g (48 mmol) bisphenol-A-bischlorocarbonic acid ester in methylene chloride after the addition of 10.1 ml 1 % aq. Triethylamine solution polycondensed at pH 13. After about 10 minutes of stirring, the copolycarbonate precipitates like a gel and is worked up as described in Example 5.

Yield: 25 g (99 %) of white copolycarbonate N content: Ber. 2.22 % Gef. 2.20 % COOH content: Ber. 3.58 % found 3.33%

The product can absorb approximately 19 times its own weight in Cl _2.

Example 13

Copolycarbonate of bisphenol A and (4,6-dichloro-s-triazin-yl-2) -hydroxyacetic acid (90:10 parts by mole).

According to Example 4, 9.6 g (42 mmol) of bisphenol A, 3.76 g (94 mmol) of NaOH and 2.24 g (0.01 mol) of (4,6-dichloro-s-triazin-yl-2) -hydroxyacetic acid in 200 ml of water 4 3tdn. implemented at 70-80 ⁰ C. After cooling to room temperature one leaves under

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Intensive stirring, a solution of 16.96 g (48 mmoles) of bisphenol-carbonic acid ester in 200 ml of CH ₂ Cl ₂ run in, 10 ml of 1% aqueous triethylamine solution are added and condensation at pH 13. After 10 minutes of stirring, the triazine falls -containing polycarbonate from gelatinous and is worked up as described in Example 5.

Yield: 22.9 g (95 %) of triazine-containing copolycarbonate N content: calc. 1.74% Gef.1.70 %

COOH content: Ber. 1.87 % found 1.75%

Example 19

Copolycarbonate of bisphenol A and S- (4,6-dichloro-s ~ triazin-yl-2) -4-mercaptobenzoic acid (90:10 parts by mole).

According to a specification for the preparation of 2-arylthio-4,6-dichloros-triazines (J. Drabek and M Skrobal, Chem. Zvesti Γ7, 482 [1963]) 1.84 g (0.01 mol) of cyanuric chloride and 1 , 54 g (0.01 mol) of 4-mercaptobenzoic acid reacted with the addition of 0.8 g (0.02 mol) of NaOH in acetone / water at 0-5 ⁰ C. The reaction mixture is then treated with a solution of 9.6 g (42 mmol) of bisphenol A and 3.36 g (34 mmol) of NaOH in 50 ml of water and heated to 70-80 ° C. for 5 hours, the acetone from the Mixture is distilled off. After cooling to room temperature, 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester are reacted as described under Example 13 and the polycarbonate formed is worked up as described in Example 5.

Yield: 24.6 g (99 %) triazine-containing copolycarbonate N content: calc. 1.69 % found 1.55%

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Example 20

Copolycarbonate from l, l-bis- (4-hydroxyphenyl) -cyclohexane, Bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -p-aminobenzoic acid (42: 48: 10 mole parts).

Analogously to Example 15, 11.3 g (42 mmol) of 1,1-bis (4-hydroxyphenyD-cyclohexane) with 2.85 g (10 mmol) of N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid reacted and the resulting mixture of Dihydroxyverbxndungeh with 19.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester condensed. The resulting copolycarbonate is worked up as described in Example 5.

Yield: 26 g (97 %) triazine-containing copolycarbonate N content: calc. 2.08 % Gef. 2.0%

Example 21

Copolycarbonate from 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane and N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid (90: 10 molar parts).

Analogously to Example 15, 11.95 g (42 mmol) of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane are obtained with 2.85 g (10 mmol) of N- (4,6-dichloro-striazin-yl-2) -p-aminobenzoic acid reacted, then leaves a solution of 19.2 g (48 mmol) of bischlorocarbonate of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane run in 170 ml of methylene chloride, stir after the addition of 1.36 g (13.5 mmol) of triethylamine 3 hours after and works up as described under Example 5.

Yield: 31 g (94%) triazine-containing copolycarbonate N content: calc. 1.70% found 1.65 %

Le A 15 223 - 36 -

50981 A / 1189

Example 22

Copolycarbonate of bisphenol A and N- (4,6-dichloro-s-triazinyl-2) -p-aminobenzamide (90:10 molar parts) According to Example 4, 9.6 g (42 mmol) of bisphenol A, 3.36 g ( 84 mmol) of HaOH and 2.84 g (10 mmol) of N- (4,6-dichloro-s-triazinyl-2) -p-aminobenzamide in 170 ml of H ₃ O for 5 hours at 90-95 ° C. A solution of 16.96 g (84 mmol) of bisphenol-A-bischlorocarbonic acid ester in 270 ml of CH-Cl _{2 is then} added at 20-25 ° with vigorous stirring and, after the addition of 10.1 ml of 1 percent strength, is added. aqueous triethylamine solution condensed at pH 13 for 1 hour. The gelatinous precipitated polycarbonate is worked up as described in Example 5.

Yield: 21.6 g (87 %) of copolycarbonate N content: calc. 2.83 % found 2.75%

The IR spectrum (KBr compact) clearly shows that a Araid groups-containing polycarbonate is present.

The N- (4,6-dichloro-3-triazin-yl-2) -p-aminobenzamide used was obtained by reacting 18.4 g (0.1 mol) of cyanuric chloride with 13.6 g (0.1 mol) of p -Aminobenzamide in acetone / water (1: 1 parts by volume) with the addition of 8.4 g (0.1 mol) NaHCO ₃ at 0 - 3 ° C.

Yield: 51.6 g (91 %) ; Melting point> 300 ° C Cl content: Ber. 25.1 % Gef. 24.9 %

Example 23

Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazine-

y1-2) -p-aminobenzenesulfonic acid amide (90:10 parts by mole)

Analogously to Example 22, 9.6 g (42 mmol) of bisphenol A are initially used with 3.2 g (10 mmol) of N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzenesulfonic acid amide reacted and then condensed with 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester. Approximately The triazine-containing copolycarbonate falls 20 minutes after the addition of triethylamine gelatinous'.

Le A 15 225 - 37 -

509814/1189

Yield: 25 g (100%)

N content: Ber. 2.79% Gef. 2.7 %

The N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzenesulfonic acid amide used was obtained by reacting 18.4 g (0.1 mol) of cyanuric chloride with 17.2 g (0.1 mol) of 4 Aminobenzenesulfonic acid amide in acetone / water (1: 1 parts by volume) with the addition of 8.4 g (0.1 mol) of NaHCO ₃ at 0-3 ° C.

Yield: 53.5 g (84 %) of the white powdery product Schitip. :> 300 ° C

Cl content: Ber. 22.3 % Gef. 22.1 %

Example 24

Copolycarbonate from bisphenol A and 4,4'-bis [4-chloro-6-diethanolamino-s-triazin-2-yl] -amino-2,2'-stilbene disulfonic acid: (99: 1 mole parts).

According to Example 4, 22.6 g (99 mmol) of bisphenol A, 7.92 g (198 mmol) of NaOH and 847 mg (ImMoI) of di-Na salts of 4,4'-bis- [4-chloro-6 heated 95 ⁰ C - -diäthanolamino-s-triazin-2-yl] amino> -2, 2'-StIHDeUdISuIfOnSaUTe in 175 ml HO 5 hrs at 90.. Then is cooled to 20 ⁰ C and after addition of 450 mg (3 mmol) p-fert.-butylphenol and 175 ml of CH ₃ Cl ₂ at pH 12 with intensive Stir η with 14.9 g (0.15 mol) ₂ COCl implemented. Then 10.1 ml of 1% aq. Triethylamine solution was added and the mixture was stirred at pH 12 for 1 hour. After acidification with dil. H ₃ PO ₄ , the aq. Phase separated and the organic phase was added dropwise to methanol, the polycarbonate precipitating.

Yield: 24.3 g (94 %)

\ _rel (0.5 g. product in 100 ml CH ₂ Cl ₂ , 25 ° C): 1.245 N content: Ber. 0.54 % found 0.53

The product shows a blue fluorescence when irradiated with UV light.

Le A 15 225 - 38 -

5098U / 1 189

23A6935

Example 25

Copolycarbonate of bisphenol A and 4,4'-bis- [4-chloro-6-diethanolamino-s-triazin-2-yl] -amino-2,2'-stilbene disulfonic acid (90:10 parts by mole).

Analogously to Example 24, 20.5 g (0.09 mol) of bisphenol A and 8.47 g (0.01 mol) of 4,4'-bis [4-chloro-6-diethanolamino-striazin-2-yl] -amino-2,2'-stilbene disulfonic acid reacted with the addition of 7.2 g (0.18 mol) of NaOH in 210 ml of H ₂ O, then 210 ml of CH ₂ Cl ₃ and 0.75 g (5 mmol) of p -tert-butylphenol was added and phosgenated with 11.9 g (0.12 mol) COCl. After adding 10.1 ml of 1% aq. Triethylamine solution is stirred for 1 hour at pH 12.5. After acidification, the polycarbonate, in which all of the methylene chloride is absorbed, precipitates out gritty. After drying for 24 hours at 80 ° C./15 torr, 30 g (99%) of copolycarbonate remain.

N content: Ber. 4.61% Gef. 4.4%

Example 26

Copolycarbonate of bisphenol A and 4,4'-bis- [4-chloro-6-anilinos-triazin-2-yl] -amino-2,2'-stilbene disulfonic acid (99: 1 parts by mole).

Analogous to Example 24, 22.6 g (99 mmol) of bisphenol A and £ 0.824 (1 wl-fr. 1) ·;, 4'-Βΐ3 - ^ - οΜοΓθ-6-3ηΐ11ηο-β-ΐχ · 1ρ.ζίη- 2-7ΐ7-αΐη1ηο-2, 2 '-etilbendisulfonsäure-di-Na-salt in the presence of 7.92 g (198 mmol) of NaOH in 175 ml water at room temperature after addition of 175 ml CH ₂ Cl ₃ and 0, 45 g (3 mmol) of p-tert-butylphenol are _{phosgenated with 14.9 g (0.15 mol) of COCl 3} at pH 13 and, after addition of triethylamine (10.1 ml of 1% aqueous solution), the mixture is stirred for 1 hour . After acidification, with dist. Water washed and the organ. Phase was added dropwise to methanol, the polycarbonate precipitating flaky white.

Le A 15 223 - 39 -

5098H / 1189

Lrel ^ ⁰ ' ^{5 g produ: kt in l0} ° ¹ ^ ^{1 CH} 2 ^C1 2' ²⁵ ° ^c ^ ^: * # 287 N-content: calc. 0.54% Gef. 0.49%

The product shows a green-blue fluorescence when irradiated with UV light.

LeA 15 225 - 40 -

50981 A / 1189

Claims (1)

Claims: 9 * 3 ARQ ^ ξ 1. Polycarbonates based on aromatic bishydroxy compounds, in particular based on Bls- (hydroxyphenyl) alkanes, the H-triazine compounds as links between each 2 moles of aromatic bishydroxy compounds via one oxygen atom each same on the one hand and via carbon atoms of the s-triazine rings on the other hand, the s-triazine rings are bonded to at least one other carbon atom Organic radicals with functional groups bound via oxygen, nitrogen or sulfur "carry. 2. Polycarbonates containing s-triazine rings with functional groups based on aromatic dihydroxy compounds, characterized in that they contain s-triazine rings of the following general formula 1, (D in the Z is -0-, -S-, -NH- or -NR ¹ -, R alkylene radicals with Λ - 20 carbon atoms, cycloalkylene radicals with 5-12 carbon atoms, mono- or polynuclear arylene or carbon-bonded heteroarylene radicals with up to 14 carbon atoms, mono- or polysubstituted mono- or polynuclear arylene or carbon-bonded heteroarylene radicals with up to 14 ring carbon atoms, with substituents such as alkyl, alkoxy or alkyl mercapto groups with 1-4 carbon atoms, halogen atoms such as chlorine or bromine, -NO- or Le A 15 2? J> - 41 - 5 O 9 8 1 4/1 1 B 9 -CN come into question, alkylarylene radicals with a total of up to 30 carbon atoms, or aralkylene radicals with a total of means up to 30 carbon atoms R ^{1 is} alkyl radicals with 1 to 20 carbon atoms, cycloalkyl radicals with 5 to 12 carbon atoms, mono- or polynuclear aryl or carbon-bonded heteroaryl radicals with up to 14 ring carbon atoms. B. alkyl, alkoxy or alkyl mercapto groups with 1 to k carbon atoms, halogen atoms such. B. chlorine or bromine, -NO ₂ or -CN are possible, alkylaryl radicals with a total of up to 30 carbon atoms, aralkyl radicals with a total of up to 30 carbon atoms or hydroxyalkyl radicals with 1 to 10 carbon atoms. Q is a -COOH-, -COOR-, -CONR ³ R ⁴ -, -SO ₃ H-, -SO ₂ NR ³ R ⁴ - or aliphatic -OH group, ft R stands for alkyl groups with 1-4 carbon atoms, 4th
R and R independently of one another for hydrogen, for straight chain or branched alkyl groups with 1-4 carbon atoms or an unsubstituted, mono- or polysubstituted phenyl radical or together with the N atom form a 5- or 6-membered ring system and a is an integer from 1-4, and / or radicals of the following general formula 2 (2) Ie A 15 223 - 42 - 5098 U / 1189 R ^J and R independently of one another represent H or alkyl, hydroxyalkyl, carboxyalkyl, alkoxycarbonylalkyl groups, Cc-C, cycloalkyl, Cg-C ₁ ^ aryl groups containing 1-5 carbon atoms or together with the N atoms form a 5- or 6-membered ring system, as a link between the aromatic bishydroxy compounds contain bound via their oxygen atoms. 3. Polycarbonates according to claim 1, characterized in that they consist essentially of structural units of the following general formulas 3 and / or 4 O "ι ■ ■ ο-χ- (γ ^ϊ γ (-ο-ϊ-ο-ο) _η NyN (3) in which X is an o-, tn- or p-phenylene radical, one single or multiple substituted o-, m- or p-phenylene radical, where as substituents e.g. lower alkyl groups with 1-4 carbon atoms or halogen atoms such as chlorine or bromine come into consideration or one of the formula 5 (5) Le A 15 2? 5 - 43 - 5 0 9 8 U / 1 - 8 9 «• Η means in the 23AR ^? R. R ⁷ and R ^{8 represent} hydrogen atoms, alkyl radicals with 1-4 carbon atoms or halogen atoms, of the latter preferably chlorine or bromine atoms, have the same or different meanings, Y is a single bond, an alkylene or alkylidene radical with 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -0-, -S-, -CO-, -SO-, -SO., - or a radical of the formula 6a or 6b, , 9 C6a) (6b) R ^ to R denote alkyl groups with 1-4 carbon atoms. 11
R also stands for hydrogen or halogen atoms, js.B. Chlorine or bromine, can stand, Z, R, Q and a have the same meaning as under formula 1, Rpj and Rg have the same meaning as under formula? specified have and η is a number between 1 and 200, preferably between 3 and 100, are constructed. 4. Polycarbonates according to claim 2-3, characterized in that they have structural units of the formula 18, Ϊ ■ ϊ -σ-ο-χ-ο -, * ¹¹ NOXOC- I & ο ^(1B) ο
oxoc- Le A 15 223 - 44 - K- (J 9 θ 1 / «/ ^{1 1} 3 1 in which X has the meaning given above, are branched and the structural units mentioned 18 in Amounts from 0.01 to 5 mol-Jf-, based on the structural units 3 or 4 »are contained in the (Teeamtmolekül. 5. Polycarbonates according to claim ? - 4, characterized in that X denotes a radical characterized by the formula 5, in which 7 Π
R 'and R have the meaning given above and Y is an alkylene or alkylidene radical with 1-7 carbon atoms or a cycloalkylene or cyoloalkylidene radical with 5-12 carbon atoms. 6. Polycarbonates according to claim 5, characterized in that means. 7. Verf * ren for the production of the polycarbonates according to claim 1, characterized in that the aromatic bishydroxy compounds modified according to claim 1 with s-triazine compounds individually or with the use of correspondingly unmodified aromatic bishydroxy compounds by processes known per se with the aid of phosgene or other polycarbonate-forming derivatives of carbonic acid converted into polycarbonate. Le A 15 22? - 45 - 8. A process for the preparation of s-triazine rings containing poly carbonates of the formula 3 according to claim 3, characterized in that that aromatic bishydroxy compounds of the formula 11 containing s-triazine rings N "fj-O-X-OH (11) which one by reaction of dihalo-s-triazines of Formula 8, Shark (8th) being in the formulas S, R, Q, a and X have the meaning given above and Hal means F, Cl, Br and J, preferably Cl, with 2 equivalents of an aromatic dihydroxy compound of formula 10, HO-X-OH (10) in which X has the meaning given above, in the presence of a proton acceptor or preferably with 2 equivalents of the alkali metal salts of the aromatic dihydroxy compounds of the formula 10 according to processes known per se, alone or in a mixture with up to 199 equivalents of a dihydroxy compound of the formula 10 with Phosgene and / or a bishopric carbonic acid ester a tiner Bihy & roxjverbindunf IO and / or one of 10 available carbonic acid ester bonds Ie A 15 22? - 46 - ßAD ORIGINAL group-containing oligomeric carbonates, the sum of the equivalents of the dihydroxy compound 10, used as such and / or as their alkali metal salts and / or as their Bischlorocarbonic acid ester and / or as chlorocarbonic acid ester terminal groups produced from the dihydroxy compound 10 containing oligomeric carbonates, 199 equivalents per Equivalents of the compound 11 do not exceed, and wherein per phenolic OH equivalent at least 1.05 via -CO- bound Chlorine equivalents are used, if necessary in the presence of molecular weight limiters, according to known folycarbonate production processes, preferably the process of interfacial polycondensation. 9. A process for the preparation of polycarbonates of the formula 4 containing bistriazinyl structural units according to claim 3 »characterized in that aromatic bishydroxy compounds of the formula 12 containing bistriazinyl segments, SO-, Η HO-X-O ⁿ NOX OH (12) which can be obtained by reacting diohlorobistriazinyl compounds fier formula 9, SO, H HO, S being in the formulas 5 6
R, R and X have the meaning given above, with 2 Le A 15 223 - 47 - 0 9 8 1 1 G '} Equivalents of an aromatic dihydroxy compound of Formula 10, in the presence of a proton acceptor or preferably with 2 equivalents of the alkali metal salts of the aromatic Dihydroxy compound of the formula 10 according to known calibration Process receives, on its own or in admixture with up to 199 equivalents of a dihydroxy compound of the formula 10 with phosgene and / or a bischlorocarbonic acid ester Dihydroxy compound 10 and / or one of 10 obtainable chlorocarbonic acid ester end groups containing oligomer Carbonates, the sum of the equivalents of the dihydroxy compound 10 used as such and / or as their alkali metal salts and / or as their bischlorocarbonic acid esters and / or as carbonic acid ester end groups produced from the dihydroxy compound 10 containing oligomeric carbonates, not exceeding 199 equivalents per equivalent of compound 12, and wherein per phenolic OH equivalent at least 1.05 above -CO- bound chlorine equivalents must be used, if necessary in the presence of molecular weight limiters, according to known polycarbonate production processes, preferably the process of interfacial cipolycondensation. 10, method according to claim 8, characterized in that the reaction of dihalo-s-triazines of the formula 8 with aromatic dihydroxy compounds ^ r formula 10 in the presence a proton acceptor or preferably with the alkali salts of the dihydroxy compounds 10 according to known » Process obtainable s-triazine rings containing bishydroxy compounds 11 without separate isolation and in the same reaction vessel depending on the choice of the first reaction stage used molar ratio of 8 to 10 either alone or in a mixture with further 10 with phosgene and / or Bischlorocarbonic acid esters of the aromatic dihydroxy compounds 10 and / or aue 0 available chlorocarbonic acid ester end groups contain- :: 3en oligomeric carbonates, where the sum Le A 15223 - 48 - 5098U / - 89 ^8AD ORIGINAL of the equivalents of the dihydroxy compound 10 used as those and / or as their alkali metal salts and / or as their bischlorocarbonic acid esters and / or as from the dihydroxy compound 10 oligomeric carbonates produced containing chlorocarbonate end groups, 199 equivalents per Exceed equivalent of the compound 11, and wherein per phenolic OH equivalent at least 1.05 via -CO- bound Chlorine equivalents have to be used, possibly in the presence of molecular weight limiters, according to known ones Polycarbonate production process, preferably by the process of interfacial polycondensation, implemented 11. The method according to claim 9, characterized in that the bistrazinyl obtainable by reacting diehlor-bistriazinyl compounds of the formula 9 with aromatic dihydroxy compounds of the formula 10 in the presence of a proton acceptor or preferably with the alkali metal salts of the dihydroxy compounds 10 by processes known per se Bishydroxy compounds containing segments 12 without separate isolation and in the same reaction vessel, depending on the choice of the molar ratio of 9 to 10 used in the first reaction stage, either alone or in a mixture with further 10 with phosgene and / or bishopric carbonic acid esters of the aromatic dihydroxy compounds 10 and / or from 10 available oligomeric carbonates containing chlorocarbonic acid ester end groups, the sum of the equivalents of the dihydroxy compound 10 used as such and / or as their alkali metal salts and / or as their bischlorocarbonic acid esters and / or as produced from the dihydroxy compound 10 lt oligomers containing chlorocarbonic acid ester end groups. Carbonates, not exceeding 199 equivalents per equivalent of the compound, and at least 1.05 chlorine equivalents bound via -CO- must be used per phenolic OH equivalent, if necessary in the presence of molecular weight Le A 15 223 - 49 - 5 0 S 8 U / 1 1 8 9 limit, according to known polycarbonate manufacturing processes » preferably by the process of interfacial polycondensation, implements. 12. The method according to claims 8 and Io, characterized in that that by reacting trihalogen-s-triazines the Formula 19, (19) Shark in the Hal F, Gl, Br and J _{1 is} preferably Cl, with compounds of the formula 13, (Q ^ ₁ -WZH (13) in the Z, R, Q and a have the abovementioned meaning, obtainable in a molar ratio of 1: 1 by processes known per se Dihalo-s-triazines of the formula 8 without separate isolation and in the same reaction vessel with aromatic dihydroxy compounds of the formula 10 in the presence of a proton acceptor or preferably with the alkali salts of the dihydroxy compounds 10 by methods known per se to form s-triazine rings containing bishydroxy compounds of the formula 11, and then depending on the choice of the implementation of 8 with molar ratio 11 used either on its own or in a mixture with further 10 with phosgene and / or bischlorocarbonic acid esters of the aromatic dihydroxy compounds 10 and / or from 10 available chlorocarbonic acid ester end groups containing oligomeric carbonates, possibly in the presence of molecular weight limiters, according to known polycarbonate production processes, preferably the process of interfacial polycondensation, implements. Le A 15 223 - 50 - 50981 A / 1189 13. The method according to claims 8 to 12, characterized in that the reaction of dihalo-s-triazines of the formula 8 or dichlorobistriaziny compounds of the formula 9 and trihalo-s-triazines of the formula 19 with aromatic dihydroxy compounds 10 obtainable mixtures of s-triazine rings or bishydroxy compounds 11 or 12 containing bistriazinyl segments and trishydroxy compounds of the formula (14) » HO-X-O-ß- N Vj-O-X-OH (14) NN
O-X-OH in the X has the meaning given above, implements. 14. The method according to claims 8 to 13, characterized in that as s-triazine rings containing bis- or trishydroxy compounds those based on aromatic dihydroxy compounds of the formula 20, η —Λ / —r \ (20) in the
R ⁷ , R ⁸
Trichloro-s-triazines are implemented. 7 8
R, R and Y have the meaning given above, and di- or 15. The method according to claims 8 to 14, thereby gekenm; elehnet, that s-triazine rings containing hydroxy compounds based on 2,2-bis- (4-hydroxyphenyl) propane and di- or tric) iXor-etrazines implemented. Le A 15 223 - 51 - 0 9 I U / 1 1 '" 16. Polycarbonates containing s-triazine rings obtainable by the process of claims 7-15 17. Use of polycarbonates containing s-triazine rings with structural units of the formula 3 in which Q is -COOH or -SO, H and Z, R, a, X and η have the meaning given above, for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mixtures or solutions of these hydrocarbons with or in water or aqueous containing inorganic salts Solutions. 18. Use of polycarbonates containing s-triazine rings with structural units of the formula 3 in which Z for NH Q for GOOH a for 1 and . . CH, X stand for -ff \ -zA ' V and R has the meaning given above, for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mixtures or solutions of these hydrocarbons old or in aqueous solutions containing water or inorganic salts. Le A 15 223 - 52 - 5098U / 1