DE2346935C2 - Polycarbonates containing s-triazine rings with functional groups, their production and use - Google Patents

Description

SO ₃ H

HO ₃ S

wherein in the formulas, R ^5, R ⁶ and X have the abovementioned meanings, with 2 equivalents of m aromatic dihydroxy compound of the formula 10 in the presence of a Protonenacceptors or with 2 equivalents of the alkali metal salts of the aromatic dihydroxy compound of formula 10 by itself has received known methods , alone or in a mixture with up to 199 equivalents of a dihydroxy compound of the formula 10 with phosgene and / or a bischlorocarbonic acid ester of a dihydroxy compound 10 and / or an oligomeric carbonate obtained from 10 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 oligomeric carbonates containing chlorocarbonic acid ester end groups prepared from the dihydroxy compound 10, not exceeding 199 equivalents per equivalent of the compound 12, and where per phenolic OH equivalent at least 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.

5. Use of polycarbonates containing s-triazine rings and having structural units of the formula 3, in which Q is -COOH or -SO ₃ H and Z, R, a, X and η are as defined above, for the absorptive removal of aliphatic, cycloaliphatic, aromatic and halogenate hydrocarbons from mixtures or solutions of these hydrocarbons with or in aqueous solutions containing water or inorganic salts.

In DE-OS 14 95 141 a process for the preparation of triazine-containing polymers is described. However, the OH groups on triazine residues behave like acids and it is difficult to do so to polycondense bifunctional acids with phosgene to high molecular weight polycarbonates.

It is also to be expected that such polycarbonates are brittle. The presence of ties with quasi anhydride character

N N

Il Il

C - O - C - O - C

/ Il \

= N O N =

Furthermore, resistance to hydrolysis cannot be expected. It can be seen from this that polycarbonates according to DE-OS 14 95 141 structurally and also with regard to their property profile with the inventive Polycarbonates are not comparable.

US-PS 35 41049 describes the branching of polycarbonates by incorporating a maximum of 1 Mol% cyanuric acid chloride, with all three acid chloride substituents should react. In contrast, it was not obvious to synthesize polycarbonates

bores that still contain reactive groups, the molar percentage of reactive groups, based on diphenol use, being between 33 1/2 mol% (for η = 1 in formula 3) and 0.49 mol% (for η = 200 in formula 3). (For the two SO ₃ H groups in formula 4, the percentage is twice as high.)

It was therefore not obvious in view of the teaching of US-PS 41 049, when installing triazine-

most reactive groups to avoid. That the polycarbonates according to the invention are additionally branched can, is not primarily the subject of the present invention.

The invention relates to linear polycarbonates containing s-triazine rings, which are characterized in that they consist of structural units of the following general formula 3 and / or 4

SO ₃ H

in which

one o-, m- or p-phenylene radical, one simple or polysubstituted o-, m- or p-phenylene radical, where lower alkyl groups with 1-4 carbon atoms or chlorine are used as substituents or bromine come into question or one of the formula 5

(6b)

wherein

R ⁹ to R "denote alkyl radicals with 1-4 carbon atoms 5,

(5) R ¹¹ also stands for hydrogen or chlorine or bromine

can stand

marked residue means in which

R ⁷ and R ^{8 have} the same or different meanings, stand for Wässcrsiofiaioine, Aikyiresie with 1-4 carbon atoms or chlorine or bromine atoms,

Y is a single bond, an alkylene or alkylidene radical having 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical having 5 to 12

Carbon atoms, —Ο—, -4S—, —CO—,

—SO—, —SO ₂ - or a radical of the formula 6a or 6b means

(6 a)

Z stands for -O -, - S -, - ^{NH- or -NR 1} -,
R alkylene radicals with 1-20 carbon atoms, cycloalkylene radicals with 5-12 carbon atoms, mono- or polynuclear arylene or above carbon

Bound HcieröärylcnrcStc riiit UP TO 14 Carbon atoms, mono- or polynuclear or poly-substituted mono- or polynuclear arylene or above

Carbon-bonded heteroarylene radicals with up to 14 ring carbon atoms, with alkyl, alkoxy or alkyl mercapto groups as substituents with 1-4 carbon atoms, chlorine or bromine, - NO2 or —CN are possible, alkylarylene-

residues with a total of up to 30 carbon atoms,

or aralkylene residues with a total of up to 30

Carbon atoms means R ¹ alkyl radicals with 1 to 20 carbon atoms, Cycloalkyl radicals with 5 to 12 carbon atoms,

mononuclear or polynuclear aryl or carbon bonded heteroaryl radicals with up to 14 ring carbon atoms, where alkvl-,

Alkox or alkyl mercapto groups with 1 to 4 Carbon atoms, chlorine or bromine, - NO2 or -CN are possible, with alkylaryl radicals a total of up to 30 carbon atoms, aralkyl radicals with a total of up to 30 carbon atoms or Denotes hydroxyalkyl radicals 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 aliphatic -OH group,

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

R ³ and R ⁴ independently represent hydrogen, straight-chain or branched alkyl groups with 1 to 4 carbon atoms or an unsubstituted, mono- or polysubstituted phenyl radical, or together with the N atom form a five-membered or one-membered ring system and

a is an integer from 1 to 4,

R ⁵ and R ⁶ independently of one another represent H or alkyl, hydroxyalkyl, carboxyalkyl, alkoxycarbonylalkyl groups, C5 - C7 cycloalkyl, C6 - Cm aryl groups containing 1 to 5 carbon atoms or together with the N- Atom form a 5 or 6-membered ring system,

π is a number between 1 and 200,

are constructed.

Examples of radicals R ⁵ and R ⁶ in formula 4 which, together with the N atom, form a five-membered or o-membered ring system are pyrrolidine, piperidine or morpholine.

Preferred substituents of the formulas 3 and 4 mentioned are: Z = -NH-, -NR ¹ -, R = alkylene with 1 to 10 carbon atoms or phenylene, Q = -COOH, - SO3H or aliphatically bonded hydroxyl groups, Ri = alkyl with 1 to ö carbon atoms or hydroxyalkyl with 1 to ö carbon atoms, R5 and Rb = independently of one another hydrogen, hydroxyalkyl with 2 to 4 C, alkyl with 1 to 4 C, phenyl, η is a number between 1 and 200, preferably between 3 and 100 .

Preferred Y radicals are the isopropylidene and cyclohexylidene radicals.

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

The end groups of the new polycarbonates have no decisive influence on the properties of the products. For the sake of completeness, the following are given as end groups A for the left side of structural formulas 3 and 4 and as end groups B for the right side :

In 3 and 4, A stands for H or - CO - OR ¹² , where

R ¹² denotes a phenylene radical or a mono- or polysubstituted phenylene radical, in 3 also denotes a radical of the general formula 7,

Have meaning;

B stands for —OR ¹² , where R ^{12 has} the aforementioned meaning.

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

The new polycarbonates according to the invention are distinguished in particular by the fact that they are characterized by the Incorporation of the s-triazine structural units via the substi-

K) tuenten Q or via the sulfo group and / or via the radicals R ⁵ and R ⁶ in formula 4 are suitable for polymer-analogous reactions.

Polycarbonates with structural units of the formula 3, in which Q stands for -COOH or -SO ₃ H, show

ι ") surprisingly strong lipophilic properties, if they are in the usual polycarbonate solvents are insoluble. The lipophilic character of these modified polycarbonates can be varied to a large extent by the type and proportion of triazine segments on the one hand

2u or by changing the molecular weight on the other hand. In general, the Achievement of the desired effect Triazine proportions of the formula 3 of less than 15 mol%, preferably 10 Mol% or less than 10 mol%, based on the structural unit of the formula 3. The solubility of these Polycarbonates can include can be controlled by installing branching devices or networkers. With such products can be used e.g. B. from mixtures or solutions of aliphatic or aromatic hydrocarbons such as methylene chloride, chlorobenzene, benzene or xylene with or in water are the hydrocarbons Remove almost quantitatively by absorption, which is of great importance for the purification of industrial wastewater is.

The invention therefore also relates to the use of polycarbonates containing s-triazine rings of Formula 3, in the

Q is -COOH or -SO ₃ 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 inorganic Aqueous solutions containing salts.

A particular subject of the invention is the use of polycarbonates containing s-triazine rings of Formula 3, in the

Z for NH,
Q for -COOH,
a stands for 1.

CH ₃

means and

R has the meaning given above,
for the absorptive separation of aliphatic cycloaliphatic

—Z— (" """"^ —Z— (R> - (Q) ₀ (7) table, aromatic and halogenated hydrocarbons

substances from mixtures or solutions of these hydrocarbons with or in aqueous solutions containing water or inorganic salts.

Containing s-triazine rings according to the invention, high where Z, R, Q and a the above molecular polycarbonates can be made

N N

Ii

by first dihalo-s-triazines of the formula 8,

Shark

Hal

N N

(RHQ) ,,

wherein

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

SO ₁ H

R ⁵ and R ^{6 have} the meaning given above,

with 2 to 201 equivalents of an aromatic dihydroxy compound of the formula 10,

HO-X-OH

(10)

where X has the meaning given above,
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 either

HO--Ο-γ ^Ν Υ-Ο -X -OH

N N (11)

Z- (RHQ) ₀

a) in an organic solvent which is indifferent to reaction components 8, 9 and 10

or

b) in an aqueous alkaline medium or

c) in a one- or two-phase mixture of one which is indifferent to the reactants organic solvent and one

aqueous-alkaline phase

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

SO ₃ H

HO - XO

-NH

-f V

N N

depending on the choice of the implementation of 8 or 9 with 10 molar ratio used either on its own or in a mixture with a further 10 with phosgene and / or bishopric carbonic acid esters of the aromatic Dihydroxy compounds containing 10 and / or 10 available chlorocarbonic acid ester end groups oligomeric carbonates, where the sum of the equiva-

lente of the dihydroxy compound 10, used as such and / or as their alkali salts and / or as their bischlorocarbonic acid ester and / or as the chlorocarbonic acid ester produced from the dihydroxy compound 10 Endgroup-containing, oligomeric carbonates, 201 equivalents per equivalent of compounds 8 or 9 not exceed, and being pro phenolic

OH equivalent at least 1.05 via —CO— bonded Chlorine equivalents 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 can be used 9 as well as mixtures of 8 and 9 as well as various aromatic dihydroxy compounds 10 be reacted side by side if a corresponding carbonate copolymer is desired. aside from that it is easily possible to combine the reaction products of 8 and 9 with an aromatic Dihydroxy compound with other aromatic dihydroxy compounds and the above-mentioned polycarbonate-forming ones To implement connections.

The inventive method is characterized in that the preparation of the s-triazine-containing Bishydroxy compounds 11 and / or 12 and those based on 11 and / or 12 and optionally others Dihydroxy compounds subsequent production of the polycarbonates in the same reaction medium and in the same reaction vessel can be carried out without isolating the intermediate stages 11 or 12. A separate one 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 also consists in the fact that instead of the purified dihalo-s-triazines 8 and the solutions or suspensions that from the reaction of trihalo-s-triazines, preferably cyanuric chloride, with nucleophiles Compounds of formula 13,

(13)

in the

Z, R, Q and a have the abovementioned meaning, in a manner known per se according to those cited below References obtained, unpurified dihalo-s-triazines immediately for further condensation with aromatic dihydroxy compounds 10 are used can be.

Another variant of the production of the polycarbonates according to the invention is that the Implementation of the dihalo-s-triazines 8 and / or 9 with the bishydroxy compounds 10 in the presence of 0.01 to 5 mole percent of a trihalo-s-triazine, based on the structural unit of the formulas 3 and / or 4, in which Hai is the meaning given for 8 has, but is preferably Cl, so that trifunctional hydroxy compounds are also used as intermediates of formula 14

HO - X - O - | ^{/ N} V
NN

O-X-OH

O-X-OH

are contained in the reaction mixture, which in the subsequent reaction with polycarbonate-forming Compounds such as phosgene and / or bischlorocarbonic acid esters of bishydroxy compounds have a branch effect of the polycarbonates via s-triazine rings. The for the preparation of the homo- or copolycarbonates used dihalo-s-triazines 8 and 9, if not already known, are produced according to processes known in the chemical literature.

The dichloro-s-triazines of the formula 8, in which Hal means Cl j, are obtained, for. B. by implementing Cyanuric chloride with aliphatic or aromatic amines, alcohols, and containing functional groups Q, Phenols, mercaptans or thiophenols [see e.g. B. J. R. Thurston et al, J. Am. Chem. Soc. 73, 2981 ff. (1951); ίο H. Koopman et al, Rec. trav. chim. Pays-Bas 78, 967 (1959); H. Koopman and J. Daams, Rec. Trav. chim. Pays-Bas, 77,235 (1958); H. Nestler and H. Fürst, J. Prakt. Chem. (4), 22, 173 (1963); S. Horrobin,]. Chem. Soc. (London), 1963, 4130; DE-AS 1176 319; DE-OS 16 70 832].

The dichloro-bis-triazinylaminostilbene derivatives of Formula 9 is obtained e.g. B. by reacting aminodichlorotriazine compounds with 4,4'-diaminostilbene-2,2'-disulfonic acid or their salts according to DE-OS 16 70 832.

As dihalo-s-triazines of the formula 8, which are used for the production of s-triazine-containing polycarbonates of the Formula 3 are suitable, for example, the compounds that are available when one Cyanuric chloride with

Hydroxyacetic acid,

N-butyl hydroxyacetate,

2-hydroxypropionic acid (lactic acid),
jo 2-hydroxypropionic acid ethyl ester,

2-hydroxysuccinic acid (malic acid),

2-hydroxypropane tricarboxylic acid (l, 2,3)
(Citric acid),

Mercaptoacetic acid,
j3 2-hydroxyethanesulfonic acid (isethionic acid),

2-aminoethanol,

N-methylethanolamine,

Diethanolamine,

3-amino-1-propanoI,
l-amino-2-propanol,

Diisopropanolamine,

Dihydroxy tertiary butylamine,

Trihydroxy-tert-butylamia

Aminoacetic acid (GlycineX
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-methyi-aminoethane-suitonic acid,
3-hydroxybenzoic acid,

3-hydroxybenzoic acid ethyl ester,
(14) 4-hydroxybenzoic acid,

4-mercaptobenzoic acid,

4-hydroxybenzoic acid methyl ester,
4-hydroxybenzoic acid propyester,

S-chlorine - ^ - hydroxybenzoic acid,

4-hydroxyphthalic acid,

Phenol-3-sulfonic acid,

Phenol-4-sulfonic acid,
2,6-dichlorophenol-4-sulfonic acid,

1-naphthol-4-sulfonic acid,

1-

15th

2-naphthol-5,7-disulfonic acid, N- (2-hydroxyälhyl) cyclohexylamine, aminoacetic acid ethyl ester, ethyl δ-aminohexanoate, 2-hydroxypropionic acid methyl ester.

6-hydroxyhexanoic acid ethyl ester, Methyl mercaptoacetate.

Mercaptosuccinic acid diethyl ester, 2-hydroxyethylaniline, Aniline methanesulfonic acid, anilinoacetic acid,

Hydroxyethyl-m-toluidine, m-toluidino-methanesulfonic acid.

2-aminobenzoic acid.

2-aminobenzamide, 3-aminobenzoic acid,

4-chloro-3-aminobenzamide, ö-chloro-S-aminobenzoic acid.

S-Nilro-S-aminobenzoic acid.

o-nitro-S-aminobenzoic acid.

4-aminobenzoic acid, ethyl 4-aminobenzoate.

4-aminobenzamide, 2-nitro-4-aminobenzoic acid, 4-amino-3-methyl-benzamide.

3-anlino-4-methylbenzic acid.

5-aminoisophthalic acid, 4-aminonaphthalene-1.8-dicarboIic acid, S-amino ^ -methoxybenzoic acid.

Aniline-2-sulfonic acid, aniline-3-sulfonic acid, Aniline-3-sulfonic acid amide.

3-aminobenzenesulfonic anilide, 3-aminobenzenesulfonic acid c-N-methylanilide, δ-chloroaniline-S-sulfonic acid.

Aniline-4-sulfonic acid, 4-aminobenzenesulfonic acid camide.

Diphenylamine-4-sulphonic acid c.

4-benzylaminobenzenesulfonic acid.

2,5-dichloro-4-aminobenzolsulfonsäul ■ e.

4-aminotoluene-2-sulfonic acid, 4-aminotoluene-2-sulfonic acid anilide.

5-aminotoluene-2-sulfonic acid c.

4-aminophenyl methanesulfonic acid.

4-aminonaphthalene-i-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, ö-aminonaphthalene ^ -sulfonic acid, S-aminonaphthalene-I.S.S-trisulfonic acid.

2-mercaptobenzolhiazolesulfonic acid c

in a molar ratio of 1: 1 in a manner known per se implements.

There are, of course, numerous other dihalostriazines as well as starting materials for the production of s-triazine rings containing polycarbonates of the formula usable.

As aminodichlorotriazine compounds of formula 15,

(15) those with 4,4'-diaminostilbene-2,2'-disulfonic acid or theirs Salts to dichlorobistriazinyl compounds of the formula 9, soft for the preparation of s-triazine-containing Polycarbonates of the formula 4 are suitable, can be implemented, for example the compounds into consideration, which are available if you 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 / ϊ-aminopropionic acid ethyl ester, Aniline or cyclohexylamine. Pyrrolidine, piperidine or morpholine in a molar ratio 1: 1 known in and of itself; he implements it in a manner.

Suitable aromatic dihydroxy compounds of the formula 10 are, for. E.g .: hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl. Bis (hydroxyphenyl) alkanes, cycloalkanes. sulfides, ethers, ketones, sulfoxides or sulfones. Furthermore a. «'- bis (hydroxypheny!) - diisopropylbenzenes as well as the corresponding ring-alkylated or ring-halogenated compounds.

Some preferred aromatic dihydroxy compounds are e.g. B .:

2,2-bis- (4-hydroxypher.y!) - propane (bisphenol A).
2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane.
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
Bis (4-hydroxyphenyl) methane,
1, l-bis (4-hydroxyphenyl) cyclohexane and
Trinuclear bisphenols, such as
a.a'-bis (4-hydroxyphenyl) -p-diisopropylbenzene.

These and others for the production of the invention, Bisphenols suitable for high molecular weight polycarbonates are disclosed in US Pat. No. 2,970,131,29,91273. 29 99 835, 29 99 846, 3014891, 3028365, 3062781. 3148 172, 32 71367, 32 71368. 32 80 078 and in the DE-OS 1.5 70 703 described.

Phenol and mono- or polysubstituted phenols are also suitable as molecular weight limiters good but also monohalo-s-triazines of the general formula 16.

<Q} - <R) -Z— ^ ^N VZ- (RMQ) ,,

ι Il
NN

Shark

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

The production of the polycarbonates according to the invention containing s-triazine rings and having structural units the formula 3 can, for. B. happen 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 itself known way, e.g. B. in an 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 the Elimination of hydrogen chloride from cyanuric chloride and 13 on the one hand and, if necessary, the acidic groups present in 13 on the other hand stoichiometric amount of a proton acceptor, such as. B. NaOH or KOH implemented. That

130 263/139

The resulting dihalo-s-triazine 8 is now either isolated from the reaction mixture and purified, or as a solution or suspension in the solvent used in the reaction without further work-up used directly in the subsequent reaction with an aromatic dihydroxy compound

In a separate vessel, the aromatic dihydroxy compound and an alkali hydroxide, are preferred Sodium or potassium hydroxide, dissolved in a molar ratio of 1: 2 in so much water that about a 10% strength aqueous alkali salt solution of bisphenol is present. Water-insoluble or sparingly soluble alkali salts of Dihydroxy compounds are used in the reaction as an aqueous suspension. You can do it without Disadvantage more dilute or concentrated alkali salt solutions or suspensions are used.

A solution or is then added to this aqueous alkali salt solution or suspension of bisphenol Suspension of an isolated and purified by recrystallization, distillation or washing out, or a non-isolated dihalo-s-triazine, dissolved or suspended in water in the presence or absence of one organic solvent, such as. B. acetone, methyl ethyl ketone or dioxane, or one with water not Miscible organic solvents which are indifferent to the dihalotriazine in a molar ratio 201: 1 to 2: 1 in portions or in one portion.

As inert organic solvents you can, for. B. use chlorinated hydrocarbons such as CH _{2 Cl 2} , CHCl ₅ , CCI4, ethylene chloride and trichlorethylene, benzene, toluene, xylenes, chlorobenzene, chlorotoluenes, dichlorobenzene and higher chlorinated aromatics.

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

The well-stirred one- or two-phase mixture is then kept at a temperature between 0 and 300 ^° C., preferably between 30 and 150 ^° C., for a period of 0.2 to 20 hours. If necessary, the organic solvents remaining from the reaction of cyanuric chloride with 13, such as, for. B. acetone, distillaiiv removed. As a rule, the condensation of the dichloro-s-triazine with the dihydroxy compound has ended after 5 hours at the latest. The entire reaction up to this point is carried out under an inert gas atmosphere, e.g. B. performed 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 dihalogen-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 decisive importance for the formation of the polycarbonates according to the invention.

If you w dl prevent side reactions between the aromatic dihydroxy compound and two molecules of the dihalo-s-triazine to form of intermediates of formula 17

Ha

N N

N N

in which X, Z, R, Q, a and Hal have the above meaning to have,

occur, it is advantageous to choose a large excess of bisphenol and carry out both the addition of the

ϊ Dihalogen-s-triazines as well as the condensation increased temperature. The formation of the by-products of formula 17 affects the The overall course of the reaction is not disruptive, since these compounds are also smoothly integrated into the polycarbonate framework.

Hi builds.

The one- or two-phase mixture in which the alkali metal salts used in excess the aromatic dihydroxy compound and the alkali metal salts of the s-triazine-containing bisphenol of the formula

ι-, 11 are dissolved or suspended, one adds optionally another solvent suitable for aromatic polycarbonates, such as methylene chloride, chloroform, Carbon tetrachloride and 1,2-dichloroethane, chlorinated Aromatics such as dichlorobenzene, chlorotoluene or chlorine

JIi benzene, and continues after adding the above Molecular weight limiter in an alkaline environment at a pH value between 10 and 14, depending on the type of used bisphenol component 10 and the s-triazine-containing bisphenol 11 used, in itself

j-, as is known, with compounds which form carbonate groups such as phosgene, bischlorocarbonic acid esters or chlorocarbonic acid ester end groups obtainable from dihydroxy compounds containing oligomeric carbonates.

«Ι The two-phase interface process produced polycarbonates containing s-triazine rings, which either precipitate from the reaction mixture or are dissolved in the organic phase are isolated in the usual way by z. B. the alkaline

j-, reacting reaction mixture is acidified and the precipitated The polycarbonate is filtered off and washed neutral with water or the polycarbonate present in solution precipitates from the organic phase or the neutral washed solution of the polycarbonate is evaporated.

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

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

ι-, the polycarbonates with structural units of the formula 3. The s-triazine rings according to the invention containing new polycarbonates of the formula 3 and 4 are due to the incorporation of the s-triazine structural units via the substituents Q or via the SOjH group or via the

- ,, ι radicals R ⁵ and R ^h outstandingly suitable for polymer-analogous reactions. For example, s-triazine-containing polycarbonates containing aliphatic OH groups with aminoplasts or their defined precursors, such as. B. melamine, benzoguanamine or

Ii urea resins, phenolic resins or di- and polyisocyanates, be crosslinked to form hard coatings.

Ester- and carboxyl-group-containing polycarbonates of the formulas 3 and 4 can, for example, with Bisoxazolines or di- and polyepoxide compounds

_hl ) how glycidic esters are crosslinked to form hard coatings. The paints can optionally contain pigments and the customary paint auxiliaries.

-j) Polycarbonates with structural units of the formula 3, in

the Q is a carboxyl or SOjH group which

,, -, are insoluble in numerous organic solvents at a certain molecular weight, are suitable excellent for the absorptive separation or removal of aliphatic, cycloaliphatic ^ aromat'-

see and halogen hydrocarbons from aqueous Solutions or mixtures with water.

In the following examples, "hours" means hours, "min." = Minutes and "ex." = Example.

example 1

Copolycarbonate from 2,2-bis- (4-hydroxyphenyl) -

propane (bisphenol A) and 2-diethanolamino

4,6-dichloro-s-iriazine (95: 5 parts by mole)

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! 1.27 g (5 mmol) of 2-diethanolamino-4,6-dichloro-s-triazine, suspended in 60 ml of chlorobenzene, and 0.2 g of NaBHj are added to water while simultaneously passing in a gentle stream of nitrogen. The well-stirred two-phase mixture is heated for 4 hrs. At about 90 ⁰ C. The mixture is then allowed to cool to about 20 ° C., an intermediate product precipitating out. After adding 0.43 g (2.86 mmol) of p-tert.-butylphenol and 120 ml of CH2Cl2, the mixture is diluted with 10 percent. Hydrochloric acid to pH 11 - set 12 and introduced with vigorous stirring within about 30 minutes at 24-27 ⁰ C) 3.4 g (0.135 mol) COCl 2.. During the phosgenation, in which the intermediate product dissolves, the pH is kept between 11 and 12 by adding dropwise 1N NaOH solution. After adding 5.5 ml of 10% aqueous triethylamine solution, stirring is continued for 10 minutes at pH 11-12, the two-phase mixture becoming highly viscous. After acidification with dilute phosphoric acid, the organic phase is separated off, washed with dist. Washed neutral with water and added dropwise to methanol, the powdery white polycarbonate precipitating out.

After drying for 17 hours at 100 ° C and 15 torr 21.4 g (86%) of s-triazine-containing polycarbonate result.

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

N content: calculated 1.12%, found 1.04%
% aliphatic.OH: calc. 0.68%, found 0.62%

The polycarbonate obtained according to Example 1 is dissolved in chlorobenzene and in the boiling point with toluene diisocyanate networked. Hard products result, which precipitate from the reaction solution and turn into organic products Solvents are insoluble.

Example 2

Copolycarbonate made from bisphenol A and 2-diethanol

amino-4,6-dichloro-s-triazine (78:22 molar parts)

with chain breaker

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 NaBH4 under ^ atmosphere in 180 ml of water and heated to about () 0 -70 ⁰ C. . A suspension of 6.27 g (24.8 mmol) 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 dil. Hydrochloric acid, then 120 ml of CH2Cl2 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) COCI2 implemented at pH 11-12. After the addition of 6.3 ml!% Aq. Triethylamine solution is subsequently stirred for 1 hour at 100M and the polycarbonate is removed by evaporation of the neutral-washed organ. Phase yield: 24.2 g (93%) triazine-containing polycarbonate. J) re; (0.5 g of product in 100 ml of CH ₂ Cl ₂ , 25 ° C): 1.078

N content: calculated 5.35%, found 4.97%
OH number: calc. 107 found. 91

The polycarbonate obtained in Ex. 2 is z. B. with hexamethylolmelamine hexamethyl ether in m-cresol in the presence of p-toluenesulfonic acid at 200 ° C to form hard coatings.
κι

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. 7.2 g (0.18 mol) NaOH and 2.53 g (0.01 mol) 2-diethanolamino-4,6-dichloro-s-triazine in a solvent mixture of 180 ml of water and 60 ml

-> (i chlorobenzene with the addition of 0.09 g NaBH ₄ reacted for 4 hours at reflux temperature. After cooling, 0.27 g (1.8 mmol) p-tert.-butylphenol and 140 ml CH ₂ Cl _{2 are} added, adjusted to pH 14 with 2N NaOH solution and with vigorous stirring at pH 14 11.9 g

2ϊ (0.12 mol) of COCl2 initiated. After the phosgenation is the water Phase free from bisphenolate salt. Then 4.9 ml 1 per cent. aq. Triethylamine solution added un <i condensed. After a further stirring time of about 3 min. The approach is initially highly viscous and

κι finally clumps together so much that further stirring is no longer useful. The gel-like Swollen polycarbonate mass is suctioned off, treated several times with dilute phosphoric acid and then with Washed with water.

to r> receives After 24 hours of drying in a vacuum oven at 100 ⁰ C for about 25 g of a hard tough material.

The product is insoluble in most organic solvents.

⁴ "N content: calculated 2.29%, found 2.20%.

Example 4

Copolycarbonate from bisphenol A and N- (4,6-dichloros-triazin-2-yl) -p-aminobenzoic acid (90 : 10 mole parts)

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 mole) of N- (4,6-dichloro-s-triazin-2-yl) -p-aminobenzoic acid was added and with stirring and ^ - heated for 5 hrs at about 90-95 ⁰ C atmosphere.!. The dichloro-s-triazine dissolves during the heating process. After cooling to 20 ^° C., a clear solution is present. After adding 200 ml of CH ₂ Cl ₂ , a pH of 12 is set and, as described under Example 1, _{reacted with 11.9 g (0.12 mol) of COCI 2} at pH 12, a milky white, slightly viscous one Forms emulsion. 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 is 2 χ shaken with distilled water and ^1, added dropwise inn the entire two-phase mixture, as the, jciden phases separate only very slowly in methanol to give the polycarbonate powdery white precipitates.

Yield: 24.7 g (100%) triazine-containing polycarbonal.

N content: calculated 2.26%, found 2.22%. % COOH: calc. 1.82%, found 1.7%.

The product is in the usual polycarbonate solvents, such as. B. CH ₂ Cb, tetrahydrofuran, dioxane. and pyridine, insoluble.

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, a suspension of 68.6 g (0.5 mol) of p-aminobenzoic acid and 50.6 g (0, 5 mol) triethylamine registered in 1350 ml of acetone. The reaction ^{temperature is allowed to rise to 20 °} C. in the course of 90 minutes and stirring is continued for a further 90 minutes. The precipitated reaction product is suctioned off. with dist. Water washed free of chloride, boiled 2 χ with acetone and dried at 50 ° C / 15 Torr. Yield: 114g (80% of theory), melting point> 300 ° C.

analysis
Ber.
found

C 42.1
C41.7

H 2.11
H 2.17

N 19.65 N 19.2

Cl 24.95%; Cl 24.7%.

Example 5

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -p-aminobenzoic acid

(89.5: 10.5 molar parts)

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-diehlor-s-triazine) -yl-2) -p-aminobenzoic acid in 320 ml H ₂ O ^r ) hours at 90-95 ⁰ C converted.

After cooling, a solution of 31.8 g (0.09 mol) of bisphenol A-bischlorocarbonic acid ester in 620 ml of CH ₂ Ci _{2 is} allowed to run into the yellow solution of the sodium salts of the dihydroxy compounds within 2 min. With vigorous stirring, then 15.2 ml l% 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 sponge-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 ₂ Cl ₂ is absorbed by the triazine-containing polycarbonate. The polycarbonate is made by slurrying with dist. Water washed largely neutral and dried for 20 hours at 50 ^c / i 5 torr.

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

N content: calculated 2.38%, found 2.25%.

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

Example 6

Removal of hydrocarbons from aq.

Solutions by absorption on a copolycarbonate of bisphenol A and N- (4.6-dichloro-s-triazine-

yl-2) -p-aminobenzoic acid

(89.5: 10.5 molar parts)

A 30 cm long column with an internal diameter of 1.5 cm is prepared with 10 g of the in Example 5 Copolycarbonate filled (filling height of the very voluminous material about 20 cm). Then one leaves one after the other Solutions of hydrocarbons in water or salt solutions (50 ml each) run through the column and determines the hydrocarbon content in the aq. before and after the passage by gas chromatography. Solution (see table 1):

Table 1 (for example 6):

Solution millelgc mix Hydrocarbon content after absorption
I mg / 11 Trcnnlei- before absorption
| mg / l] 30th stung
|%] CII _: CI ₂ / dist. H ₂ O 1 1,000 1 99.7 Chlorobenzene / dist. H ₂ O 120 <5 · ') 99.2 Benzene / dist. H ₂ O UO <Γ) > 94.5 Xylene / dist. H ₂ O 30th 50
<1 ") > 96.7 CH _: Cl ₂ / chlorobenzene /
alkaline saline solution 4,500CH ₂ Ci ₂
50 chlorobenzene 10
< V) 98.9
> 98 ClhClj / chlorobenzene /
acidic saline solution 2,600 CII ₂ Cl ₂
10 chlorobenzene 99.6
> 90

") Limit of detection

Example 7

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -p-aminobenzoic acid (95 : 5 mole parts)

with chain terminator

According to Example 5, 9.1 g (0.04 mol) of bisphenol A are first added to an alkaline solution with 1.5 g (5.26 mmol!) Of N- (4,6-dichloro-s-tn; i / :: n-> i 2) p-aminobenzoic acid reacted, then 474.3 mg (3.16 mmol) of p-tert.-butylphenyl were added, a solution of 21.2 g (0.06 mol) of bisphenol-A-bischloric acid ester in 180 ml CH2CI? allowed to run in, 10.1 ml of 1% strength aqueous triethalamine solution were added and the mixture was stirred at pH 13. After about 10 minutes, the triazine-containing polycarbonate precipitates like a gel and is worked up as described under Example 5.

Yield: 26.0 g (99%) of a white granular product

N content: calculated 1.12%, found 1.02%.
COOH content: calculated 0.897%, found 0.899%.

Example 8

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -p-aniinobenzoic 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) of p-tert-butylphenol with 21.2 g (0.06 Mol) Bisphenoi-Ä-bischiorkohiensäureester with the addition of 10.1 ml of 1% aq. Triethylamine solution at pH 12-13 condensed. After 10 minutes, the copolycarbonate precipitates like a gel and is as above described worked up.

Yield: 25 g (97%)

N content: calc. 0.439%, found 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 through, the polycarbonate is dissolved in methylene chloride. After the addition of triethylamine, 1 hour at pH 12-13 stirred, the organic phase evaporated after washing neutral and 65 hours at 100 ° C / l 5 Torr dried.

Yield: 22.2 g (86%) of triazine-containing copolycarbonate.
Vre (0.5 g product in 100 mL CH ₂ Cl ₂ , 25 ° C): 1.267.

N content: calculated 0.349%, found 0.34%.

COOH content: calc. 0.434%, found 0.41%.

Example 9

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -p-aminobenzoic acid

(80: 20 Moiteile)

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-dichloros-triazin-yl-2 ) -p-aminobenzoic acid reacted in 250 ml of water and then condensed with 12.7 g (0.036 mol) of bisphenol A-bischlorocarbonic acid ester in 230 ml of CH _{2 Cl 2} with the addition of 10.1 ml of 1% aqueous triethylamine solution. Just 5 minutes after the addition of triethylamine, the polycarbonate precipitated like a gel. After a further stirring time of! Hours is worked up as described above. The neutral washed gel is dried for 30 hours at 80 ° C / l 5 Torr

Yield: 22 g (92%) white, fine-grain powder. N content: calculated 4.65%, found 4.48%. COOH content: calc. 3.74%, found 236%. Example 10 Copolycarbonate branched with cyanuric chloride BisphenolA and N- (4,6-dichloro-s-triazin-yl-2) -

p-aminobenzoic acid (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) -pammobenzoic acid are added to 190 ml Dissolved 1 N NaOH solution and added a solution of 40.5 mg (0.22 mmol) of cyanuric chloride in 50 ml of dioxane. With stirring and N ₂ atmosphere is heated for 5 hrs. At 90-95 ⁰ C, then cooled to 20 ° C and the resulting clear solution s after the addition of 150 ml CH ₂ CI ₂ at pH 12 with 11.9 g (0 , 12 mol) COCI ₂ implemented. After dilution with 150 ml of CH _{2 Cl 2} , 8.3 ml of 1% aq. Triethylamine solution was added and the mixture was 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.
Yield: 24 g (97%) white fluffy product.

N content: calc. 2.06%, found 2.08%.

Example ii

Copolycarbonate from bisphenol A and N- (4,6-dichloros-triazin-yl-2) -sulfanilic acid (90 : 10 mole parts)

2 (i According to Example 4, 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 the N- Reacted (4,6-dichloro-s-triazin-yl-2) sulfanilic acid, then reacted at pH 12 with 11.9 g (0.12 mol) COCl ₂ and after triethyl

Addition of 2i amine for 1 hour at pH 13. At the Acidification of the reaction product, the copolycarbonate precipitates as a white powder, which is filtered off with suction, through Slurry washed neutral with water, then washed with methanol and 65 hours at 80 ° C / l 5

3d torr being dried.

Yield: 23.5 g (93%) copolycarbonate.

N content: calculated 2.21%, found 2.16%.

Example 12

Copolycarbonate from bisphenol A and N- (4,6-dichloros-triazin-yl-2) -p-aminobenzoic acid ethyl ester

(85.7: 14.3 parts by mole)

4 (i 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 N ₂ O for 3 hours at 80-90 ⁼ C with a A suspension of 4.69 g (15 mmol) of N ^ .ö-dichloro-s-triazin-yl ^ Jp-aminobenzoic acid ethyl ester reacted in 60 ml of chlorobenzene. On cooling to room temperature, a gritty intermediate product precipitates. After addition of 120 ml of CH ₂ Cl ₂ is adjusted to pH 13 and reacted with 11.9 g (0.12 mol) of COCl ₂ at pH 13. After addition of 5 ml of 1% strength aqueous triethylamine solution, the mixture is stirred until the copolycarbonate becomes after about 15 minutes Gel precipitates The precipitated product is worked up as described in Example 5.

Yield: 26 g (100%) of triazine-containing copolycarbonate.

N content: calc. 3.22%, found 3.15%.

The IR spectrum (KBr pellet) clearly shows that a polycarbonate containing ester groups is present. The product is soluble in dimethylformamide.

The N- {4,6-dichloro-s-triazin-yl-2) -p-aminobenzoic acid ethyl ester used was prepared according to a procedure described by Thurston et al (J- Am. Chem. Soc. 73, 2981 [1951]) for the preparation of 2-aminodichloro-s-triazines by reacting 0.5 mol of cyanuric chloride with 04 mol of p-aminobenzoic acid ester with the addition of 0.25 mol of Na ₂ CO ₃ in acetone (200 ml I / dioxane (50 ml) / water (300 ml) at 0-5 ⁰ C produced the precipitating from the reaction mixture

Dichlorotriazine is purified by boiling with acetone.

Yield: 76%, m.p. 294-295 ° C.

Ber.
found

C 46.05 H 3.22
C 46.15 H 3.13

N 17.9
N 17.8

Cl 22.70;
Cl 22.6.

Example 13

Copolycarbonate from bisphenol A and N- (4,6-dichloros-triazin-yl-2) -glycine

According to a procedure for the preparation of 2-amino-4,6-dichloro-s-triazines (J. Thurston et al, J. Am. Chem. Soc. 76 _: 2981 [1951]) 1.84 g (0.01 Mol) cyanuric chloride and 0.79 g (10.5 mmol) of glycine with the addition of 0.84 g (21 mmol) of NaOH in acetone / H ₂ O (7:11 parts by volume) ^{reacted at approx. 0 0} C, lets stir for 1 hour and warm to room temperature. A solution of 9.6 g (42 mmol) of bisphenol A and 3.36 g (84 mmol) of NaOH in 42 ml of H ₂ O is added to this orange-red colored solution of dichlorotriazine in acetone / water, and the mixture is gradually heated to about 90 -95 ° C, the acetone being removed from the reaction solution by distillation. After removing the acetone is another 3h. stirred at 95-10O ⁰ C. The mixture is allowed to cool to room temperature, the pale yellow solution is diluted with 100 ml of water, a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonate is run in with vigorous stirring, and 10.1 ml of 1% strength aqueous triethylamine solution is added and can be stirred at pH 13. After about 15 minutes, the polycarbonate precipitates like a gel. The reaction is terminated and the polycarbonate is worked up as described in Example 5.

Yield: 22.3 g (93%) fluffy white copolycarbonate.

N content: calculated 2.32%, found 2.28%.
COOH content: calc. 1.87%, found 1.7%.

The product can absorb approximately 38 times its own weight in CH2Cl2.

Example 14

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -6-aminohexanoic acid (90 : 10 mole parts)

According to Example 13, 1.84 g (0.01 mol) of cyanuric chloride with 1.38 g (10.5 mmol) of 6-aminohexanoic acid are converted into N- (4,6-dichloro-s-triazin-yl-2 ) -6-aminohexanoic acid reacted, the resulting white suspension of 9.6 g (42 mmol) of bisphenol A condensed, originating from the first stage reaction, acetone is distilled off from the mixture, and the resulting colorless solution of the dihydroxy compounds at 20-25 ⁰ C polycondensed for 1 hour with a solution of 1636 g (48 mmol) of bisphenol A-bischlorocarbonic acid ester in methylene chloride at pH 13 after the addition of 10.1 ml of 1% triethylamine solution. The organic phase is separated off with dilute phosphoric acid and washed neutral Added dropwise methanol with the triazine-containing polycarbonate precipitated flaky white

Yield: 21.4 g (87%).

Example 15

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-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 of water for 5 hours at about 95-100 ° C., leaves a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbon acid in 170 ml of CH in the resulting milky, cloudy aqueous solution 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 14.

Yield: 24.7 g (100%) fluffy white copolycarbonate,

i) _re / (0.5 g of product in 100 ml of CH _{2 Cl 2} , 25 ° C): 1.372.

N content:
COOH content:

calc. 2.26%, found 2.08;
calc. 1.82%, found 1.7%.

N content: calc. 2 ^ 7%, found 2.12%. COOH content: calc. 1.62%, found 1.59%.

The N- (4,6-dichloro-s-triazin-yl-2) -2-aminobenzoic 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 ⁰ C in the presence of 20.3 g (0.2 mol) of triethylamine as an HCl acceptor. The reaction product obtained is washed free of chloride with dilute hydrochloric acid and then with water, boiled with acetone and dried.

Yield: 30.2 g (53%); Mp.> 330 ° C (decomposition).

Analysis:

Ber. C 42.1%, H 2.11%, Cl 24.95%;
found C 42.4%, H 2.19%, Cl 24.9%.

Example 16

Copolycarbonate of bisphenol A and N- (4,6-dichloros-triazin-yl-2) -2-aminoethanesulfonic acid

(90:10 molar parts)

According to Example 13, 1.84 g (10 mmol) of cyanuric chloride are reacted with 1.31 g (10.5 mmol) of 2-aminoethane-1-sulfonic acid (taurine) to form the corresponding dichloro-s-triazine, and the resulting white suspension is added 60-95 ⁰ C reacted with 9.6 g (42 mmol) of bisphenol A with simultaneous distilling off of the acetone in the reaction mixture, resulting in a colorless solution and finally with a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester in Methylene chloride is polycondensed at pH 13 after the addition of 10.1 ml of 1% strength aqueous triethylamine solution.

After 30 minutes stirring time the triazine-containing copolycarbonate falls gelatinous and as described in Ex. 5 worked up

Yield: 23.8 g (97%).

N content: calc. 2 ^ 7%, found 2.18%.

The product can absorb about 36 times its own weight in CH2Cl2.

Example 17

Copolycarbonate as bisphenol A and N- (4,6-dichloros-triazin-yl-2) -5-aminoisophthalic acid

(90: 10Moltene)

According to Example 13, first 1.84 g (10 mmol) of cyanuric chloride with 1.9 g (10.5 mmol) of 5-aminoisophthalic

20th

acid reacted in the presence of 1.24 g (31 mmol) NaOH at 0-5 ° C in acetone / water, the resulting light yellow suspension with 9.6 g (42 mmol) bisphenol A 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) of bisphenol-A-bischlorocarbonic acid ester in methylene chloride after the addition of 10.1 ml of 1% aqueous triethylamine solution at pH 13 polycondensed . 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: calculated 2.22%, found 2.20%.
COOH content: calculated 3.58%, found 3.33%.

The product can absorb about 19 times its own weight in CH2Cl2.

Example 18

Copolycarbonate from bisphenol A and (4,6-dichloro

s-triazin-yl-2) -hydroxyacetic acid

(90:10 molar parts)

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 4 h in 200 ml of water. reacted at 70-80 ⁰ C. After cooling to room temperature, a solution of 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester in 200 ml of CH2Cl2 is run in with intensive stirring, 10 ml of 1% aqueous triethylamine solution is added and the mixture is condensed at pH 13. After stirring for 10 minutes, the triazine-containing polycarbonate precipitates like a gel and is worked up as described in Example 5

Yield: 22.9 g (95%) of triazine-containing copolycarbonate.

N content: calc. 1.74%, found 1.70%. ^4Ü

COOH content: calc. 1.87%, found 1.75%.

Example 19

Copolycarbonate from bisphenol A and S- (4,6-dichloro

s-triazin-yI-2) -4-mercaptobenzoic acid

(90:10 molar parts)

Example 20

Copolycarbonate from 1,1 -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-hydroxyphenylj-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 the dihydroxy compounds 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 copolycarbo-

1 ^r ) nat.

According to a procedure for the preparation of 2-arylthio-4,6-dichloro-s-triazines (J. Drabek and M. Skrobal, Chem. Zwesti 17, 482 [1963]) 1.84 g (0.01 mol) Cyanuric chloride and 1.54 g (0.01 mol) of 4-mercaptobenzoic acid with the addition of 0.8 g (0.02 mol) of NaOH in acetone / water at 0-5 ° C. The reaction mixture is then reacted with a solution of 9, 6 g (42 mmol) of bisphenol A and 336 g (34 mmol) of NaOH in 50 ml of water are added and the mixture is heated to 70-80 ° C. for 5 hours, the acetone being distilled off from the mixture. After cooling to room temperature, 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester are reacted as described in Example 13 and the polycarbonate formed is worked up as described in Example 5

Yield: 24.6 g (99%) of triazine-containing copolycarbonate

N content: calc. 2.08%, found 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-s-triazin-yl-2) -p-aminobenzoic acid reacted, then a solution of 19.2 g (48 mmol) of bischlorocarbonic acid ester of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane is left run in 170 ml of methylene chloride, stir after the addition of 1.36 g (13.5 mmol) of triethylamine for 3 hours and work as described below Example 5 described on.

Yield: 31 g (94%) of triazine-containing copolycarbonate.

N content: calc. 1.70%, found 1.65%.

Example 22

Copolycarbonate of bisphenol A and N- (4,5-dichloros-triazin-yl-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 NaOH and 2.84 g (10 mmol) of N- (4,6-dichloro-s-triazin-yl-2) -p-aminobenzamide in

170 ml H ₂ O 5 hrs. At 90-95 ⁰ C is then reacted at 20-25 ° a solution of 16.96 g (84 mmol) of bisphenol A bischlorocarbonic acid in 270 ml CH2Cl2 was added with vigorous stirring and, after adding 10.1 ml 1% aqueous triethylamine solution condensed for 1 hour at pH 13. The gelatinous polycarbonate which has precipitated out 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 polycarbonate containing amide groups is present

The N- (4,6-dichloro-s-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 ) p-aminobenzamide in acetone / water (1: 1 parts by volume) with the addition of 8.4 g (0.1 mol) of NaHCO ₃ at 0-3 ⁰ C

Yield: 51.6 g (91%); m.p. > 300 ° C

50

55

60

N content: calc. 1.69%, found 1.55%.

α-content: calc. 25.1%, Found. 24.9%.

Example 23

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

s-triazin-yl-2) -p-aminobenzenesulfonic acid amide

(90: 10 molar parts)

Analogously to Example 22, 9.6 g (42 mmol) of bisphenol A are initially mixed with 3.2 g (10 mmol) of N- (4,6-dichloro-s-triazinyl-2) -p-aminobenzenesulfonic acid amide reacted and then with 16.96 g (48 mmol) of bisphenol-A-bischlorocarbonic acid ester condensed. About 20 minutes after the addition of triethylamine, the trizaine-containing copolycarbonal falls gelatinous.

Yield: 25g (100%).

N content: calc. 2.79%, found 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 -Aminobenzolsulfonsäureamid in acetone / water (l: 1 parts by volume) prepared with the addition of 8.4 g (0.1 mol) of NaHCO ₃ at 0-3 ⁰ C.

Yield: 53.5 g (84%) of a white powdery product, m.p .: > 300 ° C.

Cl content: cal. 22.3%, found 22.1%.

Example 24

Copolycarbonate from bisphenol A and 4,4'-bis-

[/ t-chloro-ö-diethanolamino-s-triazin ^ -yl] -amino-2,2'-stilbene disulfonic acid (99 : 1 mole)

According to Example 4, 22.6 g (99 mmol) of bisphenol A, 7.92 g (198 mmol) of NaOH and 847 mg (1 mmol) of di-Na salts of the 4,4'-bis [4-chloro 6-diethanolamino-striazin-2-yl] -amino-2,2'-stilbene disulfonic acid in 175 ml H ₂ O heated to 90-95 ° C for 5 hours. Then is cooled to 20 ⁰ C and after addition of 450 mg (3 mmol) of p-tert-butylphenol and 175 ml CH ₂ Cl ₂ at pH 12 reacted with vigorous stirring with 14.9 g (0.15 mol) ₂ COCl . Then 10.1 ml of 1% aq. Triethylamine solution was added and the mixture was stirred for 1 hour at pH 12. After acidification with dil. H3PO4, the aq. Phase separated and the organic phase was added dropwise to methanol, the polycarbonate precipitating. Yield: 24.3 g (94%).

7? _rc / (0.5 g product in 100 ml CH ₂ Cl ₂ , 25 ° C): 1.245.

N content: calc. 0.54%, found 0.53%.

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

Example 25

Copolycarbonate from bisphenol A and 4,4'-bis-

[4-chloro-6-di-ethanolamino-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

κι and 8.47 g (0.01 mol) 4,4'-bis [4-chloro-6-diethanolamino-s-triazin-2-yl] amino-2,2'-stilbene disulfonic acid with the addition of 7, 2 g (0.18 mol) of NaOH _{reacted in 210 ml of H 2} O, then 210 ml of CH ₂ Cl ₂ and 0.75 g (5 mmol) of p-tert-butylphenol were added at room temperature and

Ii phosgenated with 11.9 g (0.12 mol) COCl _2. After adding 10.1 ml of 1% aq. Triethylamine solution is stirred at pH 12.5 for 1 hour. After acidification, the polycarbonate, in which all of the methylene chloride is absorbed, precipitates out gritty. After 24 hours

2 (i drying at 80 ° C / 15 Torr leaves 30 g (99%) Copolycarbonate.

N content: calculated 4.61%, found 4.4%.

2> B e i s ρ i e I 26

Copolycarbonate from bisphenol A and 4,4'-bis-
^ -chloro-e-anilino-s-triazine ^ -ylj-amino-2,2'-stilbene disulfonic acid (99: 1 molar parts)

j «Analogously to Example 24, 22.6 g (99 mmol) of bisphenol A and 0.824 g (1 mmol) of 4,4'-bis- [4-chloro-6-anilino-s-triazin-2-yl] -amino-2,2'-stilbene disulfonic acid di-Na salt reacted in the presence of 7.92 g (198 mmol) of NaOH in 175 ml of water, at room temperature after addition

j, of 175 ml of CH ₂ Cl ₂ and 0.45 g (3 mmol) of p-tert-butylphenol with 14.9 g (0.15 mol) of COCl ₂ at pH 13 and, after addition of triethylamine (10.1 ml of 1% aqueous solution), stirred for 1 hour. After acidification, with dist. Water washed and the organ. Phase in

4 (i methanol was added dropwise, whereby the polycarbonate was flaky turns out white.

Yield: 23.8 g (92%).

i? _re / (0.5 g of product in 100 ml of CH ₂ Cl ₂ , 25 ^U C): 1.287.

N content: calc. 0.54%, found 0.49%.

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

Claims (4)

Patent claims: Linear polycarbonates containing l.s-triazine rings, characterized in that they are composed of Structural units of the following general formula 3 and / or 4 -0 —X - O-X-O-C (RHQ) ₀ SO ₃ H in which X is an o-, m- or p-phenylene radical, a mono- or polysubstituted o-, m- or p-phenylene radical, with lower alkyl groups having 1-4 carbon atoms as substituents or chlorine or bromine come into question or one of the formula 5 (5) 50 55 denotes in which R ⁷ and R * have the same or different meanings, represent hydrogen atoms, alkyl radicals with 1-4 carbon atoms or chlorine or bromine atoms,
Y is a single bond, an alkylene or alkylidene radical having 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical having 5 to 12 carbon atoms, -O-, -S-, -CO-, -SO-, -SO ₂ - or a radical of Formula 6a or 6b means R "
T R ⁹ R ⁹ > - C- —C— < _R 10 _R , o R ⁹
\ \
/ C.
'\ R ⁹ \
R.
> - c - < R " _R 20 wherein R ⁹ to R "denote alkyl radicals with 1-4 carbon atoms, R "can also stand for hydrogen or chlorine or bromine, Z is -O-, -S-, -NH- or -NR ¹ -,
R alkylene radicals with 1-20 carbon atoms, cycloalkylene radicals with 5-12 carbon atoms men, mononuclear or polynuclear arylene or about Carbon-bonded heteroarylene radicals with up to 14 carbon atoms, simple or polysubstituted mono- or polynuclear arylene or carbon-bonded Heteroarylene radicals with up to 14 ring carbon atoms, with alkyl, Alkoxy or alkyl mercapto groups with 1 to 4 carbon atoms, chlorine or bromine, - NO2 or —CN are possible, alkylarylene radicals with a total of up to 30 carbon atoms, or aralkylene radicals with a total of 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 zi; 14 ring carbon atoms, whereby alkyl, alkoxy or alkyl mercapto groups with 1 to 4 carbon atoms, chlorine or bromine, - NO2 or --CN are possible, alkylaryl groups with a total of up to 30 carbon atoms, aralkyl groups with a total of up to 30 carbon atoms or Denotes hydroxyalkyl radicals with 1 to 10 carbon atoms, Q is a -CCOH-, -COOR * -, -CONR ³ R ⁴ -, - SO ₃ H-, -SO ₂ NR ³ R ⁴ - or aliphatic --OH group, R ^{2 represents} alkyl groups with 1-4 carbon atoms, R ³ and R ⁴ independently represent hydrogen, 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 to 4, R ⁵ and R ⁶ independently of one another represent H or alkyl, hydroxyalkyl, carboxyalkyl, alkoxycarbonylalkyl groups, C5-Cy-cycloalkyl, Ce-Ci4-aryl groups containing 1-5 carbon atoms, or together with the N- Atoms form a 5- or 6-membered ring system, η is a number between 1 and 200, are constructed. 2. Branched polycarbonates which, in addition to the structural features of claim 1, are also trifunctional Contain units, characterized in that they have structural units of the formula 18, -cox-oγ 'yo-xocN _n ^ n ο Y II o-x-o-c- 55 60 (18) in which X has the meaning given above, are branched and the structural _{units b5} mentioned are contained in the overall molecule in amounts of 0.01 to 5 mol%, based on the structural units 3 or 4. 3. Process for the preparation of polycarbonates of the formula 3 containing s-triazine rings according to Claim 1, characterized in that aromatic bishydroxy compounds containing s-triazine rings are used of formula 11 HO - X - O - f * ^N yO - X - OH
NN (RHQ) ₀ (11) obtained by reacting dihalo-s-triazines of the formula 8 Shark shark YY N N (8) (RHQ) ₀ where in the formulas Z, R, Q, a and X have the abovementioned meaning and are Hal, F, Cl, Br and], with 2 equivalents of an aromatic dihydroxy compound of the formula 10, HO-X-OH (10) in which X has the meaning given above, in the presence of a proton acceptor or with 2 Equivalents of the alkali metal salts of the aromatic dihydroxy compounds of the formula 10 according to per se known method has received, alone or in a mixture 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 from 10 obtained chlorocarbonic acid ester end groups containing oligomeric carbonate, the sum of the equivalents of the dihydroxy compound 10 being used as such and / or as their alkali metal salts and / or as their bischlorocarbonic acid esters and / or as chlorocarbonic acid ester end groups produced from the dihydroxy compound 10 containing oligomeric carbonates, not exceeding 199 equivalents per equivalent of compound 11, and where per phenolic OH equivalent at least 1.05 chlorine equivalents bound via —CO— are used, if appropriate in the presence of molecular weight limiters, according to known Polycarbonate manufacturing process implements. 4. Process for the preparation of polycarbonates of the formula 4 containing bistriazinyl structural units according to claim 1, characterized in that aromatic bishydroxy compounds of the formula 12 containing bistriazinyl segments, SO ₃ H HO - X - O O - X - OH (12) obtained by reacting dichlorobistriazinyl compounds of the formula 9,