CA1046693A - Polycarbonates containing s-triazine compounds as linking members between two molecules of bis-hydroxy aromatic compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polycarbonates are provided based on aromatic bis-hydroxy compounds which contain s-triazine compounds as linking members between 2 mols of the aromatic bis-hydroxy compounds bonded in each case via an oxygen atom thereof, on the one hand, and via carbon atoms of the s-triazine ring, on the other, the s-triazine rings carrying, on at least one further carbon atom, organic radicals with functional groups, these radicals being bonded via oxygen, nitrogen or sulphur. The novel polycarbonates may be used as selective solvents for hydrocarbons mixed with water or for making resins or coatings.

Description

Mo-1439-Ca.
~046~93 LeA 15,223-Ca.
POLYCARBONATES ~ONTAINING S-TRIAZINE COMPOUNDS AS LINKING MEMBERS
BETWEEN TWO MOLECULES OF BIS-HYDROXY AROMATIC COMPOUNDS
-This invention relates generally to polycarbonate plastics and more particularly to polycarbonates containing one or more s-triazine rings.

It has been proposed before, for example, in U.S.
Patents 3,028,365 and 3,062,781, to make aromatic polycarbonates by reacting a bis-(hydroxyaryl)-alkane such as bis-phenol A with a carbonic acid derivative such as phosgene, a carbonic acid diester or chloro-carbonic acid ester of a di(monohydroxyaryl) alkane. It has also been proposed to include other reactive compounds in the reaction mixture to modify the properties of the polycarbonate. For example, it has been proposed by us in our Canadian application Serial No. 181,152 filed September 12, 1973 in the names of Dieter Neuray et al., to make polycarbonates which contain s-triazine rings to increase the glass transition temperature, to increase the stability of the polycarbonate against saponification and to improve its burning characteristics.

It is an object of the invention to provide novel polycarbonates adapted to be used for the separation of hydro-carbons from water. Another object of the invention is to I provide novel polycarbonates containing substituted s-triazine I rings in their structure and a method for making the novel ,, ¦ polycarbonates. A still further object of the invention is to 'l~ provide a process for separating a hydrocarbon from water with the novel polycarbonate.

!':` The foregoing objects and others are accomplished in accordance with this invention, generally speaking, by ',~ providin,g a polycarbonate plastic containing recurring units of the reaction product of two moles of an aromatic bis-hydroxy compound such as bis-phenol A with one mole of a compound having ~B LeA 15,223-Ca. ,~ ' 10~6~3 one or more s-triazine rings substituted with a carboxyl group, ester group, amide group, an aliphatically bonded hydroxyl group, sulphonic acid group or amidized sulphonic acid group bonded to a carbon atom of the ring through oxygen, nitrogen or sulphur, the recurring units being bonded together by C groups.

The present invention provides polycarbonates based on aromatic bis-hydroxy compounds, preferably based on bis-(hydroxyphenyl)-alkanes, which contain s-triazine compounds as linking members between 2 molecules of the aromatic bis-hydroxy compound, bonded in each case via an oxygen atom thereof, on the one hand, and via carbon atoms of the s-triazine rings, on the (~ther,the s-triazine rings carrying, on at least one other carbon atom, organic radicals with functional groups, these radicals being bonded via oxygen, nitrogen or sulphur.

By functional groups as used herein and in the claims is meant acid group, modified acid groups, such as ester or amide groups, aliphatic hydroxyl groups, and especially carboxyl groups, esterified or amidized carboxyl groups, sulphonic acid groups, amidized sulphonic acid groups and ali-phatically bonded hydroxyl groups. Organic radicals which have carboxyl groups or aliphatically bonded hydroxyl groups and are linked via nitrogen are preferred.

The s-triazine compounds can contain one or two s-triazine rings; in the s-triazine compounds with two s-tria-zine rings, these rings are linked via organic radicals whichcan carry functional groups, and these organic radicals can be linked via oxygen or sulphur, but preferably via nitrogen, to one carbon atom of each of two triazine rings.

The invention further provides a process for the preparation of the novel polycarbonates, according to which the LeA 15,223 -2-104~693 aromatic bis-hydroxy compounds, which are modified with s-tria- 1:
zine compounds containing functional groups, are converted, ~
by themselves, or with conjoint use of correspondingly unmodified -aromatic bis-hydroxy compounds, into a polycarbonate according to processes which are in themselves known, with the aid of phosgene or other polycarbonate-forming derivatives of carbonic acid.

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

The polycarbonates according to the invention can contain s-triazine rings of the following general formula N ~ N ( ) Z
I in which (Rt--~Q)a Z represents -0-, -S-, NH- or -NR1- or -N-(R*~-~Q*)a*, , R and R* are identical or not identical and denote : 15 alkylene ra~icals with 1 - 20 carbon atoms, cycloalkylene radicals with 5-12 carbon atoms, mono-nuclear or polynuclear arylene radicals, or hetero-arylene radicals bonded via carbon, with up to 14 carbon atoms, monosubstituted or polysubstituted mononuclear or polynuclear arylene radicals, or heteroarylene radicals bonded via carbon, with up to , 14 ring carbon atoms, possible substituents being, for example, alkyl, alkoxy or alkylmercapto groups with 1-4 carbon atoms, halogen atoms, such as chlor-ine .or bromine, -N02 or -CN, alkylarylene radicals with a total of up to 30 carbon atoms, or aralkylene LeA 15,223 -3-~046~93 radicals with a total of up to 30 carbon atoms, Rl denotes alkyl radicals with 1 to 20 carbon atoms, cycloalkyl radicals with 5 to 12 carbon atoms, mononuclear or polynuclear, unsubstituted or substituted aryl radicals, or heteroaryl radicals bonded via carbon, with up to 14 ring carbon atoms, possible substituents being, for example, alkyl, alkoxy or alkylmercapto groups with 1 to 4 carbon atoms, halogen atoms, such as, for example, chlorine or bromine, -NO2 or -CN, alkylaryl radicals with a total of up to 30 carbon atoms, aralkyl radicals with a total : 15 of up to 30 carbon atoms, or hydroxyalkyl radicals with 1 to 10 carbon atoms, Q and Q* are identi.cal or not identical and denote a -COOH, -COOR2, -CoNR3R4, -SO3H, -So2NR3R4 or aliphatically bonded -OH group, R2 represents alkyl groups with 1-4 carbon atoms, ; R3 and R4 independently of one another represent hydrogen, straight-chain or branched alkyl groups with 1-4 carbon atoms or an unsub-stituted, monosubstituted or polysubstituted phenyl radical or conjointly with the N atom - form a 5-membered or 6-membered ring system and a and a* are identical or not identical and denote an integer from 1 to 4, :
: as linking members between the aromatic bis-hydroxy compounds, and bonded via the oxygen atoms of the latter. Instead of the rad.icals, or additionally to the radicals, of the general .
, LeA 15,223 -4_ 104~;~;93 ~ormula 1, the polycarbonates according to the invention can contain radicals of the general formula 2

(2) HO3~ N~_~N~

/N\ /N

in which R5 and R6 independently of one another represent H
or alkyl, hydroxyalkyl, carboxyalkyl or alkoxy-carbonylalkyl groups containing 1-5 carbon atoms, cycloalkyl group~ containing 5 to 7 carbon atoms, or substituted or unsubstituted aryl groups containing 6 to 14 carbon atoms or conjointly with the N atom form a 5-membered or 6-membered ring system, such as that of pyrrolidine, piperidine or morpholine as linking members between the aromatic bis-hydroxy compounds and bonded via the oxygen atoms of the latter.

Preferred substituents of the stated formulae 1 and 2 are:
Z = -NH- or -NR -, or -N-(R*)-(Q*)a*
R and R* are identical or not identical and denote alkylene with 1 - 10 carbon atoms or phenylene, Q and Q* are identicàl or not identical and denote -COOH, -SO3H or aliphatically bonded hydroxyl groups, LeA 15,223-Ca. -5-~ "' ' .
,................. . . .. ~ - - .

104Ç~693 Rl = alkyl with 1-6 carbon atoms or hyroxyalkyl with 1-6 carbon atoms and R and R = independently of one another, hydrogen, hydroxyalkyl with 2-4 carbon atoms, alkyl with 1-4 carbon atoms, phenyl and sulphoxy-phenyl.

The new polycarbonates containing s-triazine rings may consist essentially of identical or non-identical structural units of the following general formulae 3 and/or 4 O-X-o-l~'N ~ ~ ~3) l N ~ N
~R) --~Q) or ; S03H 0 0-X-0 r ~ ~ H ~ CH;CH ~ NH- ~ -(-0-X-0-C) in which X denotes an o-, m- or p-phenylene radical or a mono-substituted or polysubstituted o-, m- or p-phenylene ' radical, wherein possible substituents are, for example, lower alkyl groups with 1-4 carbon atoms or halogen atoms, such as chlorine or bromine, or preferably denotes a radical characterized by the formula 5 .` , ' '' .
LeA 15,223 -6-iO46693 R7 R7 : -~
~ Y ~ ' , ''.

R8 R8 , in which R7 and R8 represent hydrogen atoms, alkyl radicals with 1-4 carbon atoms or halogen atoms, among the latter preferably chlorine or bromine atoms, and have identical or different meanings, and Y denotes a single bond, an alkylene or alkylidene radical with 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -S-, -CO-, -SO-, -SO2- or a radical of the formula 6a or 6b Rl 1 ~ C 10 _c~cR3 R10 R10 Rl O ' :

(6a) (6~) :
wherein R9 to R11 denote alkyl radicals with 1-4 carbon atoms and Rll can also represent hydrogen or halogen atoms, such as chlorine or bromine, , . ..
Z, R, Q, a, R and R have the same meaning as indicated under the formulae 1 and 2 and ::
~ n is a number between 1 and 200, preferably between ¦ 3 and 100.

I LeA 15,223 -7-Preferred Y radicals are the isopropylidene radical and the cyclohexylidene radical.

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

The end groups of the new polycarbonates do not have a decisive influence on the properties of the products.
For the sake of completeness, the following may be mentioned as end groups A for the left-hand side of the structural formulae 3 and 4 and as end groups B for the right-hand side:

A in 3 and 4 may represent H or -CO-OR12, wherein R12 denotes a phenyl radical or a monosubstituted or polysubstituted phenyl radical, A in 3 may additionally represent a radical of the general formula 7 (Q)a -~R)-Z- ~ ~ -Z (R~-~Q)a N N
~ ' wherein Z, R, Q and a have the abovementioned meaning, and B represents -ORl , wherein R12 has the abovementioned meaning.

Polycarbonates containing s-triazine rings and possessing functional groups were not previously known.

LeA 15,223 -8-! ' .

104~93 The new polycarbonates according to the invention are distinguished, in particular, in that as a result of the incorporation of the s-triazine structural units of the formulae 1 or 2 via the substituent Q in the formula 1 or via the sulpho group and/or via the radicals R and R6 in the formula 2, they are suitable for polymer-analogous reactions.

Polycarbonates with structural units of the formula

3, in which Q represents -COOH or -SO3H
surprisingly display absorbing properties for organic solvents if they are insoluble in the customary solvents for polycarbonates.
This property of these modified polycarbonates can be varied widely through the nature and proportion of triazine segments, on the one hand, or through changing the molecular weight, on the other. In general, propertie~ of triazine of the formula 1 or less than 15 mol-%, preferably between 10 mol-~ and 1 mol-~, relative to the structural units of the formula 3, are necessary to achieve the desired effect. The insolubility of these polycarbonates can be controlled, inter alia, through incorpo-ration of branching agents or cross-linlcing agents. For example, with such products it is possible to remove hydrocarbons almost ! quantitatively from mixtures thereof with water, or solutions thereof in water. Examples of such hydrocarbons are aliphatic ;~ or aromatic hydrocarbons such as methylene chloride, chloro-2X benzene, benzene or xylene. Such utility of the products of this invention is of great importance for the purification of industrial effluents by removing hydrocarbons therefrom.

The invention therefore, contemplates the use of polycarbonates, containing s-triazine rings, of the formula 3 ' LeA 15,223-Ca. -9-~ ' ' '.

- : .: - , .

10~;93 in which Q denotes -COOH or -SO3H and Z, R, a, X and n have the abovementioned meaning for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mixtures or solu-tions of these hydrocarbons with, or in, water or aqueous solutions containing inorganic salts.

Another embodiment of the invention contemplates the use of polycarbonates, containing s-triazine rings, of formula 3, in which Z represents NH, Q represents -COOH, a represents 1, X denotes ~ CH ~ and R has the abovementioned meaning for the absorptive removal of aliphatic, cycloaliphatic, aromatic or halogenated hydrocarbons from mixtures or solu-tions of these hydrocarbons with, or in, water or aqueous solutions containing inorganic salts.

High molecular polycarbonates provided by the invention, containing s-triazine rings, can be prepared by first reacting dihalogeno-s-triazines of the formula 8 Hal N Hal (8) N

(Rt-~Q)a wherein LeA 15,223 -10-,,.,, ,.. , . .. , . . ,. .. ...... , , , :

~046~93 Hal denotes F, C1, Br and I, but preferably C1, and Z, R, Q and a have the abovementioned meaning or dichloro-bis-triazinyl compounds of the formula 9 CH=CH ~ ~

/ N / N (9) R5 R6 R/5 ~R6 wherein R5 and R6 have the abovementioned meaning with 2 to 201 equivalents of an aromatic dihydroxy compound of the formula 10 HO-X-OH (10) wherein x has the abovementioned meaning 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, according to customary processes for the preparation of trisubstituted ~-triazines, either a) in an organic solvent which is inert to the reactants 8, 9 and 10, or b) in an aqueous alkaline medium or c) in a I one-phase or two-phase mixture of an organic solvent which is ¦ 20 inert towards the reactants and an a~ueous alkaline phase, at temperatures between 0 and 300C, preferably between 30 and 150C, using reaction times of between 0.2 and 20 hours, and then reacting the aromatic dihydroxy compounds of the formulae 11 and 12, containing s-triazine rings, or their alkali metal salts LeA 15,223 -11-,. . . . . . .. . . . .

N

HO-X-O~ ~O-X-OH ( 11 ) ~ ~, :
Z ~Rt~Q) a ~O-X-~ ~NI{~CH=CH~NH~ ~O-X-OH
N ~N N ~N

N ~ \ 6 ~12) which are formed as intermediates, depending on the choice of the molar ratio employed in the reaction of 8 or 9 with 10, either by themselves or mixed with further 10, with phosgene and/or a bis-chlorocarbonic acid ester of the aromatic di-hydroxy compounds 10 and/or oligomeric carbonates obtainable from 10 and containing chlorocarbonic acid ester end groups, according to known methods for preparation of polycarbonates, preferably the phase boundary polycondensation method, with the sum of the equivalents of the dihydroxy compound 10, employed as such and/or as its alkali metal salts and/or as its bis-chlorocarbonic acid e~ter and/or as oligomeric carbonates, prepared from the dihydroxy compound 10 and con-lS taining chlorocarbonic acid ester end groups, not exceeding 201 equivalents per equivalent of the compounds 8 or 9, and with at least 1.05 chlorine equivalents bonded via -CO- being employed per phenolic OH equivalent.
..
It is possible to react, alongside one another, different dihalogeno-s-triazines of formula 8 and/or different bis-triazinyl-dichloro compounds of formula 9 and/or mixtures LeA 15,223 -12- ~:

104~i693 :
of compounds of formulae 8 and 9 and/or different aromatic dihydroxy compounds of formula lO, if a corresponding carbo-nate copolymer is desired. Furthermore, it is possible, without difficulty, to react the reaction products of formulae 8 and 9 with an aromatic dihydroxy compound with other aro-matic dihydroxy compounds and the abovementioned polycarbo-nate-forming compounds.

The process according to the invention is dis-tinguished in that the preparation of the bis-hydroxy compounds of formula 11 and/or formula 12 containing s-triazine structures and the subsequent preparation of the polycarbo-nates based on formulae 11 and/or 12 and optionally other dihydroxy compounds can be carried out in the same reaction medium and in the same reaction vessel without isolating the intermediate stages represented by formula 11 or 12.
While separate preparation of the bisphenols containing s-tri-azine is pos~ible, it i~ not necessary.

A further particular advantage of the process for the preparation of the polycarbonates of the formula 3 containing s-triazine structures is that instead of the purified dihalogano-s-triazines of formula 8 it is also possible to employ ~olutions or suspensions of unpurified di-halogeno-s-triazines, obtained from the reaction of tri-halogeno-s-triazines, preferably cyanuric chloride, with nucleophilic compounds of the formula 13 :
(Q)a ----------~R) ~-H (13) in which ;
z., R, Q and a have the abovementioned meaning as described for fomula l, in a manner which is in itsel~ known, directly for the ~urther condensation with aromatic dihydroxy LeA 15,223 -13- -.
, ~
.

~0~93 compounds of formula 10, A further variant of the preparation of the poly-carbonates according to the invention is that the reaction of the dihalogeno-s-triazines of formula 8 and/or formula 9 with the bis-hydroxy compounds of formula 10 is carried out in the presence of 0.01 to 5 mol percent of a trihalogeno-s-triazine, based on the structural unit of the formulae 3 and/or 4, wherein Hal has the meaning indicated for 8 but preferably denotes Cl so that the reaction mixture also contains, as intermediate products, trifunctional hydroxy compounds of the formula 14 HO-X-O r ~ O-X-OH (14) N ~ N
O-X-OH
which on subsequent reaction with polycarbonate-forming com-pounds such as phosgene and/or bis-chlorocarbonic acid esters of bis-hydroxy compounds effect a branching of the poly-carbonates via s-triazine rings.
. .
Where they are not already known, the dihalogeno-s-triazines of formulae 8 and 9 used for the preparation of the homopolycarbonates or copolycarbonates according to the invention are prepared according to processes known from the ~ :
chemical literature for preparing similar compounds.

The dichloro-s-triazines of the formula 8 in which Hal denotes Cl are obtained,.for example, by reaction of cyanuric chloride with aliphatic or aromatic amines, alcohols, phenols, mer-LeA 15,223 -14-~04~69.3 captans or thiophenols carrying functional groups Q [see, for example, J.R. Thurston et al., J. Am. Chem. Soc. 73, 2981 et seq. (1951); H. Koopman et al., Rec. trav. chim. Pays-Bas 78, 967 (1959); H. Koopman and J. Daams, Rec. trav. chim.
Pays-sas 77, 235 (1958); H. Nestler and H. Furst, J. prakt.
Chem. [4] 22, 173 (1963); S. Horrobin, J. Chem. Soc. [I,ondon]
1963, 4130; DAS (German Published Specification) 1,176,319;
DOS (German Of~enlegungsschrift) 1 670 832~

The dichloro-bis-triazinylaminostilbene derivatives of the formula 9 are obtained, for example, by reaction of aminodichlorotriazine compounds with 4,4'-diaminostilbene-2, 2'-disulphonic acid or its ~alts according to DOS (German Offenlegungsschrift) 1 670 832.

Examples of dihalogeno-s-triazines of the formula 8 which are suitable for the preparation of polycarbonates, containing s-triazine structures, of the formula 3, are the compounds obtainabla by reacting cyanuric chloride in a manner which is in itself known, in the molar ratio 1:1 with hydroxy-acetic acid, hydroxyacetic acid n-butyl ester, 2-hydroxy-propionic acid (lactic acid), 2-hydroxypropionic acid ethyl ester, 2-hydroxysuccinic acid ~malic acid),2-hydroxypropane-1,2,3-tricarboxylic acid (citric acid), mercaptoacetic acid, 2-hydroxyethanesulphonic acid (isethionic acid)~ 2-amino-ethanol, N-methylethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, diisopropanolamine, dihydroxy-tertiary butylamine, trihydroxy-tert.-butylamine, aminoacetic acid (glycine), methylaminoacetic acid, 3-aminopropionic acid,

4-aminobutyric acid, 6-aminohexanoic acid, ll-aminoundecanoic acid, aminosuccinic acid, 2-aminoglutaric acid, methionine, 2-aminoethanesulphonic acid (taurine), N-methylaminoethane-sulphonic acid, 3-hydroxybenzoic acid, 3-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acid, 4-mercaptobenzoic acid, LeA 15,223 -15-: , ....

l04~a3 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid propyl ester, 3-chloro-4-hydroxybenzoic acid, 4-hydroxy-phthalic acid, phenol-3-sulphonic acid, phenol-4-sulphonic acid, 2,6-dichlorophenol-4-sulphonic acid, 1-naphthol-4-sulphonic acid, 1-naphthol-3,6-disulphonic acid, 2-naphthol-6-sulphonic acid, 2-naphthol-s,7-disulphonic acid, N- (2-hydroxyethyl)-cyclohexylamine, aminoacetic acid ethyl ester~
6-aminohexanoic acid ethyl ester, 2-hydroxypropionic acid methyl ester, 6-hydroxyhexanoic acid ethyl ester, mercapto-acetic acid methyl ester, mercaptosuccinic acid diethyl ester, 2-hydroxyethylaniline, anilinomethanesulphonic acid, anilino-ace~ic acid, hydroxyethyl-m-toluidine, m-toluidino-methane-sulphonic acid, 2-aminobenzoic acid, 2-aminobenzamide, 3-aminobenzoic acid, 4-chloro-3-aminobenzoic acid, 4-chloro-3-aminobenzamide, 6-chloro-3-aminobenzoic acid, S-nitro-3-~minobenzoic acid, 6-nitro-3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminobenzoic acid ethyl ester, 4-aminobenzamide, 2-nitro-4-aminobenzoic acid, 4-amino-3-methylbenzamide, 3-amino-4-methylbenzoic acid, 5-aminoisophthalic acid, 4-amino-naphthalene-1,8-dicarboxylic acid, 3-amino-4-methoxy-benzoic acid, aniline-2-sulphonic acid, aniline-3-sulphonic acid, ~ .
aniline-3-sulphonic acid amide, 3-aminobenzenesulphonic acid anilide, 3-aminobenzenesulphonic acid N-methylanilide, 6-chloro-aniline-3-sulphonic acid, 4-chloroaniline-3-sulphonic acid, aniline-4-sulphonic acid, 4-aminobenzenesulphonic acid amide, diphenylamine-4-sulphonic acid, 4-benzylaminobenzenesulphonic acid, 2,5-dichloro-4-aminobenzenesulphonic acid, 4-aminotolu-ene-2-sulphonic acid, 4-aminotoluene-2-sulphonic acid anilide,

5-aminotoluene-2-sulphonic acid, 4-aminophenylmethanesulphonic acid, 4-aminonaphthalene-1-sulphonic acid, 5-aminonaphthalene-l-sulphonic acid, 6-aminonaphthalene-2-sulphonic acid, 8-aminonaphthalene-1,3,5-trisulphonic acid or 2-mercaptobenzo-LeA 15,223 -16-109~6693 thiazolesulphonic acid.

Of course, numerous other dihalogene-s-triazines of ~ormula 8 can also be used as starting compounds for the preparation of polycarbonates of the formula 3, containing s-triazine rings.

Examples of aminodichlorotriazine compounds of the formula 15 ,R5 Cl N ~ R6 N ~ N (15) - Cl which can be reacted with 4,4'-diaminostilbene-2,2'-disul~
phonic acid or its salts to give dichloro-bis-triazinyl com-- pounds of the formula 9, which are suitable for the preparation of polycarbonates of the formula 4 containing s-triazine structures, are the compounds obtainable by reacting cyanuric chloride with ammonia, methylamine, ethylamine or butylamine, dimethylamine, diethylamine or dipropylamine, mor,oethanolamine or diethanolamine, N-methylethanolamine, aminoacetic acid, 4-aminobutyric acid or 6-aminohexanoic acid, aminoacetic acid ethyl ester or ~-aminopropionic acid ethyl ester, aniline, aniline-3-sulphonic acid, aniline-4-sulphonic acid or cyclo-hexylamine, pyrrolidine, piperidine or morpholine in a molar ratio of 1:1, in a manner which is in itself known.

Examples of suitable aromatic dihydroxy com-pounds of the formula 10 are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl,bis-(hydroxyphenyl)-alkanes, -cycloalkanes, -sulphides, -ethers, -ketones, -sulphoxides or -sulphones, and also ~,a'-bis-(hydroxyphenyl)-diisopropylbenzenes and the LeA 15,223 -17-10~6693 corresponding nuclear-alkylated or nuclear-halogenated compounds.

Some preferred aromatic dihydroxy compounds are, for example: 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-di-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxy-phenyl)-propane, bis-(4-hydr~xyphenyl)-methane; 1,1-bis-(4-hydroxyphenyl)-cyclohexane and trinuclear bisphenols, such as ~,~'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene.

These are further bisphenols suitable for the pre-paration of the high molecular polycarbonates according to the invention are described in US Patent Nos. 2,970,131; 2,991,273;
2,999,835; 2,99~,846; 3,014,891; 3,028,365; 3,062,781;
3,148,172; 3,271,367; 3,271,368 and 3,280,078 and in DT-OS
1,570,703.

Suitable agents for limiting the molecular weight are phenol and monosubstituted or polysubstituted phenols, but also monohalogeno-s-triazines of the general formula 16 N
(Q~a ~R)-Z- ~ ~Z~(~) (Q)a (1~) Hal in which Z, R, Q, a and Hal have the meaning already mentioned above for formula 8.

These compounds arise as by-products in the preparation of the corresponding dihalogen derivatives.

LeA 15,223-Ca.

iO4~693 The preparation of the polycarbonates according to the invention, containing s-triazine rings and comprising structural units of the formula 3 can, for example, be effected as follows:

First, the trihalogeno-s-triazine, for example, cyanuric chloride, is reacted with a nucleophilic compound of the formula 13 in a molar ratio of 1:1 in a manner which is in itself known, for example, in an aqueous medium in the ; presence or absence of organic solvents for the cyanuric chloride, such as, for example, acetone, methyl ethyl ketone or dioxane, with the addition of the stoichiometric amount of a proton acceptor, such as, for example, NaOH or KO~, ~hich is necessary for the elimination of hydrogen chloride from cyanuric chloride and formula 13, on the one hand, and, if relevant, for the neutralization of, on the other hand, ~j acid groups present in the compound of formula 13. The resulting dihalogeno-s-triazine of formula 8, is now either isolated from the reaction mixture and purified or is employed directly without further working up, as a solution or sus-pension in the solvents used in the reaction, in the sub-sequent reaction with an aromatic dihydroxy compound.

In a separate vessel, the aromatic dihydroxy compound and an alkali hydroxide, preferably sodium hydroxide or potassium hydroxide, in the molar ratio of 1:2, are dissolved in sufficient water to produce approximately a 10% ~ -strength aqueous alkali metal salt solution of the bisphenol.
Water-insoluble or sparingly soluble alkali metal salts of dihydroxy compounds are employed as an a~ueous suspension in the reaction. It is also possible to use, without dis-advantage, more dilute or more concentrated alkali metal salt solutions or suspensions.

LeA 15,223 -19-~046693 A solution or suspension of a dihalogeno-s-tri-azine which has been isolated and been purified by recrystal-lization, distillation or elution, or of a non-isolated dihalogeno-s-triazine, dissolved or suspended in water, in the presence or absence of an organic solvent such as, for example, acetone, methyl ethyl ketone or dioxane or of a water-immiscible organic solvent which is inert towards the di-halogenotriazine, is now added in portions, or as one portion, in the molar ratio of 201:1 to 2:1 to this aqueous alkali metal salt solution or suspension., As inert organic solvents it is possible to use, for example, chlorinated hydrocarbons such as CH2C12, CHC13, CC14, ethylene chloride and trichloroethylene, benzene, toluene, ~ ~-xylenes, chlorobenzene, chlorotoluenes, dichlorobenzenes and more highly chlorinated aromatic compounds to prepare the suspension or solution of dihalogeno-s-triazine.

It is aqually possible first to take the dichloro-triazine solution or suspension and to add the alkali metal salt solution or suspension of the bisphenol.

The well-stirred one-phase or two-phase mixture is now kept at a temperature between 0C and 300C, preferably between 30 and 150C, for a period of 0.2 to 20 hours. If appropriate, the organic solvents, such as for example, acetone, which have been left from the reaction of cyanuric chloride with a compound of formula 13 are removed by dis-tillation in the course of this reaction stage. Ac a rule, the conden ation of the dichloro-s-triazine with the di-hydroxy compound is complete not later than after 5 hours.
The entire reaction up to this point is carried out under an inert gas atmosphere, for example, under nitrogen. The LeA 15,223 -20-iO~16~93 lk~lli salts of th~ bisphenols of the formula 11, containin~3 s-triazin~ rings! which are formed, are mor~ or less re~dily w~lt~r-soluble, depending on the nature of the dih~lo~eno-s-triazine used and of the aromatic dihydroxy compound used, so that after the condensation has taken place, either a solution, an emulsion or a suspensicn is present, though this is not of decisive importance with regard to the formation of the poly- ~-carbonates according to the invention.

If it is desired to prevent the occurrence of side-reactions between the aromatic dihydroxy compound and two molecules of the dihalogeno-s-triazine with formation of intermediate products of the formula 17 Hal r ~ O-X_O~ Hal (17) )~(Q)a ( )~(Q)a in which 15 X, Z, R, Q, a and Hal have the abovementioned meaning it is advantageous to choose a large excess of bisphenol and to effect both the addition of the dihalogeno-s-triazine and the condensation at an elevated temperature. However, the formation of the by-products of the formula 17 does not inter-fere with the overall course of the reaction since these com-pounds are also smoothly built into the polycarbonate structure.

' If desired, a solvent suitable for aromatic polycar-bonates, such as methylene chloride, chloroform, carbon tetra-chloride and 1,2-dichloroethane, or chlorinated aromatics, such as dichlorobenzene, chlorotoluene or chlorobenzene, is also added to the one-phase or two-phase mixture in which the alkali metal salts of the aromatic dihydroxy compound, optionally .~ LeA 15,223 -21-~046693 ~
~m~)lc)y~l in c~xcess, ~In(l th~ .llkali met~] s(~lts ~f thc ~)isphenol tll.~ rormula 11, containin~l s-tri~zine structures, arc ~is-~c~lv~!~ or sus~cn~ed, and a~ter ~d~ition of the a(lont For linlitin~l th~ mol~ul~r wciqht, alrea~y mcntioncd abovc, thc r~action with compounds forming c~rbonat~ grou~,s, such as ~rbonic acid derivatives, for exam~lc, ~hosgene, bis-chloro-carbonic acid esters or oligomcric carbonates obtainable from dil~ydroxy com~ounds and containing chlorocarbonic acid ester cnd groups, is carried out in a known manner as discloscd in th~ aforesaid patents in an alkaline medium at a pll value be-tween 10 and 14, depending on the nature of the bisphenol com-pone~lt 10 which is used and of the bisphenol 11, containing s-triazine structures, which is used.

The polycarbonates containing s-triazine rings and prepared according to the two-phase boundary process, which either precipitate from the reaction mixture or are dissolved in the organic phase, are isolated in the usual manner, for : example by acidifying the reaction mixture which reacts alka~
line and filtering off the polycarbonate which precipitate~s and washing it with water until neutral, or precipitating the polycarbonate present in solution from the organic phase or evaporating the solution of the polycaxbonate which has been washed until neutral.
':
; The polymers thus obtained are low molecular or high molecular depending on the amount of chain stopper added.

When using dihalogeno-s-triazines of the formula 8, in which Q denotes a -COOH, -S03H or aliphatic OH group it is also possible, if desired, to prepare, by the process described above, polycarbonates containing s-triazine rings branched or `
LeA 15,223 -22-10~6~3 crosslinked via the -COOH, -SO3H or aliphatic OH group, by carrying out the formation of the polycarbonate at a high pH
value, preferably at a pH value >13.

The polycarbonates with structural units of the formula 4 are prepared analogously to the polycarbonates with structural units of the formula 3.

The new polycarbonates containing s-triazine rings, according to the invention, of the formula 3 and 4, are out-standingly suitable for polymer-analogous reactions by virture of the incorporation of the s-triazine structural units of the formula 1 and 2, through the substituent Q in the formula 1 or through the SO3H group or through the radicals R5 an~ R6 in the formula 2. For example, polycarbonates containing s-tri-azine structures and containing aliphatic OH groups can be crosslinked with aminoplasts or their defined intermediate products such as, for example, melamine resins, benzoguanamine resins or urea resins, phenolic resins or organic diisocyanates and polyisocyanates, to give hard coatings.

Polycarbonates of the formulae 3 and 4, containing 2~ ester groups and carboxyl groups, can be crosslin~ed, for example, with bis-oxazolines or diepoxide and polyepoxide com-pounds such as glycidyl esters to give hard coatings. The lac-quers can optionally contain pigments and the customary lacquer - auxiliaries.

Polycarbonates with structural units of the formula 3 in which Q denotes a carboxyl or sulphoxyl group which are insoluble, at a certain molecular weight, in numerous organic solvents, are outstandingly suitable for the absorptive isola-LeA 15,223 -23-.

tion or removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from aqueous solutions or mixtures with water.

In the examples which follow "hrs." denotes hours, "mins." denotes minutes and "Ex." denotes example.

LeA 15,223 -24-~0~l~69.3 Ex~mple 1 _ _ _ Copolycarbonate from 2,2-bis-(4-hydroxyphenyl)-pro-pane (bisphenol A) and 2-diethanolamino-4,6-dichloro-s-triazine (95:5 molar parts), with chain stopper.

1.27 g (5 mmols) of 2-diethanolamin~-4,6-dichloro-s-triazine, suspended in 60 ml of chlorobenzene, and 0.2 g of NaBH4, are added to a solution of 21.7 9 (0.095 mol) of bis-phenol A and 7.6 g (0.19 mol) of NaOH in 180 ml of water, while simultaneously passing in a gentle stream of nitrogen. The well-stirred two-phase mixture is heated to about 90C for 4 hours. It is then allowed to cool to about 20C, whereupon an intermediate product precipitates. After addition of 0.43 g (2.86 mmols) of p-tert.-butylphenol and 120 ml of CH2C12, the pH is adjusted to 11-12 with 10% strength hydrochloric acid and 13.4 g (0.135 mol) of COC12 are passed in over the course of about 30 minutes at 24-27C, while stirring vigorously.
During the phosgenation, in the course of which the intermediate product dissolves, the pH value is kept between 11 and 12 by dropwise addition of 1 N NaOH solution. After addition of 5.5 ml of 1~ strength aqueous triethylamine solution, the mix-ture is stirred for a further 10 minutes at pH 11-12, during which time the two-phase mixture becomes highly viscous. After acidification with dilute phosphoric acid, the organic phase - is separated off, washed with distilled water until neutral and added dropwise to methanol, whereupon the polycarbonate precipitates as a white powder.

After drying for 17 hours at 100C and 15 mm Hg, 2~.4 g (86%) of polycarbonate containing s-triazine are ob-tained.

LeA 15,223 -25-~046693 The relative viscosity (0.5 g of product in 100 ml of CH2C12 at 25OC) is 1.254.

N content: calculated 1.12~, found 1.04%
% aliphatic OH: calculated 0. 6a% ~ found 0.62~

The polycarbonate obtained according to Example 1 is -dissolved in chlorobenzene and crosslinked with toluylene diiso-cyanate at the boil. Hard products result, which precipitate from the reaction solution and are insoluble in organic sol-vents.

Example 2 . _ . .

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

20.1 g (0.088 mol) of bisphenol A and 7.04 g (0.176 mol) of NaOH are dissolved in 180 ml of water under a N2 at-15 mosphere, with addition of 0.2 g of NaBH4, and the solution is warmed to approx. 60-70C. A suspension of 6.27 g (24.8 mmols) of 2-diethanolamino-4,6-dichloro-s-triazine in 60 ml of chloro-benzene is added dropwise thereto and the reaction is allowed to take place for 2 hours at 80-90C while stirring vigorously.
After cooling to room temperature, the pH is adjusted to 11 with dilute hydrochloric acid, 120 ml of CH2C12 and 1.315 g ~ ;
(8.75 mmols) of p-tert.-butylphenol are then added and the mixture is reacted with 9.3 g (0.094 mol) of COC12 at pH 11-12 in accordance with Example 1. After addition of 6.3 ml of 1% strength aqueous triethylamine solution, the mixture is stirred for a further hour at pH 11 and the polycarbonate is isolated by evaporating the organic phase which has been washed until neutral.

LeA 15,223 -26-1~4~;93 Yi(?ld: 24.2 ~ (93~) of polycarborlate containing triazine ~r 1 (0-5 ~ of product in 100 ml of CH2C12, 25C): 1.078 N content: calculated 5.35~, found 4.96%
OH number: calculated 107, found 91 The polycarbonate obtained in Example 2 can, for example, be stoved together with hexamethylolmelamine hexa-methyl ether in m-cresol, in the presence of p-toluenesulphonic acid, at 200C, to give hard coatings.

Example 3 Crosslinked copolycarbonate from bisphenol A and 2-diethanolamino-4,6-dichloro-s-triazine (90:10 molar parts) with chain stopper.

Analogously to Example 1, 20.6 g (0.09 mol) of bis-phenol A, 7.2 g (0.18 mol) of NaOI~ and 2.53 g (0.01 mol) of lS 2-diethanolamino-4,6-dichloro-s-triazine are reacted in a sol-vent mixture of 180 ml of water and 60 ml of chlorobenzene, with the addition of 0.09 g of NaBH4, for 4 hours at ~he reflux tem-perature. After having cooled, 0.27 g (1.8 mmols) of p-tert.-- butylphenol and 140 ml of CH2C12 are added, the pH is adjusted to 14 with 2 N NaOH solution and 11.9 g (0.12 mol) of COC12 are passed in at pH 14 wlth vigorous stirring. After the ~ phosgenation, the aqueous phase is free of the bisphenolate ; salt. 4.9 ml of 1 per cent strength aqueous triethylamine solution are then added and the mi*ture is condensed. After stirring for about 3 minutes longer, the mixture first becomes highly viscous and finally gums up to the point that further stirring no longer serves any purpose. The polycarbonate mass which has swollen like a gel is filtered off, repeatedly treated with dilute phosphoric acid and then rinsed with water.
LeA 15,223 -27-~0~693 ...

~ fter dryin~1 for 24 h(>ur~ . a vacuum dryin(l ~-at,inc~t O, ~ t ~5 ~l o~ .lr~l viscouC; mass are o~,tain~.

~ ro~luct is insolul~le in most or(Janic solvents.

N ~ont~nt: c.~lculat~d 2.29~, found 2.20 5 I;'.xam_1~ 4 Co~olycarbonate from bisphenol ~ and N-(4,6-dichloro-s-triazille-2-yl)-p-amino~enzoic acid (90:10 molar parts).

2.85 g (0.01 mol) of N-(4,6-dichloro-s-triazine-2-yl)-p-aminobenzoic acid are added 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, 0.2 g of NaBH4 also being added, and the mixture is heated to approx. 90-95C for 5 hours while stirring under a N2 atmosphere. During the heating period, the dichloro-s-triazine dissolves. After cooling to 20C, a clear solution is obtained. After adding 200 ml of CH2C12, the pH value is adjusted to 12 and the mixture is reacted with 11.9 g (0.12 -~
mol~ of COC12 at pH 12 as described under ~xample 1, whereupon a milky white, slightly viscous emulsions forms. The pH is then ad~usted to 13, 8 ml of 1% strength aqueous triethylamine solution are added and the mixture is stirred for a further hour at pH 13.

After acidifying with dilute phosphoric acid, the - mixture is twice extracted by shaking with distilled water and the entire two-phase mixture - since the two phases only sep-arate very slowly - i9 then added dropwise ~O methanol where-upon the polycarbonate precipitates as a white powder.

Yield: 24.7 g (100%) of polycarbonate containing triazine.
N content: calculated 2.26%, found 2.22%
LeA 15,223 -28-10~;93 % C~OH: calculat~d 1.82%, found 1.7%

The product is insoluble in the customary sol~ents for polycarbonate, such as, for e~ample, C~2C12, tetrahydro~
~urane, dioxane and pyridine.

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

A suspension of 68.6 g (0.5 mol) of p-aminobenzoic acid and 50.6 g (0.5 mol) of triethylamine in 1,350 ml of acetone is introduced into a solution of 92.2 g (0.5 mol) of cyanuric chloride in 650 ml of acetone at 0-5C. The reaction tempera-ture is allowed to rise to 20C over the course of 90 minutes ~ -and the mixture is stirred for a further 90 minutes. The re-action product which precipitates is filtered off, washed with distilled water until free of chloride, extracted by hoiling twice with acetone and dried at 50C/15 mm Hg.

Yield: 114 g (80% of theory), melting point >300C
Analysis: calculated C 42.1% H 2.11 N 19.65 Cl 24.95 found 41.7~ 2.17 19.2 24.7 Example 5 ; 20 Copolycarbonate from bisphenol A and N-(4,6-dichloro- -- s-triazinyl-2)-p-aminobenzoic acid (89.5:10.5 molar parts).

18.3 g (0.08 mol) of bisphenol A, 7.~ g (0.18 mol) of ~aOH and 5.7 g (0.02 mol) of N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid in 320 ml of H2O are reacted for 5 hour~
at 90-95C, analogously to Example 4.

After cooling, a solution of 31.8 g (0.09 mol) of bisphenol A bis-chlorocarbonic acid ester in 620 ml of CH2C12 LeA 15,223 -29-~0~6693 is allowed to rnn into the yellow solution of the sodium salts of the dihydroxy compounds over a period of 2 minutes, with vigorous stirring, 15.2 ml of 1% strength aqueous triethylamine solution are then added and the mixture is stirred further, while keeping the pH value of the aqueous solution at 12. The two-phase mixture becomes very viscous within a short time.
After about 20 minutes, the reaction is discontinued since a white spongy gel precipitates and stirring no longer serves any purpose. The reaction mixture is acidified with dilute phosphoric acid and the gel formed is filtered off. The fil-trate consists exclusively of the aqueous phasç, the entire CH2C12 being absorbed by the polycarbonate containing triazine.
The polycarbonate is washed until substantially neutral by -, suspending it in distilled water and is dried for 20 hours at 50C/15 mm Hg.

Yield: 46.5 g (99%) of floçculent white polycarbonate containing , triazine.
; N content: calculated 2.38~, found 2.25%

The product is soluble in dimethylformamide (DMF~.

- 20 % COOH (in DMF): calculated 1.91%, found 1.70%.

Example 6 Removal of hydrocarbons from aqueous solutions by ~, abæorption on a copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid (89.5:10.5 molar parts).
, A 30 cm long column of internal diameter 1.5 cm is filled with 10 g of the copolycarbonate prepared in Example 5 (packing height of the very voluminous material: about 20 cm).
LeA 15,223 _30_ 10~6g3 ~';olut:ioll.s ol~ hy(lrocarl)c)ns in wat~r, an(l ~alt ~;olu~:ic)n~ ,n ml i n ~nCI) (`a~t?) ar(~ 0We(~ to run .~uccc~s~ivoly t:hrou-Jh the (ol~ ln un(l tho hy(lroc.3rbon colltent in tho a(1ueous .st)llJtion, l~e ror~ a~ f ~er ~)a~;sa~J~ tl~l ouc~h the column, is (l~terminccl ~-y 5 (~a~ ro~ to(lr~lplly (~ q'c~

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LeA 15, 223 -32-10~6693 Exam~le 7 Copolycarbonate from bisphenol A and N- (4,6-dichloro-s-triazinyl-2)-p-aminoben7Oic acid (95: 5 molar parts) with cllain stopper.

Analogously to Example 5, 9.1 g (0.04 mol) of bisphenol A are first reacted in alkaline solution with 1.5 g (5.26 mmols) of N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid, 474.3 mg (3.16 mmols) of p-tert.-butylphenol are then added, a sol~
ution of 21.2 g (0.06 mol) of bisphenol-A bis-chloro-carbonic acid ester in 180 ml of CH2C12 is then allowed to run in, 10.1 ml of 1% strength aqueous triethylamine solution are added and the mixture is stirred further at pH 13. After about 10 min-utes, the polycarbonate containing triazine precipitates as a ;
jelly and is worked up as described under Example 5.

Yield: 26.0 g (99~) of a white granular product 15 N content: calculated 1.12%, found 1.02~
COOH content: calculated 0.897~, found 0.899%

Example 8 Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid (98:2 molar parts) with chain stopper.
~..
- a) Analogously to Example 5, 9.1 g ~0.04 mol) of bisphenol A
are reacted with 0.57 g (2 mmols) of N-t4,6-dichloro-s-tri-azinyl-2)-p-aminobenzoic acid and then condensed, in the pres-ence of 383 mg (2.55 mmols) of p-tert.-butylphenol, with 21.2 g (0.06 mol) of bisphenol A bis-chlorocarbonic acid ester, with the addition of 10.1 ml of 1% strength aqueous triethylamine solution, at pH 12-13. After 10 minutes, the copolycarbonate LeA 15,223 _33_ ~04669~

precipitates as a jelly and is worked up as described above.

Yield: 25 g (97%) N content: calculated 0.439~, found 0.41~

b) If the reaction described under a) is carried out in the presence of 766 mg (5.11 mmols) of p-tert.-but~lphenol, the polycarbonate remains dissolved in methylene chloride. After the addition of triethylamine, the mixture is stirred for a further hour at pH 12-13, the organic phase is washed until neutral and then evaporated, and the residue is dried for 65 hours at 100C/15 mm Hg.

; Yield: 22.2 g (86%) of copolyearbonate containing triazine.
~rel (0-5 g f product in 100 ml of C~2C12, 25C): 1.267 N content: calculated 0.434%, found 0.41%
COOH content: calculated 0.349%, found 0.34%

Example 9 Copolycarbonate from bisphenol A and N-(4,6-dichloro-- s-triazinyl-2)-p-aminobenzoic acid (80:20 molar parts).

Analogously to Example 5, 10 g (0.044 mol) of bis-phenol A, 8 g (0.2 mol) of NaOH and 5.7 g (0.02 mol) of N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid are reacted in 250 ml of water and then condensed with 12.7 g (0.036 mol) of ~- bisphenol A bis-chlorocarbonic acid ester in 230 ml of CH2C12 - with the addition of 10.1 ml of a 1% strçngth aqueous tri-ethylami~e solution. 5 minutes after the addition of the triethylamine, the polycarbonate already precipitates as a jelly. After stirring for a further hour, the mixture is worked up as described above. The gel is washed until neutral and dried for 30 hours at 80C/15 mm Hg.
LeA 15,223 -34-1046~i93 Yield: 22 g (92%) of a white, finely granular powder N content: calculated 4.65~, found 4.48%
CQOH cont~nt: calculated 3.74%, found 2.96 Example 10 Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid (90:10 molar parts), branched by means of cyanuric chloride.

Analogously to Example 4, 20.6 g (0.09 mol) of bis-phenol A and 2.85 g (0.01 mol) of N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid are dissolved in 190 ml of 1 N NaOH
solution and a solution of 40.5 mg (0.22 mmols) of cyanuric chloride in 50 ml of dioxane is added. The mixture is heated to 90-95C for 5 hours while stirring under a N2 atmosphere and is then cooled to 20C, and the resulting clear solution is mixed with 150 ml of CH2C12 and then reacted with 11.9 g (0.12 mol) of COC12 at pH 12. After dilution with 150 ml of CH2C12, 8.3 ml of 1% strength aqueous triethylamine solution are added and the mixture is stirred for a further hour at pH 12-13. After acidifying with dilute phosphoric acid, the polycarbonate containing triazine precipitates as a gel and is worked up as described in ~xample 5.

Yield: 24 g (97~) of white flocculent product.
N content: calculated 2.06~, found 2.08%.

Example 11 .
Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-sulphanilic acid (90:10 molar parts).

20.6 g (0.09 mol) of bisphenol A, 7.2 g (0.18 mol) of NaOH and 3.43 g ~0.01 mol) of the Na salt of N-(4,6-dichloro-LeA 15,223 -35- -~0~6693 s-triazinyl-2!-sulphanilic acid are reacted in accordance with Example 4, the mixture is then reacted with 11.9 g (0.12 mol) of COC12 at pH 12 and after addition of triethylamine the whole is stirred for a further hour a~ pH 13. On acidifying the reaction product, the copolycarbonate precipitates as a white powder which is filtered off, washed until neutral by sus-pending it in water, then rinsed with methanol and dried for 65 hours at 80C/15 mm Hg.

Yield: 23.5 g (93%) of copolycarbonate N content: calculated 2.21%, found 2.16%.

Example 12 Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid ethyl ester (85.7:14.3 molar parts). ;-Analogously 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 H2O is reacted for 3 hours at 80-90C with a suspension of 4.69 g (15 mmols) of N-(4,6-dichloro-s-triazinyl-2)-p-amino-benzoic acid ethyl ester in 60 ml of chlorobenzene. On cooling to room temperature, a gritty intermediate product precipitates.
After addition of 120 ml of CH2C12, the pH is adjusted to 13 and the mixture is reacted with 11.9 g (0.12 mol) of COC12 at - pH 13. After addition of 5 ml of 1% strength aqueou~ triethyl-amine solution the mixture is stirred ~urther until the copoly-carbonate precipitates as a gel after about 15 minutes. The precipitated product is worked up as described in Example 5.

Yield: 26 g (100%) of copolycarbonate containing triazine.
N content: calGulated 3.22~, found 3.15 LeA 15,223 -36-10~6693 The IR spectrum (KBr pressing) shows unambiguously that the material is a polycarbonate containing ester groups.
The product is soluble in dimethylformamide.

The N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid ethyl ester used was prepared according to an instruction given by Thurston et al. ~J. Am. Chem. Soc. 73, 2981 [19513) for the preparation of 2-amino-dichloro-s-triazines by reaction of 0.5 mol of cyanuric chloride with 0.5 mol of p-aminobenzoic acid ester, with addition of 0.25 mol of Na2CO3, in acetone (200 ml)/dioxane (50 m ~water (300 ml), at 0-5C. The dichloro-triazine which precipitates from the reaction mixture is puri-! fied by boiling with acetone.

Yield: 76~, melting point 294-295C
Calculated: C 46.05 H 3.22 N 17.9 Cl 22.7 Found: 46.1S 3.13 17.8 22.6 Example 13 .y ' ~
- Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-glycine. ~
., :
~ FolIowing an instruction for the preparation of 2- ~ --~ 20 amino-4,6-dichloro-s-triazines (J. Thurston et al., J. Am. Chem.
Soc. 76, 2981 [1951~), 1.84 g (0.01 mol) of cyanuric chloride ~ and 0.79 g (10.5 mmols) of glycine are reacted, with addition I of 0.84 g (21 mmols) of NaOH, in acetone/H2O (7:11 parts by volume) at approx. 0C and the mixture is stirred for a further '~ 25 hour and allowed to warm to room temperature. A solution of .~ 9.6 g (42 mmols) of bisphenol A and 3.36 g (84 mmols) of NaOH
in 42 ml of H2O is added to this orange-red colored solution of ~ -the dichlorotriazine in acetone/water and the mixture is grad-ually heated to about 90-95C, during which time the acetone ~ -LeA 15,223 -37-- ', ' . ' ' ' ~ , ' '" ' ' . ~', is removed from the reaction solution by distillation. After removing the acetone, the mixture is stirred for a further 3 hours at 95-100C. It is then allowed to cool to room tempera-ture, the light yellow solu~ion is diluted with 100 ml of water, a solution of 16.96 g (48 mmols) of bisphenol A bis-chlorocar-bonic acid ester is allowed to run in while stirring vigorously, 10.1 ml of l~ strength aqueous triethylamine solution are added and the mixture is stirred further at pH 13. After about 15 minutes, the polycarbonate precipitates as a jelly. The reac-tion is stopped and the polycarbonate is worked up as described in Example 5.

Yield: 22.3 g (93%) of a flocculent white copolycarbonate N content: calculated 2.32%, found 2.28~
COOH content: calculated 1.87%, found 1.7~ -The product is able to absorb approx. 38 times its own weight of CH2C12.

Example 14 Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-6-aminohexanoic acid (90:10 molar parts).

Analogously to Example 13, 1.84 g (0.01 mol) of cyanuric chloride are reacted with 1.38 g (10.5 mmols) of 6-amino-hexanoic acid to give N-(4,6-dichloro-s-triazinyl-2)-6-aminohexanoic acid, the resulting white suspension is condensed with 9.6 g (42 mmols) of bisphenol A, while distilling from the mixture the acetone originating from the first reaction stage, and the resulting colorless solution of the dihydroxy compounds is polycondensed at 20-25C with a solution of 16.96 g (48 mmols) of bisphenol A bis-chloro-carbonic acid ester in methylene chloride at pH 13 for 1 hour after having added 10.1 LeA 15,223 -38-ml of 1% stren~th triethylamine solution. The organic phase is separated off, acidified with dilute phosphoric acid, washed un-til neutral and added dropwise to methanol, whereupon the poly-carbonate containing triazine precipitates in a white flocculent form.

Yield: 21.4 g (87%) ~rel (0~5 g of product in 100 ml of CH2C12, 25C): 1.535 N content: calculated 2.27~, found 2.12~
COOH content: calculated 1.62~, found 1.59~ ;

Example 15 ; Copolycarbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-2-aminobenzoic acid.

Analogously to Example 4, 9.6 g (42 mmols) of bis-phenol A, 3.76 g (94 mmols) of NaOH and 2.85 g (10 mmols) of N-(4,6-dichloro-s-triazinyl-2)-2-aminobenzoic acid in 180 ml of water are reacted for S hours at approx. 95-100C, a solu-tion of 16.96 g (48 mmols) of bisphenol A bis-chlorocarbonic acid ester in 170 ml of CH2C12 is allowed to run into the resulting milky turbid aqueous solution, 10.1 ml of 1% strength aqueous triethylamine solution are added and thç mixture is condensed for 1 hour at pH 13. The viscous organic phase is worked up as described in Example 14.

Yield: 24.7 g (100%) of a flocculent white copolycarbonate nrel (0~5 g of product in 100 ml of CH2C12, 25C): 1.372 N content: calculated 2.26%, found 2.08%
COOH content: calculated 1.82~, found 1.7%

The N-(4,6-dichloro-s-triazinyl-2)-2-aminobenzoic acid used was prepared by reaction of 36.8 g (0.2 mol) of cyanuric LeA 15,223 _39_ , . ", . ' ~: ,, :1046693 chloride and 27.4 g (0.2 mol) of 2-aminobenzoic acid in 520 ml of acetone at 0-2C in the presence of 20.3 g (0.2 mol) of triethylamine as an HCl acceptor. The reaction product obtained is washed with dilute hydrochloric acid and then with water un-til free of chloride and is boiled with acetone and dried.

Yield: 30.2 g (53~); melting point >330C (decomposition) Analysis: Calculated C 42.1% H 2.11% Cl 24.95%
Found 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 molar parts).

.
Analogously to Example 13, 1.84 g (10 mmols) of cyanuric chloride are reacted with 1.31 g (10.5 mmols) of 2-aminoethane-l-sulphonic acid (taurine) to give the corresponding dichloro-s-triazine, the resulting white suspension is reacted, at 60-95C, with 9.6 g (42 mmols) of bisphenol A while simul-` taneously distilling off the acetone present in the reaction mixture, giving a colorless solution,and finally the product is polycondensed with a solution of 16.96 g (48 mmols) of bis-- 20 phenol A bis-chlorocarbonic acid ester in met~ylene c~loride at - pH 13 after addition of 10.1 ml of 1% strength aqueous triethyl-amine solution.

After stirring for a further 30 minutes, the copoly-carbonate containing triazine precipitates as a jelly and is worked up as described in Example 5.

Yield: 23.8 g ~97%) N content: calculated 2.27%, found 2.18%

LeA 15,223 -40-,: :

' ' .

1046f~93 The product is able to absorb approx. 36 times its own weight of CH2C12.

Ex~mple 17 Copolycaxbonate from bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-5-aminoisophthalic acid (90:10 molar parts).

Analogously to Example 13, 1.84 g (10 mmols) of cyanuric chloride are first reacted with 1.9 g (10.5 mmols) of - 5-aminoisophthalic acid in the presence of 1.24 g (31 mmol~) of ; NaOH in acetone/water at 0-5C, the resulting light yellow suspension is condensed with 9.6 g (42 mmols) of bisphenol A -~
at 60-90C for 5 hours, and finally the aqueous solution of the dihydroxy compounds is polycondensed by the phase boundary process with a solution of 16.96 g (48 mmols) of bisphenol A
bis-chlorocarbonic acid ester in methylene chloride at pH 13 ~-after addition of 10.1 ml of 1% strength aqueous triethylamine solution. After stirring for approx. 10 minutes longer, the copolycarbonate precipitates as a jelly and is worked up as described in Example 5.

Yield: 25 g (99%) of white copolycarbonate N content: calculated 2.22%, found 2.20%
COOH content: calculated 3.58%, found 3.33%
., ~ .
The product is able to absorb approx. 19 times its own weight of CH2C12.

Example 18 Copolycarbonate ~rom bisphenol A and (4,6-dichloro-s-triazinyl-2)-hydroxyacetic acid (90:10 molar parts)~

Analogously to Example 4, 9.6 g (42 mmols~ of bisphenol - LeA 15,223 -41-lV4~f~93 A, 3.76 g (94 mmols) of NaOH and 2.24 g (0.01 mol~ of (4,6-dichloro-s-triazinyl-2)-hydroxyacetic acid are react~d in 200 ml of water for 4 hours at 70-80C. After cooling to room temperature, a solution of 16.96 g ~48 mmols) of bisphenol A
bis-chlorocarbonic acid ester in 200 ml of CH2C12 is allowed to run in while stirring vigorously, 10 ml of 1% strength aqueous triethylamine solution are added and the mixture is condensed at pH 13. After stirring for a further 10 minutes, the polycarbonate containing triazine precipitates as a jelly and is worked up as described in Example S.

Yield: 22.9 g (95~) of copolycarbonate containing triazine N content: calculated 1.74%, found 1.70~
- COOH content: calculated 1.87~, found 1.75%

Example 19 Copolycarbonate from bisphenol A and S-(4,6-dichloro-s-triazinyl-2)-4-mercaptobenzoic acid (90:10 molar parts).

According to an instruction for the preparation of 2-arylthio-4,6-dichloro-s-triazines (J. Drabek and M. Skrobal, Chem. Zvesti 17, 482 [1963]), 1.84 g (0.01 mol) of cyanuric chloride and 1.54 g (0.01 mol) of 4-mercaptobenzoic acid are reacted, with addition of 0.8 g (0.02 mol) of NaOH, in acetone/
water at 0-5C. A solution of 9.6 g (42 mmols) of bisphenol A
and 3.36 g (34 mmols) of NaOH in 50 ml of water is then added to the reaction mixture and the whole is heated to 70-80C
for 5 hours, while distilling the acetone from the mixture.
; After cooling to room temperature, the product is r~acted, as described under Example 13, with 16.96 g (48 mmols) of bis-phenol A bis-chlorocarbonic acid ester and the polycarbonate formed is worked up as described in Example 5.
LeA 15,223 -42-.

: : .

~046693 Yield: 24.6 g (99~) of copolycarbonate ccntaining triazine N content: calculated 1.69%, found 1.55%

Example 20 Copolycarbonate from 1,1-bis-(4-hydroxyphenyl)-cyclo-hexane, bisphenol A and N-(4,6-dichloro-s-triazinyl-2)-p-amino-benzoic acid (42:48:10 molar parts).

Analogously to Example 15, 11.3 g (42 mmols) of 1,1-bis-(4-hydroxyphenyl)-cyclohexane are reacted with 2.85 g (10 mmols) of N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzoic acid and the resulting mixture of the dihydroxy compounds is con-densed with 19.96 g (48 mmols) of bisphenol A bis-chlorocarbon-ic acid ester. The resulting copolycarbonate is worked up as described in Example 5.

- Yield: 26 g (97~) of copolycarbonate containing triazine N content: calculated 2.08%, found 2.0%

Example 21 Copolycarbonate from 2,2-bis-(3,5-dimethyl-4-hydroxy-phenyl)-propane and N-(4,6-dichloro-s-triazinyl-2)-p-amino-benzoic acid (90:10 molar parts).

Analogously to Example 15, 11.95 g (42 mmols) of 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane are reacted with 2.85 g (10 mmols) of N-(4,6-dichloro-s-triazinyl-2)-p-amino- -benzoic acidi a solution of 19.2 g (48 mmols) of bis-chloro-carbonic acid ester of 2,2-bis-(3,5-dimethyl-~-hydroxyphenyl)-- propane in 170 ml of methylene chloride is then allowed to run in and after addition of 1.36 g (13.5 mmols) of triethyl-; amine the mixture is stixred for a further 3 hours and then worked up as described under Example 5. ~ ~-LeA 15,223 -43-104~;693 Yield: 31 g (94~) of copolycarbonate cont~ining tria~ine N content: calculated 1.70~, found 1.65%

Example 22 Copolycarbonate from bisphenol ~ and N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzamide (90:10 molar parts).

Analogously to Example 4, 9.6 g (42 mmols) of bis-phenol A, 3.36 g (84 mmols) of NaO~ and 2.84 g (10 mmols) of N- (4,6-dichloro-s-triazinyl-2~-p-aminobenzamide in 170 ml of H2O are reacted for 5 hours at 90-95C. A solution of 16.96 g (84 mmols) of bisphenol A bis-chlorocarbonic acid ester in 270 ml of CH2C12 is then added at20-25,while stirring vigor-ously, and after adding 10.1 ml of 1~ strength aqueous tri-ethylamine solution the mixture is condensed for 1 hour at pH
13. The polycarbonate which precipitates as a jelly is worked up as described in Example 5.

Yield: 21.6 g ~87%) of copolycarbonate N content: calculated 2.83%, found 2.75%

The IR spectrum (KBr pressing) shows unambiguously that the material is a polycarbonate containing amide groups.

The N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzamide used was prepared by reaction of 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) of NaHCO3, at 0-3C. ~ -Yield: 51.6 (91%); melting point >300~C
Cl content: calculated 25.1%, found 24.9%

Example 23 Copolycarbonate from bisphenol A and N-(4,6-dichlo~o-LeA 15,223 -44-. ' ' ~ . ' :

1046~;93 s-triazinyl-2)-p-aminobenzenesulphonic acid amide (90:10 molar parts).

Analogously to Example 22, 9.6 g (42 mmols) ~f bis-phenol A are first reacted with 3.2 g (10 mmols) of N- (4,6-dichloro-s-triazinyl-2)-p-aminobenzenesulphonic acid amide, and the product is then condensed with 16.96 g (48 mmols) of bis-phenol A bis-chlorocarbonic acid ester. About 20 minutes after the addition of triethylamine, the copolycarbonate containing triazine precipitates as a jelly.

Yield: 25 g (100%) N content: calculated 2.79%, found 2.7~

The N-(4,6-dichloro-s-triazinyl-2)-p-aminobenzene-sulphonic acid amide used was prepared by reaction of 18.4 g ; (0.1 mol) of cyanuric chloride with 17.2 g (0.1 mol) of 4-aminobenzenesulphonic acid amide in acetone/water (1:1 parts by volume), with the addition of 8.4 g (0.1 mol) of NaHCO3, at 0-3C.

Yield: 53.5 g (84%) of a white pulverulent product Melting point: >300C
Cl content: calculated 22.3%, found 22.1%

Example 24 Copolycarbonate from bisphenol A and 4,4'-bis-[4-- chloro-6-diethanolamino-s-triazine-2-yl]-amino-2,2'-stilbene-disulphonic acid (99:1 molar parts).

Analogously to Example 4, 22.6 g (99 mmols) of bis-phenol A, 7.92 g (198 mmols) of NaOH and 847 mg ~1 mmol) of the di-Na salt of 4,4'-bis-[4-chloro-6-diethanolamino-s-triazine-2-yl]-amino-2,2'-stilbenedisulphonic acid in 175 ml of H2O
LeA 15,223 -45-10~6g3 are heated to 90-95C for 5 hours. The mixture is ~hen cooled to 20C and after adding 450 mg (3 mmols) of p-tert.-butyl-phenol and 175 ml of cH2C12 the mixture is reacted with 14.9 g (0.15 mol) of COC12 at pH12, with vigorous stirring. 10.1 ml 5 of 1~ strength aqueous triethylamine solution are then added and the mixture is stirred for a further hour at pH 12. After acidifying with dilute H3PO4, the aqueous phase is separated of f and the organic phase is added dropwise to methanol, where-upon the polycarbonate precipitates.

Yield: 24.3 g (94%) ~ rel (0-5 g of product in 100 ml of CH2C12, 25C): 1.245 N content: calculated 0.54%, found 0.53%

On irradiation with UV light, the product shows a blue fluorescence.

Example 25 Copolycarbonate from bisphenol A and 4,4'-bis-[4-chloro-6-diethanolamino-s-triazine-2-yl]-amino-2,2'-stilbene-disulphonic acid (90:10 molar parts).

Analogously to ~xample 24, 20.5 g (0.09 mol) of bis-phenol A and 8.47 g (0.01 mol) of 4,4'-bis-[4-chloro-Ç-di-ethanolamino-s-triazine-2-yl]-amino-2,2'-stilbenedi~ulphonic acid are reacted, with the addition of 7.2 g (0.18 mol) of NaOH in 210 ml of H2O, 210 ml of CH2C12 and 0.75 g ~S mmols) of p-tert.-butylphenol are then added at room temperature and the mixture is then phosgenated with 11.9 g ~0.12 mol) of COC12, After adding 10.1 ml of 1% strength ~queous triethyl-amine solution, the mixture is stirred for a further hour at pH 12.5. After acidification, the polycarbonate, in which the entire methylene chloride is absorbed, precipitates as a gritty LeA 15,223 -46-104t~ 3 product. After 24 hours' drying at 80C/15 mm Hg, 30 g ~99~) of copolycarbonate are left.

N content: calculated 4.61~, found 4.4%

Example 26 Copolycarbonate from bisphenol A and 4,4'-bis-~4-chloro-6-anilino-s-triazine-2-yl]-amino-2,2'~stilbenedisulphonic acid (99:] molar parts).

Analogously to Example 24" 22.6 g t99 mmols) of bis-; phenol A and 0.824 g ~1 mmol) of the di-Na salt of 4,4'-bis-[4-chloro-6-anilino-s-triazine-2-yl]-amino-2~2~-stilbenedisul-phonic acid are reacted in the presence of 7.92 g (198 mmols) of NaOH in 175 ml of water, the product is phosgenated at room ; temperature with 14,9 g (0.15 mol~ of COC12 at pH 13 after addition of 175 ml of CH2C12 and 0.45 g (3 mmols) of p-tert.-butylphenol and after addition of triethylamine (10.1 ml of a 1% strength aqueous solution) the mixture is stirred for a ~
further hour. After acidification, the mixture is washed with ~-distilled water and the organic phase is added dropwise to methanol, whereupon the polycarbonate precipitates as a white flocculent material.

Yield: 23.8 g (92%) el (0-5 g of product in 100 ml of CH2C12, 25C): 1.287 N content: calculated 0.54%, found 0.49%
. .
On irradiation with W light, the product shows a green-blue fluorescence.

Any of the other bis-hydroxy compounds and particularly the bis(hydroxyaryl)alkanes, and s-triazine compounds disclosed ~ as suitable herein may be used to prepare the novel polycarbo-- LeA 15,223 -47-104~i693 nates in accordance with the foregoing working examples.

Although the invention has been described in detail for the purpose of illustration, it is to be understood tlla~
such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

LeA 15,223 -48-.

',

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polycarbonate consisting essentially of structural units of the following formulae 3 and/or 4:

(3) (4) in which Z represents -O-, -S-, -NH- or -NR1- or -?-(R*)-(Q*)a*

R and R* are identical or not identical and denote alkylene radicals with 1-20 carbon atoms, cyclo-alkylene radicals with 5-12 carbon atoms, mono-nuclear or polynuclear arylene radicals, or heteroarylene radicals bonded via carbon, with up to 14 carbon atoms, monosubstituted or poly-substituted mononuclear or polynuclear arylene radicals, or heteroarylene radicals bonded via carbon, with up to 14 ring carbon atoms and substituted with alkyl, alkoxy or alkylmercapto groups with 1-4 carbon atoms, halogen atoms, -NO2 or -CN, alkylarylene radicals with a total of up to 30 carbon atoms or aralkylene radicals with a total of up to 30 carbon atoms, R1 denotes alkyl radicals with 1 to 20 carbon atoms, cycloalkyl radicals with 5 to 12 carbon atoms, mononuclear or polynuclear aryl radicals, or heteroaryl radicals bonded via carbon, with up to 14 ring carbon atoms, unsubstituted or substituted with alkyl, alkoxy or alkylmercapto groups with 1 to 4 carbon atoms, halogen atoms, -NO2 or -CN, 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 and Q* are identical or not identical and denote a -COOH, -COOR2, -CONR3R4, -SO3H, -SO2NR3R3 or aliphatic OH group, R2 represents alkyl groups with 1-4 carbon atoms, R3 and R4 independently of one another represent hydrogen, straight-chain or branched alkyl groups with 1-4 carbon atoms or an unsubstituted, monosubstituted or polysubstituted phenyl radical or conjointly with the N atom form a 5-membered or 6-membered ring system and a and a* are identical or not identical and denote an integer of from 1 to 4 inclusive, R5 and R6 independently of one another represent H
or alkyl, hydroxyalkyl, carboxyalkyl or alkoxy-carbonyl-alkyl groups containing 1-5 carbon atoms, C5-C7- cycloalkyl groups or C6-C14-aryl groups or conjointly with the N atom form a 5-membered or 6-membered ring system, X denotes an o-, m- or p-phenylene radical or an o-, m- or p-phenylene radical, monosubstituted or polysubstituted with alkyl groups having 1-4 carbon atoms or halogen atoms or denotes a radical characterized by the formula 5 (5) in which R7 and R represent hydrogen atoms, alkyl radicals with 1-4 carbon atoms or halogen atoms and have identical or different meanings, and Y denotes a single bond, an alkylene or alkylidene radical with 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -S-, -CO-, -SO-, -SO2- or a radical of the formula 6a or 6b (6a) (6b) wherein R9 to R11 denote alkyl radicals with 1-4 carbon atoms, and R11 can also represent hydrogen or halogen atoms, and n is an integer between 1 and 200.

2. A polycarbonate consisting essentially of structural units of the following formulae 3 and/or 4:

(3) (4) which are branched through structural units of the formula 18 (18) in which X, Z, R, Q, a, R5, R6 and n have the same meaning as in Claim 1 and the said structural units of formula (18) are present in amounts of 0.01 to 5 mol %, based on the structural units 3 and/or 4, in the complete molecule.

3. Polycarbonates according to Claim 1 characteriz-ed in that X denotes a radical characterized by the formula 5 in which R7 and R8 have the same meaning as in Claim 1 and Y is an alkylene or alkylidene radical with 1-7 carbon atoms or a cycloalkylene or cyclo-alkylidene radical with 5-12 carbon atoms.

4. Polycarbonates according to Claim 3, character-ized in that X denotes .

5. A process for the preparation of polycarbonates containing s-triazine rings, comprising reacting according to the methods for preparation of polycarbonates, aromatic bis-hydroxy compounds containing s-triazine rings, of the formula (11) in which formula Z, R, Q, a and X have the same meaning as in Claim 1, by themselves or mixed with up to 199 equivalents of a dihydroxy compound of the formula 10, HO-X-OH (10) in which X has the same meaning as in Claim 1, with phosgene and/or a bis-chlorocarbonic acid ester of a di-hydroxy compound of formula 10 or an oligomeric carbonate, con-taining chlorocarbonic acid ester end groups, obtainable from a compound of formula 10, the sum of the equivalents of the dihydroxy compound of formula 10, employed as such or as its alkali metal salts or as its bis-chlorocarbonic acid ester or as oligomeric carbonates, containing chlorocarbonic acid ester end groups, prepared from the dihydroxy compound of formula 10, not exceeding 199 equivalents per equivalent of the compound 11 and at least 1.05 chlorine equivalents bonded via -CO-being employed per phenolic OH equivalent.

6. The process according to Claim 5 wherein the bis-hydroxy compounds 11 are produced by reaction of dihalogeno-s-triazines of the formula 8 (8) in which Z, R, Q, a and X have the same meaning as in Claim 1 and Hal denotes F, Cl, Br or I
with aromatic hydroxy compounds of the formula 10 in the presence of a proton acceptor, with-out separate isolation and in the same reaction vessel as the reaction of compounds 11 either by themselves or mixed with an additional compound of formula 10 depending on the choice of the molar ratio of compounds of formula 8 to formula 10 used in the preparation of compound 11, with phosgene or bis-chlorocarbonic acid esters of the aromatic dihydroxy compounds 10 or oligomeric carbonates, containing chlorocarbonic acid ester end groups, obtainable from the compound of formula 10, the sum of the equivalents of the dihydroxy compound of formula 10, employed as such or as its alkali metal salts or as its bis-chlorocarbonic acid ester or as oligomeric carbonates, containing chlorocarbonic acid ester end groups, prepared from the dihydroxy compound of formula 10, not exceeding 199 equivalents per equivalent of the compound 11, and at least 1.05 chlorine equivalents bonded via -CO- having to be employed per phenolic OH equi-valent.

7. A process for the preparation of polycarbonates containing bis-triazinyl structural units, comprising reacting according to the methods for preparation of polycarbonates, aromatic bis-hydroxy compounds containing bis-triazinyl segments, of the formula 12 (12) in which formula R5, R6 and X have the same meaning as in Claim 1, by themselves or mixed with up to 199 equivalents of a dihydroxy compound of the formula 10, HO-X-OH (10) in which X has the same meaning as in Claim 1, with phosgene or a bis-chlorocarbonic acid ester of a dihydroxy compound 10 or an oligomeric carbonate, containing chloro-carbonic acid ester end groups, obtainable from the compound of formula 10, the sum of the equivalents of the dihydroxy compound of formula 10, employed as such or as its alkali metal salts or as its bis-chlorocarbonic acid ester or as oligomeric carbonates, containing chlorocarbonic acid ester end groups, prepared from the dihydroxy compound of formula 10, not exceeding 199 equivalents per equivalent of the compound 12, and at least 1.05 chlorine equivalents bonded via -CO- having to be employed per phenolic OH equivalent.

8. The process according to Claim 7 wherein the dihalogeno-bis-triazinyl compounds of formula 9 (9) obtained by reaction of aminodichloro-triazine compounds of formula 15 (15) in which R5 and R6 have the same meaning as in Claim 1 with 4,4'-diaminostilbene-2,2'-disulphonic acid or its salts, are reacted, without separate isolation and in the same reaction vessel, with aromatic dihydroxy compound of the formula 10, in the presence of a proton acceptor to a compound of the formula 12, and thereafter, depending on the choice of the molar ratio used in the reaction of compounds of formula 9 with formula 10, the compound of formula 12 is reacted either by itself or mixed with a further compound of formula 10, with phosgene or bis-chlorocarbonic acid esters of the aromatic dihydroxy compounds 10 or oligomeric carbonates containing chlorocarbonic acid ester end groups, obtainable from a compound of formula 10.

9. The process according to Claim 7, characterized in that the bis-hydroxy compounds of formula 12 containing bis-triazinyl segments are obtained by reaction of dichloro-bis-triazinyl compounds of the formula 9 (9) wherein R5 and R6 independently of one another represent H
or alkyl, hydroxyalkyl, carboxyalkyl or alkoxy-carbonyl-alkyl groups containing 1-5 carbon atoms, C5-C7- cycloalkyl groups or C6-C14-aryl groups or conjointly with the N atom form a 5-membered or 6-membered ring system, with aromatic dihydroxy compounds of the formula 10 in the presence of a proton acceptor without separate isolation and in the same reaction vessel as the reaction of compounds of the formula 12 either by themselves or mixed with additional compounds of the formula 10 depending on the choice of the molar ratio of compounds of formula 9 to formula 10 used in the preparation of compound 12, with phosgene or bis-chlorocarbonic acid esters of the aromatic dihydroxy compounds of formula 10 or oligomeric carbonates, containing chlorocarbonic acid ester end groups, obtainable from a compound of formula 10, the sum of the equivalents of the dihydroxy compound of formula 10, employed as such or as its alkali metal salt or as its bis-chlorocarbonic acid ester or as oligomeric carbonate, containing chlorocarbonic acid ester end groups, prepared from the dihydroxy compound of formula 10, not exceeding 199 equivalents per equivalent of the compound of formula 12, and at least 1.05 chlorine equivalents bonded via -CO- having to be employed per phenolic OH equivalents.

10. The process of Claim 9 wherein 0.01 to 5 mol percent based on the ultimate polycarbonate of the tris-hydroxy compound of formula 14, (14) in which X has the same meaning as in Claim 1 are reacted with bis-hydroxy compounds of formula 12.

11. The process of Claim 5 wherein X is derived from aromatic di-hydroxy compounds of the formula 20, (20) in which R7, R8 and Y have the same meaning as in Claim 1.

12. The process of Claim 5 wherein X is derived from 2,2-bis-(4-hydroxyphenyl)propane.

13. The process of Claim 9 wherein X is derived from aromatic dihydroxy compounds of the formula 20, (20) in which R7, R8 and Y have the same meaning as in Claim 1.

14. The process of Claim 9 wherein X is derived from 2,2-bis-(4-hydroxyphenyl)propane.

15. The process of Claim 5 wherein the compounds of formula 11 are prepared by reacting a dihalogeno s-triazine of formula 8 (8) in which Z, R, Q, a and X have the same meaning as in Claim 1 and Hal denotes F, Cl, Br or I

with two equivalents of an aromatic dihydroxy compound of formula 10 HO-X-OH (10) in which X has the same meaning as in Claim 1, in the presence of a proton acceptor.

16. The process of Claim 7 wherein the compounds of formula 12 are obtained by reaction of dichloro-bis-tri-azinyl compounds of the formula 9 (9) in which R5 and R6 have the same meaning as in Claim 1 with two equivalents of an aromatic dihydroxy compound of the formula 10, HO-X-OH (10) in which X has the same meaning as in Claim 1.
in the presence of a proton acceptor.

17. The process of Claim 5 wherein 0.01 to 5 mol percent based on the ultimate polycarbonate of the tris-hydroxy compound of the formula 14 (14) in which X has the same meaning as in Claim 1 are reacted with the bis-hydroxy compounds of formula 11.

18. The polycarbonates of Claim 2 wherein X is derived from aromatic dihydroxy compounds of the formula 20, (20) in which R7, R8 and Y have the same meaning as in Claim 1.

19. The polycarbonates of Claim 2 wherein X is derived from 2,2-bis-(4-hydroxyphenyl)propane.

20. Process according to Claim 5 characterized in that the dihalogeno-s-triazines of the formula 8, (8) in which z, R, Q and a have the same meaning as in Claim 1 and Hal denotes F, Cl, Br or I
obtained by reaction of trihalogeno-s-triazines of the formula 19, (19) in which Hal denotes F, Cl, Br and I with compounds of the formula 13 (13) in which Z, R, Q and a have the same meaning as in Claim 1, in the molar ratio of 1:1, are reacted, without separate isolation and in the same reaction vessel, with aromatic di-hydroxy compounds of the formula 10 in the presence of a proton acceptor to form a compound of the formula 11, and thereafter, depending on the choice of the molar ratio used in the reaction of the compounds of formula 8 with formula 10, the com-pound of formula 11 is reacted either by itself or mixed with further com-pound of formula 10, with phosgene or bis-chlorocarbonic acid esters of the aromatic dihydroxy compounds of formula 10 or oligomeric carbonates, containing chlorocarbonic acid ester end groups, obtainable from a compound of formula 10.

21. A process for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mix-tures or solutions of these hydrocarbons with, or in, water or aqueous solutions containing inorganic salts which comprises contacting the aqueous mixture with a polycarbonate containing s-triazine rings, having the structural units of formula 3, (3) in which Q denotes -COOH or -SO3H and Z, R, a, X and n have the same meaning as in Claim 1.

22. A process for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mix-tures or solutions of these hydrocarbons with, or in, water or aqueous solutions containing inorganic salts which comprises contacting the solution with a polycarbonate containing s-triazine rings, with structural units of formula 3, (3) in which Z represents -NH-, Q represents -COOH, a represents 1 and X represents and R and n have the same meaning as in Claim 1.