JPS5823825A - Manufacture of branched polycarbonate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polycarbonates improved by the introduction of residues of compounds containing a-triazine rings, their preparation and their use as adsorbents.

The present invention comprises a combined divalent residue of at least one bisphenol and an 8-triazine adduct of at least lyu, wherein the divalent % a-) lyasine compound residue is exists between two bisphenol residues, and two 8-triazinyl broken carbon atoms of each 8-triazonyl compound residue are bonded to one oxygen atom of the adjacent bisphenol residue, and #8-triazonyl Each 8 in the adduct residue
- The triazinyl group has an organic group containing a functional group as described below as a substituent, or is bonded to another 8-triazonyl ring by the organic group, and the acid L The polycar attached to the carbon atom of the 8-triazinyl ring provides the nate.

The term "8-triazinylated adduct" herein means a compound containing at least one 8-triazine ring.

As used herein, "functional group" refers to an acid group (e.g. -COOH or FisO,H), a modified acid group (e.g. an ester or aodo group, especially an esterified or azated carboxylic or sulfonic acid group). group) or alcoholic hydroxyl group.

In two important forms of the invention 11, the 8-triazine compounds each have one 8-triazine ring, and 93 8-,
Includes 17 ajiruo. #Organic groups may be bonded through oxygen or sulfur, but preferably two Os
- To bond to each of the 01 element atoms of the triazine ring.

Suitable polycarbonates of the general formula c and e are as follows:
B is a bisphenol residue, Tllm-triazinyl compound is a copper group, and n is a number from 1 to 200, more preferably from 3 to 100.

According to another preferred embodiment of the invention, the polycarbonate contains 0.0
It is branched by introducing 1 to 5 molar trivalent residues of the 1it-) Reagel compound.

Preferably, the #3 valent residue is of the formula %.Furthermore, the present invention comprises at least one divalent bisphenol residue and at least one divalent a, triazinyl compound residue. A process for the preparation of polycarbonates as described above, which comprises reacting at least one monomer of KjIt acid, either by itself or together with bisphenols, with a polycarbonate-forming derivative of KjIt acid.

Finally, the present invention provides an axillary hydrocarbon and water or salt aqueous solution, which is characterized by adsorbing hydrocarbons and hydrocarbons (Harakiri group, aliphatic group, and aromatic groups) to the polycarbonate of the present invention. To remove the hydrocarbons from a mixture of
4 for giving.

The polycarbonate according to the present invention has the general formula (1)% formula%
) [In the above formula, 1 is 10-1-s-1-NH-1 or -NE
'or -N-<R''+JrQ'')*, and R and R* each have an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 120 carbon atoms, a mononuclear or polynuclear arylene group, Denotes carbon-mediated hetero-arylene radicals with carbon numbers 141, mono- or polysubstituted mononuclear or polynuclear arylene groups, carbon-mediated hetero-arylene radicals with up to 14 carbon atoms, with the possible substituents e.g. Alkyl, alkoxy or alkyl mercapto group of number 1 to 4, chlorine atom such as chlorine or ﾆ element, -No or -〇N, alkylarylene group with total carbon number of 201 or aralkylene group with total carbon number of up to 30 R' is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a mononuclear or polynuclear unsubstituted or substituted aryl group, or a group bonded through a carbon having a prime number of 141 to 9 Denotes a heteroaryl group, provided that possible substituents include, for example, an alkyl, alkoxy or alkylmercapto group having 1 to 4 carbon atoms, a fibrillated halogen atom of chlorine or bromine, -No! Or-
〇N, an alkylaryl group with a metal prime number of 301, an aralkyl group with a total of 30 carbon atoms, or a human-xyalkyl group with 1 to 10 carbon atoms, and Q and Q are! 1000H%-COOR- independently of V%
, C0NRaB', -8o,H.

-8 indicates an OH group bonded to NE or aliphatic,
However, R1 represents an alkyl group having 1 to 4 carbon atoms, and RI and No. 8 are each llC'1! Hydrogen at the top, carbon number 1-4
represents a straight-chain or branched alkyl group or an unsubstituted, mono- or polysubstituted phenyl group, or together with the N atom forms an S-membered or six-membered ring system, and α and a are independent of each other represents an integer of 1 to 4] may be contained as a bridge member between the aromatic bishydroxy compounds and bonded via the oxygen atom of the latter. General ceremony! Instead of or in addition to the group,
The polycarbonate of the present invention has the general formula (2) [In the above formula, Ha and R are independently H or an alkyl, hydroxyalkyl, carboxyalkyl, or alkoxycarbonylalkyl group having 1 to 5 carbon atoms, C1 to
C, cycloalkyl group, or substituted or unsubstituted C6-C
84 represents an aryl group, or together with an N atom, S
or a six-membered ring system, for example forming a pyrrolidone, piperidine or morpholine ring system, may be contained as a bridging member between the aromatic bishitoxy compounds and bonded via the oxygen atom of the latter.

Suitable substituents of formulas (1) and (2) above are as follows: Z=-NH-1 or -NR'- or -N-(R++
Q ) *, α R and R = alkylene or phenylene having 1 to 10 carbon atoms independently of each other, Q and 0 - independently of each other 11C-COOH, -8o, H
or aliphatically bonded nine hydroxyl group, R' = alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms, R1 and R@ = independently of each other hydrogen, hydroxyalkyl having 2 to 4 carbon atoms; , alkyl having 1 to 4 carbon atoms, phenyl and hisulfoxy 7-ethyl.

8-) The novel polycarbonate containing a riazine ring has the general formula (3) and/or (4) or a polysubstituted 0-1m- or p-phenylene group, provided that possible substituents are, for example, lower alkyl having 1 to 4 carbon atoms or chlorine or bromine), rogene atoms, or preferably those of the formula (5 ), where 8 and RS represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, preferably a chlorine or bromine atom, and may be the same or different, and Y is a collective bond, alkylene or alkylidene having 1 to 7 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 12 carbon atoms, -0-1-S-1-CO-1-SO-1-S
O, -1 or formula (6α) or (6b) (6G) (6b) represents an O group, provided that R- to 11 represents an alkyl group having 1 to 4 noble atoms, and R''
may represent hydrogen or a halogen atom such as chlorine or bromine, Z, R, Q, α, R1 and R have the same meanings as shown in formulas (1) and (2), and n is It may consist essentially of 1 to 20 (1, preferably 3 to 100) identical or non-identical structural units.

Preferred radicals Y are isopropylidene and cyclohexylidene.

Weight average molecular weight determined by light scattering method (7Llh
+) is generally 10,000 or more, preferably 2,000 or more
It is 0-200000. Of course, a low molecular weight polycarbonate 4hIK containing an 8-) riazine ring can be prepared.

The end groups of the new polycarbonates do not have a decisive effect on the properties of the product. K for completeness, structural formula (3)
And as the terminal group A for the left @I/C and the terminal group B for the right side of (4), the following 4 can be mentioned: 0) and (4) VC & represents AIdH or COORn, However, R11 represents a 7-El group or a polysubstituted or polysubstituted phenyl group; And B represents a -OR story, where R1 has the same meaning as above.

So far, polycarbonates having S-triazine rings and containing functional groups have not been known.

Novel polycarbonates prepared by Motoya @ can be prepared by the formula (1) via the substituent Q in the case of formula (1) or via the sulfo group in the case of formula (2) and/or via the groups Rゝ and R. ) or (
As a result of introducing the 8 + 177dine structural unit in 2), it is particularly noteworthy that it is suitable for reactions similar to polymers.
1c special feature.

Polycarbonates having structural units of the formula G) in which Q represents -COOH or -8O,H surprisingly exhibit organic solvent absorption properties when K, polycarbonate (K), is insoluble in the usual solvents. The properties of these refreshed polycarbonates can be varied widely, on the one hand, by the nature and proportion of the triazine segments, and on the other hand, by varying the molecular weight. In general, a ratio of K of 15 mole or less, preferably 10 to 1 mole, of the triazine of formula (1) relative to the structural unit of formula (1) to achieve the desired effect is sufficient. The insolubility of these polycarbonates can be adjusted, inter alia, by introducing branching or crosslinking agents.

For example, using such products, aliphatic or aromatic hydrogenation, such as methylene arid, coolbene,
It is possible to remove hydrocarbons almost quantitatively from mixtures or aqueous solutions of benzene or xylene with water in seconds.
This is extremely useful for purifying industrial wastewater! Ami.

It is therefore a further object of the invention to adsorb and remove skeletal hydrocarbons from aqueous mixtures or solutions of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons or from aqueous solutions containing inorganic salts. 9 [, containing li-triazid/ll, Q represents -COOH or -8O,H, and Z%R1α
,

A special object of the present invention is to adsorb and remove aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons from mixtures or solutions with water or aqueous mineral solutions containing inorganic salts. Since it contains an 8-triazine ring, Z represents NH, Q represents -COOH, α represents 1, and CH.

The object of the present invention is to provide a method of using a polycarbonate of formula (3), in which R is as defined above.

The high molecular weight polycarbonates of the present invention containing El + ) IJ Azishimaro are prepared according to conventional methods for the preparation of trisubstituted B-triazines: a) in an organic solvent inert to the following reactants 8.9 and 10; ) in an aqueous alkaline medium, or C
) in one or two phases of the reactants and an organic solvent inert to the aqueous alkaline phase of the formula (8) [wherein Ha I represents F, CζB de and I, preferably Ct; Z, R, Q and 6 have the same meanings as above.
) [In the above formula, R1 and R. have the same meanings as above] and the compound eyelid of the formula (10)%
2 to 201 equivalents of an aromatic dihydroxy compound of the formula % (10) [in the above formula, 0 to 300°C, preferably 30 to 150°C using 2 to 201 equivalents of alkali metal salt.
The reaction is allowed to take place for 2 to 20 hours and then according to known methods for the preparation of polycarbonates, preferably interfacial polycondensation methods, depending on the choice of the molar ratio used for the reaction of 8 or 9 with 10, the 8- Triazine ring-containing dihydropal compounds of formulas 11 and 12 or alkali metal salts thereof, either by themselves or mixed with KIO, are prepared from phosgene and/or aromatic dihydroxy compounds 10 and/or biscour carbonate esters and sulfuric acid. reacted with a carbonate oligomer containing a chlorocarbonate end group, but as such and/or as its alkali metal salt and/or as its biscour carbonate and/or prepared from a dihydroxy compound 10 and containing a chlorocarbonate group. The sum of the equivalents of 10 dihydroxy compounds used as carbonate oligomers does not exceed 201 equivalents per equivalent of compound 8 or 9, and at least 1.05 chlorine equivalents bonded via 100- to 7 enolic It can be produced by using K for 1 equivalent of OH.

Furthermore, different dihalogeno-8-) lyazine 8 and/or
or bistriazinyl dichlor compound 9 and/or because it is different
Alternatively, it is also possible to use mixtures of 8 and 9 and/or different aromatic dihydroxy compounds 10 to prepare the corresponding desired compounds. It is also possible to react the group di-metallic compound with the droxylated metal and the above-mentioned polybonate-forming compound.

The method involves the production of bishydroxy compounds 11 and/or 12 containing an 8-) riazine structure, and the subsequent production of 11
and/or the preparation of polycarbonates based on 12 and optionally other dihydroxy compounds as intermediates 11 or 11! It has the feature that it can be carried out in the same reaction medium and in the same reactor without separation. #-) Although it is possible to produce bisphenol containing riazine in a separate process, it is not necessary.

A further special advantage of the process for preparing polycarbonates of formula 3 containing 8-triazine structures is that purified dihalogen-
8-) Replacement of riazine 8 K with trihalogeno-B-triazine, preferably cyanuric chloride, according to a method known per se and formula % formula % (13) [In the above formula, Z, R, Q and a have the same meanings as above. The crude di-I-lognow-8-triazine solution or suspension obtained from the reaction with the nucleophilic compound can be used directly for the further condensation with the aromatic dihydroxy compound 10.

An alternative method for producing polycarbonates according to the invention involves the reaction of dihalogeno-8-triazines 8 and/or 9 with bishydroxy compounds 10 of formulas 3 and/or 4 (where Ha
g has the meaning indicated for 8, but preferably indicates CI) based on the structural unit of 0.01-! The reaction mixture contains as an intermediate a 3-caphatic hydroxy compound of formula 14, followed by a polycarbonate-forming compound such as phosgene and/or a bischloro of a bishydrohydroxy compound. 1ii-) The polycarbonate is split into limbs via the liazine ring by reaction with a carbonate ester.

The dino-cogeno 8-triazines 8 and 9 used for the preparation of the homopolycarbonates or polycarbonates according to the invention are not known, but are prepared according to methods known from the chemical literature.

The dichloro-8-triazine of 28, where Hag indicates Ct, is prepared, for example, by reacting cyanuric chloride with an aliphatic or aromatic amino acid having a blind group Q, an alcohol, a phenol, a mercaptan or a thiophenol. [For example, J,
R, Thurmton et al., J, Am.
Chem, Sac, jJ) = 2981 (1951);
H., Koopmax et al., Ram, t.
rav, chin, Pays-Bag 7 @,
967 (1959); H, Koopman and J, Dahms (Z) 1ams), RaC, trav, chin
, Pανa-EeLllu, 235 (1958),
H, Nestlar and H, full x) (F
:Lrat), J, prakt, Cham, [4:)
22.173 (1963); S, Horobiy (Hor
rob(fL), J.

aha, see, [Lv%doIS] 196
3.4130; see DE 1,176,319; DE 1,670,832].

Dichloro-bis-triazinyl 7f/stilbene derivatives of the formula 9 are described, for example, in German Offenlegungsschrift No. 1.670.832.
According to the No. 4,4.4'
-Diaminostilbene-2; Produced by reacting with 2'-disulfonic acid or a salt thereof.

An example of a dihalogeno-8-) riazine of formula 8 suitable for the production of a polycarbonate of formula 3 having an 8-triazine structure is obtained by combining cyanuric chloride and the following compound into 1
: Hydroxyacetic acid, hydroxyacetic acid n-butyl ester, 2-hydroxypropionic acid (lactic acid), 2-hydroxypropionic acid ethyl ester, 2-hydroxysuccinic acid (apple acid), 2-hydroxypropane-1,
2,3-)licarboxylic acid (citric acid), mercaptoacetic acid, 2-hydroxyethanesulfonic acid (isethionic acid),
2-aminoethano-,h,N-methylethanolamine, jetanolamine, 3-amino-1-glopanol, 1-amino-2-glopanol, diimpropaturamine, dihydroxy-tart-butylamine, tri-tart-butylamine, Aminoacetic acid (glycine), methylanoacetic acid, 3-ainoprobionic acid, 4-aminobutyric acid, 6-annohexanoic acid, 11-a2
Nocundeonic acid, aminoco-I-phosphoric acid, 2-aminoglutaric acid, methionine, 2-a? Noethanesulfo/acid (taurine), N-methylaminoethanesulfonic acid, 3-hydroxybenzoic acid, 3-k)'roxybenzoic acid ethyl ester, 4-hydroxybenzoic acid, 4-mercaptobenzoic acid, 4-hydroxybenzoic acid Methyl ester, 4-hydroxybenzoic acid pumavir ester, 3-chloro-4-
Hydroxybenzoic acid, 4-hydroxyphthalic acid, phenol-3-sulfonic acid, phenol-4-sulfonic acid, 2*6-sylphenol-4-sulfonic acid, 1-7to-4-sulfonic acid, 1 -7toll-3,6-disulfonic acid, 2-naphthol-6-sulfonic acid, 2-7toll-5,7-disulfonic acid, N-
(2-Hydroxyethyl)-cyclohexylamine, amine acetic acid ethyl ester, 6-aminohexanoic acid ethyl ester, 2-hydroxypropionic acid ethyl ester, 6-hydroxyhexanoic acid ethyl ester, mercaptoacetic acid methyl ester, mercaptocono\diethyl phosphate ester, 2-hydroxyethylaniline, anilinomethanesulfonic acid, anilinoacetic acid, hydroxyethyl-toluidine, tn-toluidino-methanesulfonic acid,
2-aminobenzoic acid, 2-aminobenzamide, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminobenzoic acid,
Chlor-3-aminobenzamide, 6-chloro-3-aminobenzoic acid, 5-ethrow-3-annobenzoic acid, 6-
Nitro-3-aminobenzoic acid, 4-aminobenzoic acid, 4
-Ainobenzoic acid ethyl ester, 4-ainobenzoic acid, 2-etro-4-aminobenzoic acid, 4-aino-3-methylbenzoic acid, 3-aino-4-methylbenzoic acid, 5-aminointutaric acid, 4 -aminonaphthalene-1,8-dicarboxylic acid, 3-amino-4-methoxy-
Ansa S aS, aniline-2-nurphonic acid, aniline-3
-Sulfonic acid, i177 + 3-sulfonic acid a? J/-4 -Sulfonate, 4-aminobenzenesulfonic acid, diphenylamine-4
-sulfonic acid, 4-benzylaquinobenzenesulfonic acid, 2,5-dichloro-4-aminobenzenesulfonic acid,
4-Aminotoluene-2-sulfonic acid, 4-aminotoluene-2-sulfonic acid anilide, 5-aminotoluene-
2-sulfonic acid, 4-aminophenylmethanesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-acrylic acid)
~Naphthalene-1-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-1,3,5
-4 lisulfonic acid or 2-mercaptobenzothiazole sulfonic acid. Of course many other dihalogeno-B-triazines of formula 8 can also be used as starting compounds for the preparation of polycarbonates of formula 3 containing S-triazine rings.
.

4. Dichloro-bis-triazinyl compounds of formula 9 suitable for the preparation of polycarbonates of formula 4 containing l-triazine structures by reaction with 4'-cyaquinostirpene-2,2'-disulfonic acid or salts thereof. An example of an afnodic triazine compound of formula 15 which can give
Ethylamine or butylaquine, diethylamine, diethylamine or dibutylene, monoethanolamine or diethanolamine, N-methylethanolane, aminoacetic acid, 4-aminobutyric acid or 6-adenohexanoic acid, aminoacetic acid ethyl ester or β - Amib tetrapionic acid ethyl ester, aniline, aniline-3-sulfonic acid, aniline-4-sulfonic acid or cyclohexylamine, pyrrolidone, piperidine, obtained by reacting with mole 7 olin in a molar ratio of 1:1. It is a compound that is

Examples of suitable aromatic dihydroxy compounds of formula 10 are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, -cycloalkane, -sulfide, -ether, -ketone, -sulfoxide or - sulfone, and further α, α
'-bis-(hydroxyphenyl)-diisopropylbenzene and the corresponding nuclear alkylated or nuclear chemotactic compound.

Some suitable aromatic dihydroxy compounds include, for example, t
2.2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2.2-bis-(3,S-'
) methyl-4-hydroxyphenyl)-propane, 2.
2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,Is-dibromo-4-hydroxyphenyl)-propane, bis-(4-
hydroxyphenyl)-methane, 1,1-bis-(4-
Hydroxyphenyl)-Schifftetrahexane and trinuclear bisphenyl, for example α,α'-binu(4-hydroxy-7-esteryl)-p-diisopropylbenzene.

Production of high molecular weight polycarbonate according to the present invention 11 Kpm
These and other bisphenols are
No. 970,131, No. 2,991,273, No. 2.9
No. 99.83i, No. 2,999.846, No. 3,01
No. 4,891, No. 3.028,365, No. 3,062
, No. 781, No. 3,148,172, No. 3,271,
No. 367, No. 3,271,368 and No. 3.280.
No. 078 and German Offenlegungsschrift No. 1.570,703.

Suitable reagents for limiting the molecular weight include phenols and 7/'-substituted or polysubstituted phenols, as well as monohapes of the general formula 16 [wherein ZSR, Q, α and Hα1 are as defined above] Geno S-) riazine. These compounds are produced as by-products during the preparation of the corresponding dihalogen derivatives.

8-) The polycarbonate according to the present invention containing a lyazine ring and consisting of the structural unit of formula 3 can be produced, for example, as follows.

First, following the omniscient method, on the one hand, the removal of hydrogen halides from cyanuric chloride and 13 and on the other hand! the presence of an organic solvent such as acetone, methyl ethyl ketone, or dioxane for cyanuric chloride, with the addition of a stoichiometric amount of the proton acceptor (e.g. NaOH or KOH) necessary for neutralization of the acid groups present in 13 or By reacting a triazine, e.g. cyanuric chloride, with a nucleophilic compound of formula 13 in a molar ratio of 1=1 in the absence of K, e.g. It is separated from the reaction mixture and used directly in the subsequent reaction with the aromatic dihydroboxy compound without purification or as a solution or suspension in the solvent used for the reaction without further work-up.

In a separate container, a 1:2 molar ratio of aromatic dihydroxy compound and alkali metal hydroxide, preferably sodium hydroxide or potassium hydroxide, are dissolved in sufficient water to give about 1:2 molar ratio.
An aqueous solution of an alkali metal salt of 0-bisphenol is prepared. The alkali metal salts of dihydroxy compounds which are insoluble or poorly soluble in water are used in the reaction as aqueous suspensions. Furthermore, diluted or concentrated alkali metal salt solutions or suspensions can also be used without losses.

Isolated and purified dihalogeno-8-)riazine by recrystallization, distillation or elution, or a water-immiscible compound which is inert towards organic solvents or dihalogenotriazines such as acetone, methyl ethyl ketone or dioxane.
To this aqueous alkali metal salt solution or suspension, 201: Portion by portion or −[
i5] K: Add.

Inert organic fIJ's include, for example, chlorinated hydrocarbons such as Ct, CHCJ, CCl, ethylene talide and hydrochloroethylene, benzene, toluene, xylene, chlorobenzene, chlorotoluene, dichlorobenzene and Furthermore, higher chlorinated aromatic compounds can be used.

It is also possible to take the IJ azine solution or suspension and add the alkali metal salt solution or suspension of bisphenol.

The well-stirred one- or two-phase mixture is maintained at a temperature of 0 to 300°C, preferably 30 to 150°C, for 0.2 to 20 hours. Suitably, the organic solvent, eg acetone, free from the reaction of cyanuric chloride with 13 is distilled off during this reaction step. Generally, the condensation of dichloro-sf triazine and dihydroxy compound is completed within 5 hours. All reactions up to this point are carried out under an inert gas atmosphere, e.g. The resulting alkali salts of bisphenols of formula 11 containing an 8-triazine ring are more or less readily soluble in water, depending on the nature of the dihalogeno-8-triazine and the aromatic dihydroxy compound used.

Therefore, solutions, emulsions, or suspensions exist in condensation. This is less important for the production of polycarbnate according to the present invention.

Paper preparation 17 [in the above formula, X
, Z%R%Q, a and HaL are synonymous with the above. ] If you want to prevent the formation of intermediate products, choose a large excess of bisphenol and dino-so-geno 13-
It is advantageous to carry out both the addition of the triazine and the condensation at elevated temperatures. However, the formation of by-products of formula 17 does not interfere with the overall course of the reaction since these compounds are incorporated into the polycarbonate structure.

If desired, an alkali metal salt of an aromatic dihydroxy compound is optionally used in excess and 8-)! J One-phase or two-phase mixture K in which an alkali metal salt of a bisphenol of formula 11 containing an azine structure is dissolved or suspended (K, aromatic polycarbonate) K a suitable solvent, such as methylene chloride, chloroform, carbon tetrachloride and 1 .2-dichloroethane,
or chlorinated aromatics such as dichloroluene/, chlorotoluene or polyalbenzene and, after addition of the aforementioned molecular weight limiting reagents, prepared from compounds which form carbonates, such as phosgene, bischlorocarbonate or dihydroxy compounds and The bisphenol components 10 and 8 were reacted with carbonate oligomers containing chlorocarbonate end groups according to known methods.
Depending on the properties of bisphenol 11 having a triazine structure, it is carried out in an alkaline medium at a pH of 10 to 14.

6-triazine ring and prepared according to the two-phase interfacial method, precipitated from the reaction mixture or added to the organic phase K11lljl
li L, the polycarbonate present in the solution is acidified according to conventional methods, e.g. by acidifying the reaction mixture with alkaline acid, separating the precipitated polycarbonate into two parts, and washing this until neutral, or removing the polycarbonate present in solution. The stone polycarbonate is precipitated from the organic phase, or the washed polycarbonate solution is evaporated and isolated in a stone sink.

The nine-heavy metal body formed by VCl2 has a low molecular weight or a high molecular weight depending on the amount of the chain terminator added.

Using a dihalogeno-8-) riazine of formula 8, where Q represents -COOH, -8o, H or an aliphatic OH group, the production of polycarbonate can be carried out at high pH according to the method described above, if desired.
-COO by working at a pH > 13.
It is also possible to produce polycarbonates containing 8-) lyazine rings branched or crosslinked with H1-8o, H or aliphatic OH.

Polycarbonate having the structural unit of formula 4 can be produced on the same machine as polycarbonate having the structural unit of formula 3.

The novel polycarbonates containing an 8-) riazine ring of formulas 3 and 4 according to the present invention have the 8-) riazine structural unit of formulas 1 and 2 introduced, so that the substituent Q of formula 1 can be Due to the H groups or due to the groups R- and R. of formula 2, they are very suitable for polymer-like reactions. For example, polycarbonates containing an S-)IJ azine structure and containing aliphatic OH groups may be aonoplasts or limited intermediate compositions thereof, such as melamine resins, penzoguatine resins or urea resins, phenolic resins. Alternatively, crosslinking with diincyanates and polyisocyanates provides a hard coating.

Polycarbonates of formulas 3 and 4 containing ester and carboxyl groups give hard coatings when crosslinked with, for example, binuoquinazoline or dieboxide and polyepoxide compounds, such as glycidyl esters,
The lacquers may optionally contain pigments and customary ratchet auxiliaries.

Polycarbonates with structural units of formula 3, in which Q represents a carboxyl or sulfoxyl group and are inert to many organic solvents at a certain molecular weight, are aliphatic, cycloaliphatic, aromatic and I
- Extremely suitable for the adsorption separation or removal of logenated hydrocarbons from aqueous solutions or mixtures with water.

Example 1 2.2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and 2-diethanolamine 4
, 6-dichloro-day-triazine (95:5 molar parts) with a chain terminator.

Bisphenol A21.7F (0,095
A solution of NaOH (7,6 mol) and NaOH (0,194 mol) was suspended in Chlorbe/Cane 60-Kl with a gentle flow of nitrogen and 2-jetanolamino-4,6-dichloro-B-triazine 1.27 F. (5 moles) and N
aBH,0.2f was added.

The two-phase mixture was then thoroughly mixed and heated to about 90°C for 4 hours. This was then cooled in a trench at about 20° C. and the intermediate product precipitated. p-tart-butylphenol 0.43f (2,86 orimoles) and C horse C1,120
After adding td, adjust the pH to 11-121/10 with chronic hydrochloric acid.
C94@l, COCl113.4 with vigorous stirring
f (0,135 mol) at 24-27° C. for about 30 minutes. During this phosgenation, the intermediate product dissolves, but the pH value is adjusted to 11-1 by adding 1N NaOH dropwise.
9,111 aqueous tri-ethylamino solution kept at 2.5
- After adding KIO, the mixture was further adjusted to pH 11-12 for KIO min.
Stir and round. During this period, the two-phase mixed eyelid became very viscous and after acidification with dilute phosphoric acid, the organic phase was separated, washed with distilled water until neutral and added dropwise to methanol.

At this time, polycarbonate precipitated as a white powder.

When dried for 17 hours at 100°C and 15 mHg, polycarbonate 21.4F (8
6) was obtained.

This relative viscosity (C 鵡”m100m/medium product 0.5f,
25°C) was 1.254.

N content 2 Calculated value: 1.12, analytical value: 1.04 - Aliphatic OH tatami: #0.68, #0.62 The polycarbonate produced in Example 1 was dissolved in chlorobenzene, and toluene was added at the boiling point. Crosslinked with range incyanate. The hard product precipitated from this reaction solution was insoluble in organic solvents.

Example 2 Bisphenol A and 2-jetanolamino-4,6
- dichloro-8-triazine (78:224 parts) with a chain terminator.

Bisphenol 120.1F (0,088 mol) and N
xOH7,04F (0,176 mol) was added to 180 sdK# of water under an atmosphere of N, NaBH,0,2F was added, and the solution was warmed to about 60-70<0>C.

This was added to 6.27 f (2-') ethanolamino-4,6-dichloro-8-) riazine in 60 td of chlorobenzene.
Add dropwise a suspension of 24,8 pores, and then carry out the reaction at 80 to 90°C for 2 hours with vigorous stirring. After cooling to room temperature, the pH was adjusted to IIKvI4 with dilute hydrochloric acid.
1,120 w of CH,C and 1,315 f (8,75 tl, 1 mol) of Up-tart-butylphenol are added and the mixture is then treated with CO at pH 11-12 according to Example 1.
Cl, 9.3 f (0,094 mol) was reacted.

After adding 6.3 ml of a sachet of aqueous trietheran solution, the mixture was stirred for a further hour at pH 11, the organic phase was washed to neutrality and the polycarbonate was isolated by evaporation.

Yield Nitriazine-containing polycarbonate 24.
2t<93) ηr @l (CH, Cl, 100-middle man product 0.5
f, 26℃): 1.078 N content calculated value 5.35, analytical value 4.96 OK number:
#107, IQ1 A hard coating was obtained by heating the polycarbonate prepared in Example 2 with nihexitemethytetra-meran hexamethyl ether in the presence of F-toluenesulfonic acid to 200''C in inert-cresol.

Example 3 Bisphenol A and 2-diethanol A Z No 4.6
-Gikuru 11-) Reazin' (90:104 parts)
Copolycarbonate crosslinked with chain terminators from.

As in Example 1, K, bisphenol A 20.6t (0,
094 mol), NaOH 7,2f (0,18 mol) and 2-jetanolamino-4,6-dichloro-8-triazid/2.53f (0,014 mol) in NaBH.

180 Wd of water and 60 Wd of chlorobenzene while adding
- Reacted for 4 hours at reflux temperature in a mixed solvent. After cooling, p-1art-butylphenol 0.27 F (
1,8 mmol) and CH, Cl! 140 m was added, the pH was adjusted to 14 with 2N NaOH solution, COCl,
11.9? (0.12 mol) was passed through at pH 14 with vigorous stirring. After this phosgenation, the aqueous phase was free of bisphenol salts.

Then 11) IJ ethyl aine aqueous solution 4.9- was added and the mixture was condensed and run. After about 3 minutes of stirring, the mixture first became very viscous and finally became rubbery, which was no longer of any use even with continued stirring. The gel-like swollen polycarbonate mass was separated, treated repeatedly with dilute phosphoric acid, and then washed with water.

When dried for 24 hours in a vacuum drying chamber at 100° C., a hard and viscous material 251 can be obtained.

The product was insoluble in most organic solvents.

N content: calculated value 2.29%, analyzed value 2.20n
Example 4 Bisphenol A and HN-(4#6-Sif-o-triazin-2-yl)-p-annobenzoic acid (9
0:10 molar parts).

Bisphenol A 20.6f (0,09
-+L) and NaOH7,6f (0,19 mol) in a solution of N-<4,6-dichloro-8-triazine-2-
yl)-araminobenzoic acid L8BF (0.01 mol)
was added and NaBH, 0.2f was also added, and the mixture was heated with stirring under an atmosphere of N for 5 hours at about 90-9B
During this heating period, the dichloro-8-triazine dissolves.

After cooling to 20° C., a clear solution was obtained. Then CH,
After adding Cl, 200- the pH is adjusted to 12,
The mixture was prepared as described in Example 1 (COCl at pH 12,
9 reacted with 11.9 F (0.12 mol).

At this time, a milky white, slightly viscous solution is obtained. Then p
Adjust H to 13 and add 8-1 H of aqueous triethylamine solution
was added and the mixture was stirred for an additional hour at pH 13.

After acidifying with dilute phosphoric acid, the mixture was shaken and extracted twice with distilled water, and the whole two-phase mixture was extracted, since the fractionation was very slow.
Added dropwise to methanol. At this time, polycarbonate precipitated as a white powder.

Yield Nitriazide/containing polycarbonate 24.7F (
100) N content 2 calculated value 2.2696. Analysis value 2.221
1C0OH ringing: Calculated value 1.82, Analyzed value 1.7
This product was, for example, insoluble in CH, Cl, 2, tetrahydrofuran, dioxane and pyridine.

Used nine N-(4,6-dichloro-8-triazine-2-
4k) -1-I7 Benzoin was prepared as follows: Cyanuric chloride 922F (0,54
) A layered suspension of 135 mol of acetonate/6 m, 6 t (0.5 mol) of p-benzoic acid and 750.6 F (0.5 mol) of triethylamine was added to the solution.
1 reaction temperature introduced at ~S℃ is 20℃ per 90 minutes
Raise the temperature under a heavy pressure and stir the mixture for an additional 90 minutes. The precipitated reaction product was separated, washed with distilled water to remove chlorine, extracted twice with acetone under boiling, and washed at 50°C/15°C.
■Dried with HQ.

Yield: 114 f (80 parts of theory), melting point >300°C.

Analysis 2 calculated value C42, 1% // 2.11 N19.
65 C124, Q5 analysis value 417% 2.1
7 19,2 24.7 Example 5 Bisphenol A and N-(4,6-dichloro-8-triazinyl-2)-p-ami7benzoic acid (89,5:
10.5 mole parts).

Bis7E/-kAl 8.3 in the same manner as Example 4
f (0,08%), Na OH7,2y (0,18
mol) and N-<4.6-dichloro-8-triazinyl-2)-p-amine benzoin 5.7 f (0.02 mol) were reacted for 5 hours at 90-9 BC in tH, 0320 m.

After cooling, a solution of bisphenol A bischlorocarbonate 81.8 F (0.09 mol) in % CH, C1,620- is introduced into the yellow solution of the sodium salt of the dihydroxy compound with vigorous stirring over a period of 2 minutes, Next, 1 and 2-hydrochlorinated triethylamine solutions 1 and 2- are added, and the p of the aqueous solution is
The mixture was further stirred while keeping the H at 12. Two-phase mixtures become very viscous in a short period of time9. After about 20 minutes, a spongy gel precipitated and stirring was no longer possible, so the reaction was stopped.6 The reaction mixture was made acidic with dilute phosphoric acid, and the resulting gel was separated with P. F*a is exclusively an aqueous phase, and all CM, Cl, are adsorbed on polycarbonate containing triazine.Then, the polycarbonate is suspended in distilled water and the inside! Wash until kK, 50℃/1! ! It was dried at 1IIH for 20 hours.

Yield: Cottony white polycarbonate containing nitriazine 46.5F (99%) N content: calculated 2.38%, analyzed 2.25% The product was dissolved in dimethylformamide (DMF).

C0OH (in DMF) Calculated value: 1.91 Excellent, Analytical value: 1.70 Example 6 Bisphenol A and N-(4,6-dichloro-day-)
Triagel-2)-p-aminobenzoic acid (89,5:
Removal of hydrocarbons from aqueous solutions by adsorption onto copolycarbonates from 10.5 molar parts).

A column of internal diameter 1.5 steel and length 30a++ was packed with 10F copolycarbonate prepared in Example 6 (packing height approximately 110 m with very K bulky material).

This column was loaded with an aqueous solution of hydrocarbon and a salt solution (in each case 50%
-) was passed through the column continuously, and the content of hydrocarbons in the aqueous solution before and after passing through the column was determined by gas chromatography (Reference Table 1): Example 7 Bisphenol A and UN-(4,6-dichloro-8 Copolycarbonate with chain terminator from -triazinyl-2)-p-aminebenzoic acid (95:5 molar parts).

Similar to Example 5, Bi-X7E/-L A9.1? (0,04 mol) to N-(4,6
-dichloro-8-triazinyl-2)-p-aminobenzoic acid 1.5F (5,26 mmol) and then p-tert-butylphenol 474.3μ (3,
16 mmol), then CH2Cl, 180-
Medium bisphenol A bischloro carbonate 21.29
A solution of (0.06 mol) was introduced, 10.1 - of 1% aqueous triethylamine solution was added and the mixture was stirred at pH 13. After about 1°, the triazine-containing polycarbonate precipitated out as a sherry and was processed as described in Example 5.

Yield Amount 2 White granular product 26. (1 (99chi).

N content: calculated value 1.12%, analytical value 1.02%C0
OH content: 0.897%, ttO
, 899% Example 8 Bisphenol A and A/-(4,6-dichloro-8-
Copolycarbonate with chain terminator from triazinyl-2)-p-aminobenzoic acid (98:2 molar parts).

α) As in Actual Example 5, bisphenol, 49.1
f (0.04 mol) to N-(4,6-dichloro-8-triazinyl-2)-p-aminobenzoic acid o, 57f (
2 IJ mol) and then adding at p//12-13 a 1T aqueous triethylamine solution,
Bisphenol A was condensed with bischlorocarbonate. 10
After minutes, the copolycarbonate precipitated as a sherry.

This was processed as described above.

Yield: 25tC97%) N content: Calculated value 0.439g, analytical value 0.41%b)
When the reaction described under α) was carried out in the presence of 766 wg 1 (5,11 mmol) of p-tert-butylphenol, the polycarbonate remained dissolved in the methylene chloride. After addition of triethylamine,
The mixture was stirred for a further 1 hour 7) #12-13, the organic phase was washed until neutral, then evaporated and the residue
Dry at 00 C/15rtmHU for 65 hours.

Yield Cobolicarbonate containing nitriazine) 2
2.29 (86chi) ηre l (product 0.5 in CH2C12100d
f, 25 r): 1.267 N content 2 Calculated value 0.434 chi, Analytical value 0.41 chi αχH
Content; p O, 349 忤, /10.34
% Example 9 Bisphenol A and 0'N-(4,6-dichloro-8-
triazinyl-2)-p-aminobenzoic acid (80:20
copolycarbonate from molar parts).

Similarly to Example 5, bisphenol A102 (0,04
4 mol), Nα()H3P (0.2 mol) and #-(4
, 6-dichloro-8-)riazinyl-2)-p-aminobenzoic acid (5.7 y (o, o 2 mol)) was dissolved in water 250-
10.1 of the aqueous triamine solution.
#! Bisphenol A bischlorocarbonate 12.79 (0
,036 mol).

Five minutes after adding the triethylamine, the polycarbonate precipitated as a sherry. After stirring for an additional hour, the mixture was processed as described above. The gel was then washed until neutral and dried under 80 U/15 mHQ for 30 h.

Yield: White fine granular powder 22f (9z%) N content: 2 calculated value: 4.65%, analytical value: 4.484C (XJR amount:
7F 3.74%, //2.96% Example 10 Bisphenol A and UN-(4,6-dichloro-8-triazinyl-2)-p-aminobenzoic acid (90:10
cyanuric chloride branched copolycarbonate from molar part).

Bisphenol A20.6F (
0,09 mol) and N-(4,6-dichloro-8-triazinyl-2)-p-aminobenzoic acid 2.85 f(0,
01 mole) was dissolved in 190 g of INNαυH solution, and cyanuric chloride 4
22 mmol) was added.

The mixture was heated at 90-95C for 5 hours with stirring under nitrogen.
The resulting clear solution was mixed with CM, C12150d and then reacted with C()(j211.9 f (0,12 mol) at pH 12.CH2Cl, 150 m After dilution with /, 1
8.3% aqueous triethylamine solution was added and the mixture was stirred for an additional hour at pH 12-13.

When acidified with dilute phosphoric acid, the triazine-containing polycarbonate precipitated as a gel. This was then processed as in Example 5.

Yield: 24 f flocculent product (97%) N content calculated 2.06 h, analytical value 2.08 h Example 11 Bisphenol A and N-(4,6-dichloro-8-)
I7 Copolycarbonate from azinyl-2)-sulfanilic acid (90:10 molar parts).

According to Example 4, bisphenol A20.6? (0,0
9 mol), NaOH7,29 (0.18 mol) and N
-(4,6-dichloro-8-triazinyl-2)-sulfuric acid (7) N(L salt 3.4:l (0.01 mol) was reacted and the mixture was then purified with COCl at pH 12,
11.99 (0.12 mol) and after addition of triethylamine the gold body was stirred for a further hour at pH 13. When the reaction product was acidified, the copolycarbonate precipitated as a white powder. Next, this was washed separately by suspending it in water until it became neutral, then rinsing with methanol, and drying at 80C/15ym/fQ for 65 hours.

Yield: Copolycarbonate 23.5F (93T)N
Content: calculated area 2.21 cm, analytical value 2.16% Example 1
2 Bisphenol A and 0'N-(4,6-dichloro-8-
Triazinyl-2)-p-aminobenzoic acid ethyl ester (85,7:14.3 mole parts) Calanocopolycarbonate.

According to Example 1, bisphenol A2 in H2O18〇
o,6f (o,09 mol) and NaOH7,2? (0,
18 mol) of S solution t-, N-( in 60 d of chlorobenzene
4,6-dichloro-8-triazinyl-2)-p-aminobenzoic acid ethyl ester 4.69F (15 mmol)
It was made to react with a suspension of at 80-90C for 3 hours. After cooling to room temperature, a grainy intermediate product precipitated. CH2
After addition of Cl2120d, 'iJH was adjusted to 13,
The mixture was heated to pH 13 with COCl, 11.9 F (0
, 12 mol).

After addition of the 100% aqueous triethylamine solution, stirring was continued for approximately 15 minutes until the polycarbonate precipitated as a gel. The precipitated product was treated as described in Example 5.

Yield Nitriazine-containing copolycarbonate 26f
(100 pieces) N content 2 Calculated value 3.22%, Analyzed value 3.15% This JR
The spectrum (KBr method) clearly shows that this is a polycarbonate containing ester groups. This product was dissolved in dimethylformamide.

#-(4,6-dichloro-8-)riazinyl- used
2) -p-Aminobenzoic acid ethyl ester was prepared using acetone (200 d)/dioxane (50 rn/water (300 d)
) by reacting 0.5 0.5 mol of theatal chloride with the addition of 0.25 mol of Nα2CO3 at θ~5C.
on) et al. (J. Am. Chem. Soc., 7
3, 2981 (1951)) for the preparation of 2-amino-dichloro-8-triazine.

The dichlorotriazine precipitated from the reaction mixture was purified by boiling with acetone.

Yield near 6%. Melting point 294 ~ 295G Calculated value: C4
6.05 N3.22 #17.9C122.70 Analysis value: C'46.15 N3.13 N17.8
C122.6 Example 13 Copolycarbonate from bisphenol A and UN-(4,6-dichloro-8-triazinyl-2)-glycine.

Teachings for the preparation of 2-amino-4,6-dichloro-8-)riadino [Thurston et al., J. Afn.

Chetn. Soc. 76, 2981 (1951
)] of cyanuric chloride in acetone/H20 (7:1 1 parts by volume) according to 1.8 4 f (0.0,
1 mol) and Gu1 Noshi 70,97F (10.5 mmol) were reacted at approximately OC while adding N(LOHo. To an orange-red dichlort 1 noazine solution in acetone/water was added 9.62 (42 mmol) of bisphenol A in 2 rd H2O and 3.3 mmol of NaOH.
6? (84 mmol) was added and the mixture was gradually heated to about 90-95 C, during which time acetone was distilled off from the reaction solution. After distilling off the acetone,
The mixture was stirred for a further 3 hours at 95-1001:'. Then, cooled to room temperature, the light yellow solution was distilled with 100 m/ml of water and, with vigorous stirring, a solution of 16.96 f (48 ml J mol) of bisphenol A chlorocarbonate was introduced and 10.1 m of the aqueous triethylamine solution was added. Add
The mixture was further stirred at p/-713.

After about 15 minutes, the polycarbonate precipitated as a sherry. The reaction was stopped and the polycarbonate was treated as described in Example 5.

Yield: 22.3t (cotton-like white koboli carbonate)
N content: calculated value 2.32 cm, analytical value 2.28 cm I was able to do that.

Example 14 Bisphenol A and UN-(4,6-dichloro-8-)
Reazinyl 2)-6-aminohexane #! (90:1
copolycarbonate from 0 molar parts).

Similarly to Example 13, cyanuric chloride 1.84f (0,
01 mol) to 6-amino-hexanoic acid 1.38F (10
, 5 mmol) to form #-(4,6-dichloro-
8-triazinyl-2)-6-aminohexanoic acid was produced, and the resulting white suspension was mixed with bisphenol, 49.6
F (4.2 mmol), during which the acetone resulting from the first reaction step is removed from the mixture, and then after the addition of 1 tidoethylamine solution, the colorless solution of the dihydroxy compound is dissolved in bisphenol A bischlorocarbonate in methylene chloride. 16.96F (48 mlJ mole)
Polycondensation was carried out with a solution of pH 13 at 20 to 25 r for 1 hour. The organic phase was separated, acidified with dilute phosphoric acid, washed with a neutral trench and added dropwise to methanol. At this time, the triazine-containing polycarbonate precipitated in the form of white flocs.

Yield: 21.4F (87%) lrel (CH2C12100 - product 0.52
．． 25 tl'): 1.535 N content 2 Calculated value 2.27 cm, analytical value 2.12 cm C (force surface *: // 1.62 cm, p 1.59 cm Example 15 Bisphenol A and (jN -(4,6-dichloro-8
-) Copolycarbonate from IJ azinyl-2)-2-aminebenzoic acid.

Similar to Example 4, bisphenol A9.6f (42 mmol), N(L(]H3,76f (94 mmol) and N-(4,6-dichloro-8-triazinyl-2
)-2-Aminobenzoic acid 2.85F (10 mmol) was reacted in 180 °C of water at about 95 to 100 C for 5 hours,
CH,,C12170 was added to the resulting milky cloudy solution.
Bisphenol A bischlorocarbonate 16.9 in d
A solution of 6f (48 mmol) was introduced, a 10,1-tidolyethylamine water bath solution was added and the mixture was condensed for 1 hour at pH 13. The viscous organic phase was then treated as shown in Example 14.

Yield: flocculent white copolycarbonate 24.72 (
100ch) ηrel(CH2C12100rn1. Product 0.5
9.25C): 1.372 N content: Calculated value 2.26%, analytical value 2.08CυωNight amount: ,〃1.82CH,〃1.7CH used N-(4,6
-Dichloro-8-)riazinyl-2)-2-amine benzoic acid was prepared by cyanuric chloride 36.8 F in the presence of triethylamine 20.3 F (0.2 mol) as MCI acceptor in acetone 520 m/ (0.2 mol) and 2-aminobenzoic acid 27.4 f (0.2 mol) at θ~2c. The resulting reaction product was washed with dilute hydrochloric acid, then with water until free of chlorine, boiled with acetone, and dried.

Yield: 30.2f (53%); Melting point > 330C (decomposition), Analysis: Calculated value C42.1% #2.11%C12
4,95% analysis value C42,4% H2,19% C124,9% Example 16 Bisphenol A and UN-(4,6-dichloro-8-triazinyl-2)-2-aminoethanesulfonic acid (9o
: io molar parts).

Similarly to Example 13, cyanuric chloride 1.84r (10
The corresponding dichloro-8-)riazine was prepared by reacting 1.311 (10.5 mmol) of 2-aminoethane-1-sulfonic acid (taurine) with 9.6 f mmol of bisphenol A. (42 mmol)
and reacted at 60-95r.

During this time, the acetone present in the reaction mixture was simultaneously distilled off to give a colorless solution and finally the product was converted to 16.96% carbonized ester of bisphenol A bischloro in methylene chloride at p//13 after the addition of 1% aqueous triethylamine.
Polycondensation was carried out with a solution of f (48 SIJ mol).

After stirring for an additional 30 minutes, the triazine-containing copolycarbonate precipitated out in a sherry form, which was then treated as described in Example 5.

Yield: 23.8 inches (97 inches) N content: Calculated value 2.27%, analyzed value 2.18 inches The product was able to adsorb about 36 times its weight of CH2Cl2.

Example 17 Bisphenol A and UN-(4,6-dichloro-El)
Riazinyl-2)-5-aminoisophthalfi (90:
10 molar parts).

Similarly to Example 13, cyanuric chloride 1.84f (10
mmol) in acetone/water, Na()Hl, 24
The yellow suspension obtained was reacted with 1.99 (10.5 mmol) of 5-aminoisophthalic acid in the presence of F (31 mmol) at 0-5C and 9.6t (31 mmol) of bisphenol A (
After condensation with 42 mmol) at 60-90C for 5 hours and finally after addition of 10.1 m/l of 1 tidolythylamine solution, the aqueous solution of the dihydroxy compound was converted into bisphenol A bischlorocarbonate 16.96 F (48 mmol) in methylene chloride.
1 hour at 20-25C with a solution of 'I) HI
3 was polycondensed.

After further stirring for about 10 minutes, the precipitated copolycarbonate in the form of gel was treated in the same manner as in Example 5.

Yield: White, copolycarbonate 25f! (99%
) N content: Calculated value 2.22%, Analysis value 2.201CO (Facial appearance: II 3.58%, #3.33%) This product was able to adsorb about 19 times as much cH2c12 as 1%.

Example 18 Bispheno-tb,4 and (4,6-dichloro-8
-triazinyl-2)-2-hydroxyacetic acid (90:1
copolycarbonate from 0 molar parts).

Similarly to Example 4, bisphenol A9.6f (42 mmol), NaOH3,76F (94 mmol) and (4,6-dichloro-8-triazinyl-2)-2-
h) 2.24 f (10 mmol) of 'o-+cyaacetic acid was reacted in 200 d of water at about 70-80 C for 4 hours.

After cooling to room temperature, a solution of 16.96f (48 mmol) of bisphenol A bischlorocarbonate in CH,C12200 was introduced to give a solution of 10% 1% tidoethylamine aqueous solution.
．． 1- was added and the mixture was condensed with 1) HI3 for 1 hour. After stirring for an additional 10 minutes, the triazine-containing polycarbonate precipitated as a jelly and was treated as in Example 5.

Yield Nitriazine-containing copolycarbonate 22.
99 (95 Chi) N Jl: Calculated value 1.74%, Analysis value 1.7 (ICO
OI@77: p 1.87ch, # 1.7
5% Example 19 Copolycarbonate of bisphenol and S-C4,6-dichloro-8-triazinyl-2)-mercaptobenzoic acid.

Teachings for the preparation of 2-arylthio-4,6-dichloro-8-)riazine C'J, Drabek and A/;
5krobal, Chem, Zvttsti L
482 (1963)), cyanuric chloride 1.84 F (0.01 mol) and 4-mercaptobenzoic acid 1.54 F (0.01 mol) in N
(approximately 0 while adding LUIO, By (0,02 mol)
The reaction was carried out at ~5C. Bisphenol A9.6f (42 mmol) and NaOH3,36F in H2()50d
(84 mmol) and the mixture was mixed with ca.
Heated to ~80C, during which time acetone was distilled off from the reaction solution. After cooling to room temperature, the product was converted to bisphenol A chlorocarbonate 16.9% as described in Example 13.
6f (48 mmol) and the polycarbonate product was treated as described in Example 5.

Yield Nitriazine-containing copolycarbonate 24.6
f (99 h) N content calculated 1.69 h, analytical value 1.55% Example 20 1.1-bis-(4-hydroxyphenyl)-cyclohexane, bisphenol A and N-(4*6- Dichloro-E!triazinyl-2)-p-aminobenzoic acid (42
:48:10 mole parts).

In the same manner as Example 15, 1,1-bis-(4-hydroxyphenyl)-cyclohexane 11.3F (42 mmol) was added in /l/-(4,6-diC1-B-triazinyl2)-p- The mixture of dihydroxy compounds obtained by reacting with aminobenzoic acid 2,85F (10 mmol) was converted into bisphenol A bischlorocarbonate 19.96
f (48 mmol) was condensed. The resulting copolycarbonate was processed as described in Example 5.

Yield Nitriazine-containing copolycarbonate 26f
(97chi) N content 2 Calculated value 2.08chi 1 Analysis value 2.0% Example 2
1 2.2-bis-(3,5-dimethyl-4-hydroxyphenyl)-furopane and #-(4,6-dichloro-8-
triazinyl-2)-p-aminobenzoic acid (90:1
copolycarbonate from 0 molar parts).

Similar to Example 15, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane 11.959
(42 mmol) A/-(4,6-dichloro-8-)
2)-p-aminobenzoic acid 2.85F(1) containing riazine
methylene chloride 170-
Bis-chlorocarbonate of 2,2-bis-(3゜5-dimethyl-4-hydroxyphenyl)-propane 19
．． After introducing a solution of 2F (48 mmol) and adding 1.36 f (13.5 mmol) of triethylamine, the mixture was stirred for a further 3 hours and then worked up as described in Example 5.

Collection Jl:) Copolycarbonate containing riazine a1
r (94%) N amount 2 Calculated value 1.70% 1 Analytical value 1,65 Example 22 Hophenol A and N-(4,6-dichloro-8-triazinyl-2)-2-aminobenzami) '(90:1
copolycarbonate from 0 molar parts).

Bisphenol, 49.6f (42 mmol), NaOH3,369 (84 mmol) and N
-(4,6-dichloro-El-triazinyl-2)-2
-Aminobenzamide 2.84F (10 mmol) was reacted in 170°C of water at about 90-95r for 5 hours. Then, with vigorous stirring, a solution of 16.96 F (48 mmol) of bisphenol A bischlorocarbonate in CH, C 12270s/medium was introduced, 10.1 mm of an aqueous solution of 1-tidoethylamine was added, and the mixture was allowed to condense for 1 hour at pH 13. Ta. The copolycarbonate precipitated as a jelly was treated as in Example 5.

Yield: Copolycarbonate 2x, 6r (s7%)N
Content: 2.83%, analytical value: 2.75% This IR
The spectrum (KBr method) clearly shows that the product is a polycarbonate containing amide groups.

7V-(4,6-dichloro-8-triazinyl-2)-
p-Aminobenzamide was prepared by reacting cyanuric chloride 18.4P (0.1 mol) with p-aminope/zamide while adding N(LHCO58.4f (0.1 mol)) in acetone/water (1:1 parts by volume). It was produced by reacting with 13.6f (0.1 mol) at θ~3C.

Yield: 51.6F(9i), melting point>300rCl content: calculated value 25.1%, analytical value 24.9ch Example 23 Bisphenol A and N-(4,6-dichloro-8-triazinyl-2)- Copolycarbonate from p-aminobenzenesulfonic acid amide (90:10 mol parts).

Similar to Example 22, bisphenol A9.6? (42
mmol) was first converted into N-(4,6-dichloro-8-triazinyl-2)-p-aminebenzenesulfonic acid amide 3.
．． 2f (10 mmol) and then the product was converted into bisphenol A bischlorocarbonate 16.969 (
48 mmol). Approximately 20 minutes after the addition of triethylamine, the triazine-containing copolycarbonate precipitated as a jelly.

Yield: 25f (100t) N content: Calculated value 2.79%, analyzed value 2.7tN-(4,
6-Dichloro-8-triazinyl-2)-p-amine benzene sulfonic acid amide was prepared from cyanuric chloride by adding NCLHCOs 8.4 F (0.1 mol) in acetone/water (1:1 parts by volume). 18.4 F (
0.1 mol) to 4-aminebenzenesulfonic acid amide 1
It was produced by reacting with 7.2f (0.1 mol) at 0 to 3C.

Yield: sa, 5r (84%), melting point >300 CCl
Content: calculated value 22.3%, analyzed value 22.1% Example 24 Bisphenol A and 4.4'-bis-[4-nochloro-6-jetanolamino-S-) riazine-2
Copolycarbonate from -ylcyamino-2,2'-stilbenedisulfonic acid (99:1 mole part).

Similar to Example 4, 22.6t (99%) of bisphenol A
mmol), NαOH7,92f (198 mmol) and 4,4'-bis-[4-chloro-6-jetanolamino-S-)riazin-2-yl]-amino-2,2'
-Disodium salt of stilbene disulfonic acid 847■
(1 mmol) was reacted in 175 g of water at about 90-95 C for 5 hours. The mixture was cooled to 200 ℃ and p-ter
After adding t-butylphenol 450 Ilv (3 mmol) and CH2Cl2175-, the mixture was diluted with COCl214.9 f (0,15 mol) with vigorous stirring.
was reacted with at pH 12. Then 10.111! of aqueous triethylamine solution! / was added and the mixture was stirred for an additional hour at pH 12. After acidification with dilute phosphoric acid, the aqueous phase was separated and the organic phase was added dropwise to methanol. At this time, polycarbonate precipitated.

Yield: 24.3F (94%) r) re l (CH2C12100 - product 0.5
f, 25 C): 1.245 N content calculated 0.54%, analyzed 0.53 cm. When irradiated with UV, the product showed blue fluorescence.

Example 25 Bisphenol A and 4,4'-bis-[4-chloro-6-jetanol-amino-S-triazin-2-ylcyamino-2,2'-stilbenedisulfonic acid (90
210 mole parts).

As in Example 24, CM2C12210m7! Among them, 20.55' (0.09 mol) of bisphenol A and 4,4'-bis-(4-chloro-6-jetanol, 71f)-? f3j-) Reazine 2. -mail)
-Amino-2,2'-stilbenedisulfonic acid 8.47
t (o, ot mol) in H2()210g NaOH
The reaction was carried out while adding 7,2F (0,18 mol), and then 0.75F (5 mol) of p-tart-butylphenol was added.
mmol) at room temperature and then the mixture was diluted with COCl2
11, phosgenated with (1 (0.12 mol)). After addition of 10.1-tidolythylamine aqueous solution and fc, the bonate precipitated as a grainy product.

After drying at 80 C/15 mHU for 24 hours, copolycarbonate 30f (991) remained.

N content: calculated value 4.61%, analyzed value 4.4% Example 26 Bisphenol A and 4,4'-bis-[4-rib-6-anili-S-)riazin-2-yl]-amino-2 , 2'-stilbenedisulfonic acid (99:1 molar parts).

Similar to Mi7Ai9'1J24, bisphenol A22
．． 6f (99 mmol) and 4,4'-bis-[4-
524 t (1 mmol) of the diNα acid o of chloro-6-anili2-yl]-7mino-2,2'-stilbendisulfo/acid was dissolved in 175% of N in water 175
The product was phosgenated with C()C1214,9f (0.15 mol) at pH 13 after the addition of CH2Cl2175- (LOH7,929 (198 mmol)), and the product was phosgenated with C()C1214,9f (0.15 mol) and triethylamine (10% in water). 1
m/) and the mixture was stirred for 1 hour. After acidification, the mixture was added directly to methanol. At this time the polycarbonate precipitated out as a white flocculent material.

Yield: 23.8F (92%) 1rel CCH, C12100 - product 0.52
．． 25C): 1.287 N content: calculated value 0.54%, analyzed value 0.49% This product exhibited green-blue fluorescence upon UV irradiation.

The aspects and related matters of the present invention are summarized as follows: 1. At least one bisphenol and at least one
contains polymerized divalent residues of species of 8-triazine compounds, with each divalent 8-triazine compound residue containing 2
bisphenol residues, each S -1-IJ
Two 8-) IJ azinyl ring carbon atoms of the azinyl compound residue are each bonded to one oxygen atom of the adjacent bisphenol residue, and each 8-4 riazinyl term in the 8-) riazinyl compound residue is It has an organic group containing a functional group as a substituent, or the organic group
A polycarbonate that is bonded to an azinyl ring and whose bearing is carried by an oxygen, sulfur or nitrogen atom.

2. General formula [In the above formula, Bd is a bisphenol residue, and T is S-
) is a riazinyl compound residue, and n is from 1 to 200, more preferably from 3 to 100.

3. The polycarbonate of 2 above, wherein n is 3 to 100.

4. At least some of the S-) riazinyl compound residues have the general formula [wherein Z is -0-1-s-1-NH- or -NR"
Or one #-(R*)-(Q*)α books.

R and R* are each independently an alkyl group having up to 20 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a mononuclear or polynuclear arylene group optionally having one or more substituents,
a hetero-arylene group with up to 14 carbon atoms, in which the carbons are bonded to the groups Indicates an alkyl group having up to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a mononuclear or polynuclear group, or an optionally substituted heteroaryl group having up to 14 carbon atoms,
However, the carbon atom is bonded to a nitrogen atom, or is an aralkyl or alkylaryl group having up to 30 carbon atoms, or a hydroxyalkyl group having up to 10 carbon atoms, and Q and Q* are independently -COυH1-C0OR"
, -C0NR"R', -80,H.

-SO, NR3R' or an alcoholic hydroxyl group, where R2 represents an alkyl group having up to 4 carbon atoms,
R3 and R4 may be the same or different and represent hydrogen, a straight-chain or branched alkyl group having up to 4 carbon atoms, and an optionally substituted phenyl group, or together with the N atom, a 5- or 6-membered group; and α and α* each independently represent an integer of 1 to 4.

5. At least some of the residues of the S-) IJ azinyl compound have the general formula % (21 [In the above formula, R5 and R6 may be the same or different and may be H, alkyl having up to 5 carbon atoms, hydroxy Alkyl, carboxyalkyl or alkoxycarbonylalkyl group, C star to C7 cycloalkyl group, or C6 to CI4
represents an aryl group, or forms a 5- or 6-membered ring system together with the N atom.

6. The polycarbonate of 4 or 5 above, wherein any substituent present in R, R* and R' is selected from alkyl, alkoxy and alkylmercapto groups having up to 4 carbon atoms, halogen atoms, nitro groups and cyano groups.

7, the S −) +7 based on the azinyl compound residue 0
．． Polycarbonate of the above embodiment crosslinked by introducing trivalent groups of 8-)riazinyl compounds of 01 to 5 mol. .

8. The trivalent residue has the formula 7. The polycarbonate of 7 above.

9. Bisphenol is bis-(hydroxyphenyl)
- The polycarbonate of the above embodiment which is an alkane.

10. Bisphenol is a group having the general formula % ((In the above formula, X optionally has one or more substituents. -1m- is a p-phenylene group), or a group having the general formula [ In the above formula, R7 and R& represent a hydrogen atom, an alkyl group having up to 4 carbon atoms, or a rogen atom, and may be the same or different, and Y is a single bond, an alkylene or alkylidene having up to 7 carbon atoms, and Y is a single bond, an alkylene or alkylidene having up to 7 carbon atoms, and 5-12 cycloalkylene or cycloalkylidene, -0-1-S-1-CO
-1-SO-1-SO2- group] or the general formula % formula % (66) [In the above formula, R@, R″0 and R” represent the same or different alkyl groups having up to 4 carbon atoms. , and R'' may represent hydrogen or ).logen atom].

11.X is a group CH8 The polycarbonate of 10 above.

12. The polycarbonate described in 1 above in the Examples.

13. at least 1 m monomer comprising said at least one divalent bisphenol residue and said at least one divalent 8-) IJ azinyl compound residue, either by itself or together with bisphenol.

1. The method for producing polycarbonate as described in 1 above, which comprises reacting with a polycarbonate-forming derivative of carbonic acid.

14. The method of 13 above, wherein the derivative is phosgene.

15. 14 above, characterized in that the reaction is carried out by an interfacial method.
the method of.

16. The method of 13.14 or 15 above, characterized in that the reaction is carried out in the presence of at least one compound that limits molecular weight.

17. The monomer is S-) riazinylbisphenol of the general formula %() [In the above formula, phosgene and/or a bischlorocarbonate of a bisphenol of general formula io mixed with a bisphenol of general formula 10 and/or a bischlorocarbonate of a bisphenol of general formula 10 and containing a chlorocarbonate end group; A method for producing the polycarbonate characterized in 4 above according to 13 to 16 above.

18. Dihalo-8-) riazine of the general formula % formula % [in the above formula, Z%R%Q and α are as defined above] and 2 equivalents of bisphenol of the general formula 1° of the above 10 are combined into a proton acceptor. or with 2 equivalents of an alkali metal salt of the bisphenol of formula 10 to produce 8-)riazinyl biphenyl of general formula 11. the method of.

19- After the FJ pre-step B-) 17 above without isolating the lyazinylpiphenyl or transferring it to a different reaction vessel.
18. The method of 18 above, which is characterized by carrying out a reaction such as:

20, the monomer has the general formula [In the above formula, R5 and R6 have the same meaning as 5 above] Bis-8-) riadinylbisphenol.

A carbonate oligomer prepared by itself or mixed with bisphenol of general formula 10 from phosge/and/or bischlorocarbonate of bisphenol of general formula 10 and/or bisphenol of general formula IO and containing a chlorocarbonate terminal group. The method for producing polycarbonate according to Items 13 to 16 above, characterized in that the polycarbonate described in Item 5 is reacted with

21, dichloro-E+-) riazine of the general formula [in the above formula, R5 and R6 have the same meanings as in 5 above] and general formula 10 of the above 1o
2 equivalents of bisphenol in the presence of a proton acceptor, or an alkali metal salt of the bisphenol of formula 1o, 2
bis-8- of general formula 12 by reacting with equivalents
20. The method of 20 above, which comprises a pre-step of producing triazinylpiphenyl.

22. The method of 21 above, characterized in that the reaction of 20 above is carried out without isolating the S-) lyazinyl biphenyl after the preceding step or transferring it to a different reaction vessel.

23. Up to 19 g/iL of bisphenol of general formula 10 (8-) of general formula 11 depending on the case! General formula 1 mixed with 1 equivalent of J azinylbisphenol and/or his-〇-)riazinylpisphenol of general formula 12, provided that
The sum of the equivalents of 0 bisphenols does not exceed 19 g equivalent per equivalent of said S-triazinyl or bis-8-)realenylbisphenol, and the bonding is through at least 1.05 equivalents of -CO- per equivalent of phenolic -0H. 23. The above-mentioned methods 17 to 22, characterized in that the method uses lfa l .

24. Reacting at least one of the monomers and the derivative of carbonic acid forming the polycarbonate with 8-) riazinyl-trisphenol of the general formula [wherein X has the same meaning as 8 above] The method for producing the branched polycarbonate described in Item 8 above according to Items 13 to 23 above, characterized in that:

25. A method for producing the polycarbonate of 1 above as substantially described in any of the Examples.

26. The above 1 produced by any of the methods 3 to 24 above
of polycarbonate.

27. A hydrocarbon and the halogenated hydrocarbon are adsorbed onto the polycarbonate according to any one of 1 to 12 and 26 above, and the carbon water is removed from a mixture of the hydrocarbon and water or a salt aqueous solution. Method.

28. The method of 27 above, characterized in that a polycarbonate in which Q is -C00H or -8o,H is used.

29. The method of 28 above, wherein Q is -CUOH% Z is -NH and α is 1.

30. The method of 27 above substantially as described in any of the Examples.

Patent applicant: Bayer Akchengesellschaft Representative: Patent attorney Heifu Odashima

Claims (1)

[Scope of Claims] (11 Formula % Formula %) [In the above formula, X has one or more V substituents at m. -, m- or p-phenylene group, or the general formula % (in the above formula, R7 and R1 represent a hydrogen atom, an alkyl group having up to 4 carbon atoms, or a halodane atom, and may be the same or different, and Yf-1, alkylene or alkylidene with a prime number of up to 7, II cycloalkylene or cycloalkylidene with a prime number of 5 to 12. -O-, -5-1-co-, -5o-. -SO, - group, or general formula R10R10R1'I (6α) (6/)) provided that R1, 1
7@ and R11 represent the same and different alkyl groups having up to 4 carbon atoms. and R is a group in which M is hydrogen or halo (r:/ may also represent an atom). Zr1-0-, -8-1-NH- or d-NR' or -
N-<R+-+Q)
12 cycloalkylene groups, optionally with one or more substituents, or polynuclear arylene groups, up to 14 carbon atoms, carbon attached to the group X as defined above and the group Q as defined below and optionally a hetero-arylene group having a tMI group of 111IA or more, or an alkalylene or aralkylene group having a total carbon number of up to 30. R1 is an alkyl group having up to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cyclic or polynuclear aryl group, or an alkyl group having 14 carbon atoms. Indicates an optionally substituted heteroaryl group. However, the carbon atom is attached to a nitrogen:A atom, and is an aralkyl or alkylaryl group having 5 or 301 carbon atoms, or a hydroxyalkyl group having up to 10 carbon atoms. Q and Q l-J each other in 3+i2 standing -COOH. -C: 00k'', -CONR3R4, -3O,H. -8o, NR''R4 or alcoholic hydroxyl group, provided that R2 represents an alkyl group having up to 4 carbon atoms,
81 and R4 may be the same or different hydrogen or carbon? Straight chain or branched alkyl groups in 1/41 and optionally ft.
j substituted to represent fc phenyl group, or together with N atom to form a 5-negative or 6-membered system, and α and au each represent an integer from 1 to 4 in the text; Rubisphenol and the general formula [wherein R゜ and 7?] “tjh- but may be different B
or alkyl up to 5 carbon atoms, hydroxyalkyl,
Calgexialkyl or alkoxycarbonylalkyl group%C1-C, cycloalkyl group, or C("C, a
Indicates an aryl group, or together with a ViN atom, 5J
[In the above formula, X has the meaning given above] and a derivative of carbonic acid to form a polycarbonate is reacted with 8-triazinyl-trisphenol of the general formula % [wherein X has the meaning given above] shall be. #-) 0. based on the lyasin compound residue. A method for producing a branched polycarbonate by introducing a trivalent residue of the formula O1-5molti.