JPS6025049B2 - Method for manufacturing branched polycarbonate - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polycarbonates improved by the introduction of residues of compounds containing s-triazine rings, their preparation and their use as adsorbents. The present invention provides at least one biphenol and at least one
contains polymerized divalent residues of species of s-triazine compounds, where each divalent s-triazine compound residue is present between two bisphenol residues; An organic group in which two s-triazinyl ring carbon atoms are each bonded to one oxygen atom of an adjacent bisphenol residue, and each s-triazinyl ring in the s-triazinyl compound residue contains a functional group as described below as a substituent. or is bonded to another s-triazinyl ring by the organic group and bonded to the carbon atom of the adjacent s-triazinyl ring by an oxygen, sulfur or nitrogen atom. The term "s-triazinyl compound" as used herein means a compound containing at least one s-triazine ring. Furthermore, the term "functional group" as used herein refers to an acid group (e.g., 1C
OO or S03H), a modified acid group (for example an ester or amide group, especially an esterified or amidated carboxyl or sulfonic acid group) or an alcoholic hydroxyl group. In two important forms of the invention, the S-triazinyl compounds each include one S-triazine ring and two S-triazinyl groups linked by a functionalized organic group. The organic group may be bonded via oxygen or sulfur, but preferably via a nitrogen atom to each one of the two S-triazine rings.
Combined into ``actual size'' pieces of carbon. A suitable polycarbonate of the present invention has a general formula [wherein B is a bisphenol residue, T is a S-mount triazinyl compound residue, and n
is a number of 1 to 200, more preferably 3 to 100. According to another preferred embodiment of the invention, the polycarbonate contains 0.0
It is branched by introducing 1 to 5 mol% of trivalent residues of S-triazinyl compounds. Preferably the trivalent residue is of the formula. Furthermore, the present invention provides at least one monomer comprising the at least one divalent bisphenol residue and the at least one divalent S-triazinyl compound residue, either by itself or by A process for the production of polycarbonates as described above is provided, characterized in that they are reacted with a polycarbonate-forming derivative of carbonic acid together with bisphenol. Finally, the present invention is characterized in that hydrocarbons and the halogenated hydrocarbons (aliphatic, cycloaliphatic and aromatic) are adsorbed onto the polycarbonates of the invention from a mixture of said hydrocarbons and water or an aqueous salt solution. A method for removing hydrocarbons is also provided. The polycarbonate according to the present invention has the general formula '1-[wherein Z is -○-, 1S-, 1NH-, or 1NR', or 1N-(R*NaQ*)a*] R and R* are each independently an alkylene group having 1 to 20 carbon atoms, and 5 carbon atoms.
~12 cycloalkylene groups, mononuclear or polynuclear arylene groups, heteroarylene groups via carbon atoms of up to 14 carbon atoms, mono- or polysubstituted mononuclear or polynuclear arylene groups, heteroarylene groups via carbon atoms of up to 14 carbon atoms Indicates an arylene group, provided that possible substituents include, for example, an alkyl, alkoxy or alkylmercapto group having 1 to 4 carbon atoms, a halogen atom such as chlorine or bromine, -N02 or -CN, an alkylarylene group having up to 20 carbon atoms in total, or Total carbon number 30
R' is an aralkylene group with up to 14 carbon atoms, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms, a mononuclear or polynuclear unsubstituted or substituted aryl group, or an aralkylene group with up to 14 carbon atoms. Denotes a bonded heteroaryl group, provided that possible substituents include, for example, alkyl, alkoxy or alkylmercapto groups having 1 to 4 carbon atoms, halogen atoms such as chlorine or bromine, -N02 or -CN, up to 30 total carbon atoms. an alkylaryl group, an aralkyl group having up to 30 carbon atoms in total, or a hydroxyalkyl group having 1 to 10 carbon atoms, and Q and Q* are independently -COO, -COO
R2, 1CONR3R4, 1S03day, 1S02NR3
RI or an -OH group bonded to an aliphatic group, where R2 represents an alkyl group having 1 to 4 carbon atoms, and R3 and R4 each independently represent hydrogen, a straight mirror or branched alkyl group having 1 to 4 carbon atoms; or represents an unsubstituted, monosubstituted or polysubstituted phenyl group, or forms a 5- or 6-membered ring system together with the N atom, and a and a* each independently represent an integer of 1 to 4. ] may be contained as a bridging member between the aromatic shydroxy compounds and bonded via the oxygen atom of the latter. Instead of or in addition to the radicals of general formula 1, the polycarbonates of the invention have the general formula

[2' [In the above formula, R5 and R6
are independently H or an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl/carboxyalkyl group, an alkoxycarponyl alkyl group, a C5 to C7 cycloalkyl group,
or a substituted or unsubstituted C6-C,4 aryl group,
or a 5- or 6-membered ring system together with the N atom, such as pi. Forms a lydone, piveridine or morpholin ring system]
as a bridge member between the aromatic bishydroxy compounds and bonded via the oxygen atom of the latter. Preferred substituents for formulas m and 2 above are as follows: Z
=-NH1, or 1NR'- or 1N-(R*Naf
Q*) a*R and R*=alkylene or phenylene having 1 to 10 carbon atoms, independently of each other; Alkyl having 1 to 6 carbon atoms or 1 to 6 carbon atoms
6 hydroxyalkyl "R5 and R6 white independently hydrogen, hydroxyalkyl having 2 to 4 carbon atoms, 1 to 4 carbon atoms
4 alkyl, phenyl and sulfoxyphenyl. The novel polycarbonate containing an S-triazine ring has the general formula (3} and/or [4) [in the above formula, X is o-,
It represents an m- or p-phenylene group or a mono- or polysubstituted o-, m- or p-phenylene group, with the possible substituents being, for example, lower alkyl having 1 to 4 carbon atoms or a halogen atom such as chlorine or bromine. or preferably represents a group characterized by the formula {5}, provided that R7 and R6 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, particularly preferably a chlorine or bromine atom, and may be the same. and Y is a single bond, alkylene or alkylidene having 1 to 7 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 12 carbon atoms,
1○-, 1S-, 1CO-, 1SO-, 1S02-, or a group of the formula (candy) or (arc), provided that R9 to RII represent an alkyl group having 1 to 4 carbon atoms, and R
II may represent hydrogen or a halogen atom such as chlorine or bromine, and Z, R, Q, a, R5 and R6 are of formula '1
) and ■, and n is 1 to
200, preferably 3 to 100) of identical or non-identical fluting units. Preferred radicals Y are isopropylidene and cyclohexylidene. The weight average molecular weight (Mw) determined by light scattering method is generally 10,000 or more, preferably 20,000 to 2
It is 00000. Of course, low molecular weight polycarbonates containing S-triazine rings can also be produced. The new polycarbonate end group is
Does not have a decisive effect on the properties of the product. For the sake of completeness, the following may be mentioned as terminal group A to the left side of the structural formula glue and ■ and as terminal group B to the right side: glue and [A in 4' is H or C
OOR12, where R12 represents a phenyl group or a mono- or polysubstituted phenyl group, and A
further represents a group of the general formula {7}, where Z, R, Q and a have the same meanings as above, and B is -O
represents R12, where R12 has the same meaning as above. A polycarbonate containing an S-triazine ring and a functional group has not been known so far. The novel polycarbonates according to the invention can be prepared by forming polycarbonates of the formula tl- or (2) via the substituent Q in the case of the formula '1- or via the sulfo group in the case of the formula II and/or via the groups R5 and R6.
As a result of the introduction of the S-triazine structural unit, it is particularly noteworthy that it is suitable for polymer-like reactions. Polycarbonates having a structural unit of the formula (3), in which Q represents -COO days or -S03 days, surprisingly exhibit absorption of organic solvents when they are insoluble in the usual solvents for polycarbonates. The properties of the improved polycarbonate 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.
A proportion of triazine of formula (1) of up to 5 mol %, preferably from 10 to 1 mol %, is sufficient. The stability of these polycarbonates can be adjusted, inter alia, by introducing branching or crosslinking agents. For example, using such products it is possible to almost quantitatively remove hydrocarbons from mixtures or aqueous solutions of aliphatic or aromatic hydrocarbons, such as methylene chloride, chlorobenzene, benzene or xylene, with water. , which is very important for the purification of industrial wastewater. A further object of the invention is therefore to provide aliphatic
In order to adsorb and remove alicyclic, aromatic and halogenated hydrocarbons from mixtures or aqueous solutions with water or aqueous solutions containing inorganic salts, Q contains an S-triazine ring, and Q is - It is to provide a method of using a polycarbonate of formula {3} exhibiting a COO day or -S03 day and Z, R, a, X and n being as defined above. 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 from aqueous solutions containing inorganic salts. Provides a method of using a polycarbonate of the formula Z represents NH, Q represents -COO, a represents 1, X represents and t and R are as defined above, containing a triazine ring The high molecular weight polycarbonate of the present invention containing an S-triazine ring can be prepared using an organic compound inert to the following reactants 8, 9 and 10 according to a conventional method for producing trisubstituted S-triazines. in a solvent, 'b} in an aqueous alkaline medium, or {c} in one or two phases of an organic solvent inert to the reactants and the aqueous alkaline phase [where Hal is F, CI, B
and 1, preferably CI, and Z, R, Q and a are as defined above] or a dihalogeno-S triazine of the formula [9] [wherein R5 and R6 are as defined above] The dichlororubistriazinyl compound and other formulas HO
2 to 201 equivalents of an aromatic dihydroxy compound of -X-OH OQ [in the above formula, X is as defined above] in the presence of a broton acceptor,
Preferably, 2 to 201 equivalents of an alkali metal salt of an aromatic dihydroxy compound having the formula are used to react 0 to 300 times, preferably at 30 to 150°C for 0.2 to 2 hours, and then a known method for producing polycarbonate is carried out. , preferably according to the interfacial polycondensation method, and depending on the choice of the molar ratios used in the reaction of 8 or 9 with 10, are formed as intermediates, S-triazine ring-containing dihydroxy compounds of formulas 11 and 12, or alkali metal salts thereof. as such or further mixed with 10 and reacted with a bischlorocarbonate of phosgene and/or an aromatic dihydroxy compound 10 and/or a carbonate oligomer made from 10 and containing chlorocarbonate end groups, but as such and /or as an alkali metal salt thereof and/or as a bischlorocarbonate ester thereof and/or as a carbonate oligomer produced from dihydroxy compound 10 and containing a chlorocarbonate group. It can be prepared by using not more than 201 equivalents per equivalent and at least 1.05 chlorine equivalents linked via one CO- to the equivalent of phenolic OHI. Furthermore, mutually different dihalogeno-S triazines 8 and/or
or different bistriazinyl dichlor compounds 9 and/or
Alternatively, it is also possible to prepare the corresponding desired compounds using mixtures of 8 and 9 and/or different aromatic dihydroxy compounds 10. Furthermore, it is also possible without difficulty to react the reaction products of 8 and 9 with aromatic dihydroxy compounds with other aromatic dihydroxy compounds and the polycarbonate-forming compounds mentioned above. The process involves the production of bishydroxy compounds 11 and/or 12 containing an S-triazine structure and the subsequent production of polycarbonates based on 11 and/or 12 and optionally other dihydroxy compounds to separate intermediates 11 or 12. It has the feature that it can be carried out in the same reaction medium and in the same reactor without being separated. It is possible, but not necessary, to produce the S-triazine-containing bisphenol in a separate process. A further special advantage of the process for preparing polycarbonates of the formula 3 containing an S-triazine structure is that instead of the purified dihalogeno-S-triazine 8, a trihalogeno-S-triazine, preferably cyanuric chloride, and a compound of the formula ( Q) Purified dihalogeno S-triazine solution obtained from the reaction of a-(RnaZ-day (13) [in the above formula, Z, R, Q and a are as defined above] with a nucleophilic compound) Or the suspension can be used directly for further condensation with aromatic dihydrooxy compounds 10.An alternative method for the preparation of polycarbonates according to the invention is to combine dihalogeno S-triazines 8 and/or 9 with bishydroxy The reaction with compound 10 is expressed by formula 3 and/or 4 (
However, Hal has the meaning indicated for 8, but preferably indicates CI) in the presence of 0.01 to 5 mol% of trihalogeno S-triazine, and the reaction mixture is added as an intermediate. Incorporation of a trifunctional hydroxy compound of formula 14 followed by branching of the polycarbonate via this S-triazine ring by reaction with a polycarbonate-forming compound such as phosgene and/or a bischlorocarbonate of a bishydroxy compound. The dihalogeno-S-triazines 8 and 9 used for the preparation of the homopolycarbonates or copolycarbonates according to the invention are not known, but are prepared according to methods known from the chemical literature. Dichloro-S-triazines of formula 8, in which HE1 represents CI, are prepared, for example, by reacting cyanuric chloride with an aliphatic or aromatic amine having a functional group Q, an alcohol, a phenol, a mercaptan or a thiophenol [e.g. J. R
．． Thurston et al., J. Am. ch
em. S ratio. 73, 2 spots 1 (i951): Japan, Koopman (Khada pman) et al., Rec. trav. Chem.
Pa$-Bas7 & 967 (1959); Koopman and J. Daams, Rec. tra
v. chim. Pays-S77, 235 (19 spots)
, JP, Nestler and JP. Furst (
Furst), J. prakt. Chem. [4] 22
, 173 (1963); Hmrobin, S.
), J, Chem, S ratio, [London] 1963,
4130: German Publication No. 117; see German Publication No. 1670832]. The dichlororubistriazinylaminostilbene derivatives of formula 9 are described, for example, in DE 1670832'
Accordingly, it is produced by reacting an aminodichlorotriazine compound with 4,4'-diaminostilbene-2,2-disulfonic acid or a salt thereof. An example of a dihalogeno S-triazine of formula 8 suitable for the preparation of a polycarbonate of formula 3 having an S-triazine structure is obtained by combining cyanuric chloride with the following compound according to known methods:
: Compounds obtained by reacting at a molar ratio of 1: hydroxyacetic acid, hydroxyacetic acid n-butyl ester, 2-hydroxypropionic acid (lactic acid), 2-hydroxypropionic acid ethyl ester, 2-hydroxysuccinic acid (malic acid) , 2-hydroxypropane-1.
2,3-tricarboxylic acid (citric acid), mercaptoacetic acid, 2-hydroxyethanesulfonic acid (isethionic acid),
2-aminoethanol, N-methylethanolamine,
diethanolamine, 3-amino-1-propanol,
1-amino-2-pro/gnol, diisopro/gnolamine, dihydroxy-ten-butylamine, trihydroxy-ten-butylamine, aminoacetic acid (glycine), methylaminoacetic acid, 3-aminopropionic acid,
4-Aminobutyric acid, 6-aminohexanoic acid, 11-aminoundecanoic acid, aminosuccinic acid, 2-aminoglutaric acid, methionine, 2-aminoethanesulfonic acid (taurine), N-methylaminoethanesulfonic acid, 3- Hydroxybenzoic acid, 3-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acid, 4-mercaptobenzoic acid,
4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid propyl ester, 3-chloro-4-hydroxybenzoic acid, 4-hydroxyphthalic acid, phenol-
3-sulfonic acid, phenol-4-sulfonic acid, 2.6
-dichlorophenol-4-sulfonic acid, 1-naphthol-4-sulfonic acid, 1-naphthol-3,6-disulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-5,7-disulfonic acid, N-(2-hydroxy ethyl)-cyclohexylamine, aminoacetic acid ethyl ester, 6-amino/hexanoic acid ethyl ester, 2-hydroxypropionic acid methyl ester, 6-hydroxyhexanoic acid ethyl ester, mercaptoacetic acid methyl ester, mercaptosuccinic acid diethyl ester, 2-hydroxyethylani1' anilinomethanesulfonic acid, anilinoacetic acid, hydroxyethyl m-toluidine, m-
Toluidinomethanesulfonic acid, 2-aminobenzoic acid
2-aminobenzamide, 3-aminobenzoic acid, 4-
Chloro-3-aminobenzoic acid, 4-chloro-3-aminobenzamide, 6-chloro-3-aminobenzoic acid, 5-
Nitro-3-aminobenzoic acid, 6-nito. -3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminobenzoic acid ethyl ester, 4-aminobenzamide,
2-nitro 4-aminobenzoic acid, 4-amino-3-methylbenzamide, 3-amino-4-methylbenzoic acid,
5-aminoisophthalic acid, 4-aminonaphthalene-1.
8-Dicarboxylic acid, 3-amino-4-methoxy-benzoic acid, aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-3-sulfonic acid amide, 3-aminobenzenesulfonic acid anilide, 3-aminobenzenesulfonic acid N-methylanilide, 6 -Chloraniline-3-sulfonic acid, 4-chloroaniline-3-sulfonic acid, aniline-4-sulfonic acid, 4-aminobenzenesulfonic acid amide, diphenylamine-4-sulfonic acid, 4-pencylaminobenzenesulfonic acid, 2,5-dichloro-4
-aminobenzenesulfonic acid, 4-aminotoluene-2
-sulfonic acid, 4-amin/toluene-2-sulfonic acid anilide, 5-aminotoluene-2-sulfonic acid, 4-aminophenylmethanesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 8-
Aminonaphthalene-1,3,5-trisulfonic acid or 2
-Mercaptobenzothiazole sulfonic acid. Of course, many other dihalogeno S-triazines of formula 8 can also be used as starting compounds for the preparation of polycarbonates of formula 3 containing S-triazine rings. Reacting with 4,4'-diaminostilbene-2,2-disulfonic acid or a salt thereof to give a dichloroubistriazinyl compound of formula 9 suitable for the preparation of polycarbonate of formula 4 containing an S-triazine structure. Examples of aminodichlorotriazine compounds of formula 15 which can be prepared according to known methods are cyanuric chloride and ammonia, methylamine, ethylamine or butylamine, dimethylamine, jetylamine or dipropylamine, monoethanolamine or jetanolamine, N- Methylethanolamine, aminoacetic acid, 4
-aminobutyric acid or 6-aminohexanoic acid, aminoacetic acid ethyl ester or 8-aminopropionic acid ethyl ester, aniline, aniline-3-sulfonic acid, aniline-
It is a compound obtained by reacting 4-sulfonic acid or cyclohexylamine, pyrrolidone, piveridine or morpholin in a molar ratio of 1:1. Examples of suitable aromatic dihydroxy compounds of formula 10 are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(hydroxyphenyl)-alkanes,
monocycloalkane, monosulfide, monoenal, -ketone, monosulfoxide -sulfone, and also Q.Q'-bis(hydroxyphenyl)-diisopropylbenzene and the corresponding nuclear alkylated or nuclear halogenated compounds. . Some suitable aromatic dihydroxy compounds are, for example, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-bropane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, -bis-(3,5-dichloro-4-hydroxyphenyl)
-propane, 2,2-bis-(3,5-dibromo4-
hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-ethane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and trinuclear bisphenols such as Q.Q'-bis-(4-hydroxyphenyl) )
-p-diisopropylbenzene. These and other bisphenols suitable for making high molecular weight polycarbonates according to the present invention are described in U.S. Pat.
No. 0131, No. 2991273, No. 2999835, No. 29 Nada 46, No. 3014891, No. 30283
No. 65, No. 3062781, No. 3148172, No. 3271367, No. 32713 and No. 32800
No. 78 and DE 1570703. Suitable reagents for defining the molecular weight include phenols and mono- or polysubstituted phenols, as well as those of general formula 16 [
In the above formula, Z, R, Q, a and Hal have the same meanings as above]. These compounds are produced as by-products during the preparation of the corresponding dihalogen derivatives. The polycarbonate according to the present invention containing an S-triazine ring and consisting of the structural unit of formula 3 can be produced, for example, as follows. First, according to known methods, the proton acceptors (e.g. NaOH A trihalogen/-S triazine, e.g. cyanuric chloride, of formula 1 in e.g.
3 with a nucleophilic compound in a 1:1 molar ratio. The dihalogeno S triazine 8 obtained is then separated from the reaction mixture and purified or directly subjected to the next reaction with the aromatic dihydroxy compound as a solution or suspension in the solvent used for this reaction without further work-up. use.
In a separate container, a 1:2 molar ratio of the aromatic dihydroxy compound and an alkali metal hydroxide, preferably sodium hydroxide or potassium hydroxide, are dissolved in sufficient water to approx.
A 0% aqueous alkali metal salt solution of 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. Further diluted or concentrated alkali metal salt solutions or suspensions can also be used without loss. Dihalogeno S-triazine isolated and purified by recrystallization, distillation or elution, or the presence or absence of an organic solvent such as acetone, methyl ethyl ketone or dioxane or an inert, water-immiscible organic solvent for the dihalogenotriazine. A solution or suspension of the isolated dihalogeno-S-triazine dissolved or suspended in water is added to the aqueous alkali metal salt solution or suspension in a molar ratio of 201:1 to 2:1. Add in portions or all at once. Inert organic solvents include, for example, chlorinated hydrocarbons such as CI2, CHC13, CC14, ethylene chloride and trichlorethylene, benzene, toluene, xylene, chlorobenzene, chlorotoluene, dichlorobenzene and higher chlorine. aromatic compounds can be used. It is likewise possible to first take the dichlortoIJ azine solution or suspension and add the alkali metal salt solution or suspension of bisphenol. The well-incubated one-phase or two-phase mixture is maintained at a temperature of 0 to 300°C, preferably 30 to 1500°C, for 0.2 to 2 q hours. Suitably, the organic solvent, such as acetone, which is free from the reaction of cyanuric chloride with 13 is removed during this reaction step. Generally, the condensation of dichloro-S-triazine and hydroxy compound is completed within 5 hours. All reactions up to this point are carried out under an inert gas atmosphere, such as nitrogen. The resulting alkali salt of bisphenol of formula 11 containing an S-triazine ring is the dihalogeno-S-triazine and aromatic dihydre used. Depending on the nature of the compound, it is more or less easily soluble in water. After condensation, a solution, emulsion or suspension is thus present. This is of less importance with respect to the cross-forming of the polycarbonate according to the invention. A side reaction between the aromatic dihydroxy compound and two molecules of dihalogeno-S triazine results in the formation of formula 17 [wherein X, Z, R, Q, a and the ratio 1 are as defined above. ] If you want to prevent the formation of intermediate products,
It is advantageous to choose a large excess of bisphenol and to carry out both the addition of the dihalogeno S-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 aromatic polycarbonate is added to a one-phase or two-phase mixture in which an alkali metal salt of an aromatic dihydroxy compound and an alkali metal salt of a bisphenol of formula 11 containing an S-triazine structure are dissolved or suspended, optionally in excess. a suitable solvent such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane, or a chlorinated aromatic such as dichlorobenzene, chlorotoluene or chlorobenzene, and after addition of the molecular weight limiting reagents mentioned above, Compounds that produce carbonates, such as phosgene,
The reaction with a carbonate oligomer prepared from a bischlorocarbonate or a dihydroxy compound and containing a chlorocarbonate end group is carried out using an alkali, depending on the nature of the bisphenol component 10 used and the bisphenol 11 having an S-triazine structure, according to known methods. Perform at pHIO ~14 in medium. The polycarbonate containing S-triazine rings and prepared according to the two-phase interfacial process and precipitated from the reaction mixture or dissolved in the organic phase is reacted according to customary methods, e.g. by alkali IJ, by acidifying the reaction mixture; Separate the precipitated polycarbonate in a furnace, wash it until it becomes neutral,
Alternatively, the polycarbonate present in solution is isolated by precipitating it from the organic phase or by evaporating the solution of washed polycarbonate until neutral. The polymer thus produced has a low molecular weight or a high molecular weight depending on the amount of the lotus chain terminator added. diha of formula 8, where Q represents -COO, -S03 or an aliphatic OH group. With geno S-triazine, -COO days, -S03 by optionally carrying out the polycarbonate production at high pH values, preferably pH > 13 according to the method described above.
It is also possible to produce polycarbonates containing S-triazine rings that are branched or crosslinked with di- or aliphatic OH. Polycarbonate having the structural unit of formula 4 can be produced in the same manner as polycarbonate having the structural unit of formula 3. The novel polycarbonates containing S-triazine rings of formulas 3 and 4 according to the invention can be obtained by introducing S-triazine structural units of formulas 1 and 2 by the substituent Q of formula 1 or by the S03 group or by the S03 group of formula The two groups R5 and R6 make it very suitable for polymer-like reactions. For example, S
Polycarbonates containing triazine structures and containing aliphatic PH groups can be used with aminoplasts or limited intermediate products thereof, such as melamine resins, benzoguanamine resins or urea resins, phenolic resins or diisocyanates and polyisocyanates. Crosslinking gives a hard coating. Polycarbonates of formulas 3 and 4 containing ester and carboxyl groups give hard coatings when crosslinked with, for example, bisoxazolines or jepoxide and polyepoxide compounds, such as glycidyl esters. The lacquer may optionally contain pigments and customary lacquer auxiliaries. Polycarbonates of the structural unit of formula 3, in which Q represents a carboxyl or sulfoxyl group and are inert to many organic solvents at a certain molecular weight, can be prepared from aqueous solutions of aliphatic, cycloaliphatic, aromatic and halogenated hydrocarbons or water. It is extremely suitable for adsorption separation or removal of these from mixtures with Example 1 2.2-bis(4-hydroxyphenyl)-propane (bisphenol A) and 2-jetanoamino-4.
Polycarbonate water with chain stopper from 6-dichloro-S-triazine (95:5 mole parts) 180% bisphenol A21.7% (0.095 mole) and Na
To a solution of 7.6 mol (0.19 mol) of OH under a gentle nitrogen flow, chlorbenzene 60 [2]
1.27 (5 mmol) of -jetanolamino-4,6-dichloro-S triazine and 40.2 days of NaB were added. The well-mixed two-phase mixture was then heated to about 90 oo for 4 hours. It was then cooled to about 20 qC and the intermediate product precipitated. p-tert-butylphenol 0.43 mmol (2.86 mmol) and CH2CI21
After adding COC 1213.4 (0
．． 135 mol) at 24-27° C. for about 30 minutes. During this phosgenation, the intermediate product dissolved, but the pH value was kept at 11-12 by adding INNaOH dropwise. After adding 5.5M of 1% aqueous triethylamine solution, the mixture was heated for an additional 10 minutes at pH 12. During this period the two-phase mixture became very viscous. 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. 100oo and 15
Drying for 1 hour at Hg gave 21.4 mm (86%) of the polycarbonate containing S-triazine. The relative viscosity (CH2CI2100 underground product 0.5 min, 2500) was 1.254. N content: calculated value 1.12%, analyzed value 1.04% aliphatic O
H%: calculated value 0.68%, analytical value 0.62% The polycarbonate produced in Example 1 was dissolved in chlorobenzene,
It was crosslinked with tolylene di-socyanate at the boiling point. The hard product precipitated from this reaction solution was insoluble in organic solvents. Example 2 Bisphenol A and 2-jetanolamino-4/6
Copolycarbonate bisphenol A with chain terminator from dichloro-S-triazine (78:22 mole parts), 20.1 moles (0.088 mole) and 7.0 mole NaOH
4 ml (0.176 mol) was dissolved in 180 ml of water under a N2 atmosphere, about 0.2 ml of NaB was added, and the solution was warmed to about 60-70 mol. This was followed by 6.27 hours of 2-jetanol-amino-4,6-dichloro-S-triazine in 60 hours of chlorobenzene (24 hours).
．． A suspension of 8 mmol) was added dropwise thereto, and the reaction was then carried out at 80-9000 for 2 hours with vigorous stirring. After cooling to room temperature, adjust the pH to 11 with dilute hydrochloric acid, add CH 12120 skin and p-rt-butylphenol 1.3.
15 mmol (875 mmol) and the mixture was then reduced to a COC of 129.3 mmol (0
．． 0 mol) was reacted. After adding 6.3' of a 1% aqueous triethylamine solution, the mixture was kept at pH 11 for a further 1 hour, the organic phase was washed to neutrality and the polycarbonate was isolated by evaporation. Yield: polycarbonate containing triazine 24.2
Evening (93%) rel (CHBC12100's medium product 0.5 qo, 25 qo): 1.078N storage amount: Calculated value 5
．． 35%, analytical value 4.96% OH number: calculated value 107, analytical value 91 The polycarbonate produced in Example 2 was mixed with hexamethylolmelamine hexamethyl ether in m-cresol in the presence of p-toluenesulfonic acid for 20,000%.
A hard coating was obtained by heating to . Example 3 Bisphenol A and 2-jetanolami/-4・6
-Copolycarbonate crosslinked with chain terminator from -dichloro-S triazine (90:10 molar parts) Bisphenol A 20.6 molar parts (0.09 molar parts)
180 mol of water), 7.2 mol of NaOH (0.18 mol) and 2.53 mol of 2-diethanolamino-4,6-dichloro-Striazine (0.01 mol) while adding a NaB ratio of 180 mol of water and chlorobenzene. The reaction was carried out for 4 hours at reflux temperature in a mixed solvent of 60%. After cooling, add p-ten-butylphenol for 0.27 hours (1
．． 8 mmol) and CH2CI2140',
Adjust the pH to 14 with NaOH solution and add COC1211
．． pH 14 while vigorously pouring 9 yen (0.12 mol)
I let it pass. After this phosgenation, the aqueous phase was free of bisphenol salts. Then 4.9 parts of 1% triethylamine aqueous solution Z was added and the mixture was condensed. After stirring for about 3 minutes, the mixture first became very sticky and finally became rubbery, which was no longer of any use even with continued stirring. The gel-like swollen polycarbonate mass was furnaced, treated repeatedly with dilute phosphoric acid and then washed with water. 100 0
After drying for 2 hours in a vacuum drying chamber, a hard viscous material was obtained. This product was insoluble in most organic solvents. N content: calculated value 2.29%, analyzed value 2.20% Example
4 bisphenol A and N-(4,6-dichloro-S-
triazin-2-yl)-p-aminobenzoic acid (90:
10 mole parts) of copolycarbonate water 190% of bisphenol A20.6 parts (0.09 moles) and Na
N-(4.6
-dichloro-S-triazin-2-yl)-p-aminobenzoic acid (0.01 mol) was added, and NaB
A temperature of 0.2% was added and the mixture was then heated to about 90-95° C. for 5 hours under a N2 atmosphere. During this heating period, the dichloro-S-triazine dissolves. After cooling to 20qC, a clear solution was obtained. Then, after adding CH2CI2200', the pH was adjusted to 1.
The mixture was reacted with COC 121.9 (0.12 mol) at pH 12 as described in Example 1.
A milky white, slightly viscous solution was then obtained. Then p
The pH was adjusted to 13, 8 parts of a 1% aqueous triethylamine solution was added, and the mixture was heated for an additional hour at pH 13.
After acidification with dilute phosphoric acid, the mixture was extracted by shaking twice with distilled water and the entire two-phase mixture was added dropwise to methanol as the separation was very slow. At this time, polycarbonate precipitated as a white powder. Yield: 24.7 units of triazine-containing polycarbonate (1
00%) N content: calculated value 2.26%, analytical value 2.22%
COOH%: Calculated 1.82%, Analyzed 1.7% The product was resistant to e.g. CH2CI2, tetrahydrofuran, dioxane and pyridine. The N-(4,6-dichloro-S-triazin-2-yl)-p-aminobenzoic acid used was prepared as follows: Acetone 1350 was added to a solution of 92.2 mol of cyanuric chloride (0.5 mol) in acetone 650. 886 mol of p-aminobenzoic acid (0.5 mol) and 50 mol of triethylamine
．． A suspension of 6 ml (0.5 mol) was introduced at 0-5°C. The reaction temperature was increased to 20°C over 90 minutes and the mixture was stirred for an additional 9 minutes. The precipitated reaction product was filtered out, washed with distilled water until free of chlorine, extracted twice with acetone under boiling, and dried at 50 oo/15 Hg. Yield: 114 min (80% of theory), melting point >30 p0. Analysis: Calculated value C42.1% Day 2.11 NI9.65
CI24.95 analysis value C42.7% day 2.17NI
9.2CI24.7 Example 5 Bisphenol A and N
Copolycarbonate from -(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (89.5:10.5 mol parts). In the same manner as in Example 4, bisphenol AI8.3 (
0.08 mol), NaOH 7.2 mol (0.18 mol) and N-(4,6-dichloro-Striazinyl-2)-
p-aminobenzoic acid 5.7 mol (0.02 mol)
The reaction was carried out at 90-95oC in 20M for 5 hours. After cooling, a solution of 31.8 molar (0.09 mol) of CH2CI2620 bisphenol A bischlorocarbonate was introduced over a period of 2 minutes with vigorous agitation into the yellow solution of the sodium salt of a dihydroxy compound, and then 1% 15.2 mm of aqueous triethylamine solution was added and the mixture was further stirred while maintaining the pH of the aqueous solution at 12. The two-phase mixture became very viscous within a short time. After about 2 minutes, a spongy gel precipitated and the reaction was stopped because oak cassava could no longer be formed. The reaction mixture was acidified with dilute phosphoric acid and the resulting gel was heated in an oven. The furnace fluid was exclusively aqueous phase and all CH2CI2 was adsorbed onto the triazine-containing polycarbonate. Next, the polycarbonate was suspended in distilled water, washed until neutral, and
g for 2 hours. Yield: 46.5 g of flocculent white polycarbonate containing triazine (99%) N yield: Calculated value 2. % Paper, Assay 2.25% The product was dissolved in dimethylformamide (DMF). COOH% (in DMF): calculated value 1.91%, analyzed value 1
．． 70% Example 6 Bisphenol A and N-(4,6-dichloro-S triazinyl-2)-p-aminobenzoic acid (89.5:
Removal of hydrocarbons from aqueous solutions by adsorption onto copolycarbonate (10.5 molar parts) A 1.5 molar internal diameter, 30 molar column was packed with 10 molar parts of the copolycarbonate prepared in Example 5 (10 molar parts). Filled with bulky material, filling height approximately 20 meters). This column was loaded with an aqueous solution of hydrocarbon and a salt solution (in each case 50%
M) was continuously passed through the column, and the content of hydrocarbons in the aqueous solution before and after passing through the column was determined by gas chromatography (see Table 1): Table 1 o) Detection Limit Example 7 Bisphenol A and N-(4. Copolycarbonate with chain terminator from 6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (95:5 molar parts) Analogously to Example 5, 9.1 molar parts of bisphenol A (0.04 molar parts) in alkaline solution mol) to N-(4,6-dichloro-S-triazinyl 2)-p-aminobenzoic acid 1.5
p-ter (5.26 mmol), then p-ter
t-Butylphenol 474.3 o (3.16 mmol) was added, then a solution of bisphenol A bischlorocarbonate 21.2 mmol (0.06 mmol) in CI 2180M was added and 1% aqueous triethylamine solution was added.
0.1 Kite was added and the mixture was heated to pH 13. After about 1 minute, the triazine-containing polycarbonate precipitated as a jelly and was processed as described in Example 5. Yield: 26.0 hours (99%) of white granular product. N storage amount: Calculated value 1.12%, analyzed value 1.02% COO daily content: Calculated value 0.897%, analyzed value 0.899% Example 8 Bisphenol A and N-(4,6-dichloromethane) Copolycarbonate with chain terminator from S-triazinyl-2)-p-aminobenzoic acid (Satoshi: 2 mol parts) a) Similarly to Example 5, 9.1 mol of bisphenol A (0.04 mol) was mixed with N -(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid 0.57 mmol (2 mmol) and then at pH 12-13
% aqueous triethylamine solution while adding 21.2% aqueous triethylamine solution (0.06%
mole) and p-ten-butylphenol 38.3 o
(2.55 mmol). After 10 minutes, the copolycarbonate precipitated as a jelly. This was processed as described above. Yield: 25 min (97%) N content: Calculated value 0.439%, analyzed value 0.41%'b'
When the reaction described in {a} was carried out in the presence of p-tert-butylphenol 766 9 (5.11 mmol), the polycarbonate remained dissolved in the methylene chloride. After addition of triethylamine, the mixture was kept at pH 1 for an additional hour.
The organic phase was washed until neutral, then evaporated and the residue was washed at 10°C. It was dried for 6 hours with C-15-Hg. Yield: copolycarbonate containing triazine 22.2 min (86%) rel (C ratio CI 21
00 Underground products 0.5 pm, 250 o): 1.267 N total amount: Calculated value 0.4 I%, analyzed value 0.41% COO day content: Calculated value 0.349%, analyzed value 0.34% Example 9 Copolycarbonate from bisphenol A and N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (80:20 mole parts) Analogous to Example 5, copolycarbonate from bisphenol AIO (0.044 mole parts) ), NaOH8 (0.2 mol) and N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid 5.7 mol (0.0
2 mol) in 250 mol of water and then the C ratio CI2 while adding 10.1 mol of a 1% aqueous triamine solution.
The mixture was condensed with 12.7 mmol (0.036 mol) of bisphenol A bischlorocarbonate in a 230°C. Five minutes after adding the triethylamine, the polycarbonate precipitated as a jelly. After stirring for an additional hour, the mixture was processed as described above. The gel was then washed until neutral and dried under 8000/15 Hg for 3 m hours. Yield: white fine granular powder 22 min (92%) N content: calculated value 4.65%, analyzed value 4.48% COO day content: calculated value 3.74%, analyzed value 2.96% Example 10 bis Copolycarbonate branched with cyanuric chloride from Fer A and N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (90:10 molar parts) Analogously to Example 4, Bisphenol A 20.6 evenings (0
．． 09 mol) and N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid 2.85 mol (0.0
1 mol) of cyanuric chloride (0.22 molar) was dissolved in 190 molar of INNaOH solution and 40.5 molar of cyanuric chloride (0.22 molar) in 50 M dioxane.
A solution of 1 mmol) was added. This mixture was heated to 90-950 ml for 5 hours under nitrogen.
Heating to 0 and then cooling to 2000, the resulting clear solution was mixed with CQC12150' and then adjusted to pH 1
2 was reacted with COC1211.9 mol (0.12 mol). After dilution with CI 2150%, 8.3 g of a 1% aqueous triethylamine solution was added and the mixture was strained for an additional hour. When acidified with dilute phosphoric acid, the triazine-containing polycarbonate precipitated as a gel. This was then processed as in Example 5. Yield: 24 linear products (97%) N content: Calculated value 2.06%, analyzed value 2.08% Example
11 Bisphenol A and N-(4,6-dichloro-S
Copolycarbonate from -triazinyl-2)-sulfanilic acid (90:10 mol parts) according to Example 4, 20.6 mol of bisphenol A (0.09 mol), 7 mol of NaOH
．． 2 (0.18 mol) and N-(4,6-dichloro-
Na salt of S-triazinyl-2)-sulfanilic acid3.
43 (0.01 mol) and then the mixture was
React with COC1211.9 (0.12 mol) in H12 and pH the whole for another hour after addition of triethylamine.
I performed rope worship at 13. When the reaction product was made acidic, the copolycarbonate precipitated as a white powder. This was then separated in a furnace, suspended in water and washed until neutral, then rinsed with methanol and dried at 8000/15 Hg for 6 hours. Yield: Copolycarbonate 23.5 kg (%) N content: Calculated value 2
．． 21%, analytical value 2.16% Example 12 Bisphenol A and N-(4,6-dichloro-S-triazinyl-
2) -p-Aminobenzoic acid ethyl ester (85.7:
According to Example 1, a solution of 20.6 moles of bisphenol A (0.09 moles) and 7.2 moles of NaOH (0.18 moles) was mixed with chlorobenzene. The mixture was reacted with a suspension of 4.69 ml (15 mmol) of N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid ethyl ester at 80 to 90 qo for 3 hours. After cooling to room temperature, a grainy intermediate product precipitated. After addition of CH2CI2120, the pH was adjusted to 13 and the mixture was reduced to pH 13 with COC1211.9 (0.1
2 mol). After adding 5' of the 1% aqueous triethylamine solution, the mixture was stirred for approximately 15 minutes until the polycarbonate precipitated as a gel. The precipitated product was treated as described in Example 5. Yield: 26 copolycarbonates with triazine content (100
%) N content: calculated 3.22%, analyzed 3.15%. The IR spectrum (excluding KBd) clearly shows that this is a polycarbonate containing ester groups. This product was converted into dimethylformamide. N-(4,6-dichloro-S-triazinyl-2)- used
p-aminobenzoic acid ethyl ester is prepared by acetone (20
0 [)/Dioxane (50')/Water (300 [)]
0.5 mol of cyanuric chloride, 0.5 mol of p-aminobenzoic acid ester, and Na2C030.
By reacting while adding 25 mol, the reaction was carried out as described by Thurston et al. [J. Am. Chem. S
oc. , 732981 (1951)] for the preparation of 2-aminodichloro-S-triazine. The dichlorotriazine precipitated from the reaction mixture was purified by stirring with acetone. Yield: 76%, melting point 294-295 qo Calculated value: C46.05 days 3.22N17.9 CI22.
70 analysis value: C46.15 days 3.13N17.8 CI2
2.6 Example 13 Bisphenol A and N-(4.6
-dichloro-S-triazinyl-2)-copolycarbonate from glycine 2-amino-4,6-dichloro-S
- Teachings for the production of triazines [Thurston et al., J.
Am. Chem. Soc. 76, 2 spots 1 (1951)]
According to the following, 1.84 molar chloride (0.01 mol) and 0.9 glycine in acetone paste (7:11 parts by volume)
(10.5 mmol) was added to NaOHO. 84 evening (2
The reaction was carried out at approximately 0° C. while adding 1 mmol), and the mixture was stirred for an additional hour and allowed to warm to room temperature. 9.6 mmol (42 mmol) of 042 underground bisphenol A in a bright red dichlorotriazine solution in acetone/water.
and 3.36 mmol (84 mmol) of NaOH and gradually heated the mixture to about 90-950C;
During this period acetone was distilled off from the reaction solution. After distilling off the acetone, the mixture was heated for an additional 3 hours at 95-1000C. The light yellow solution was then cooled to room temperature, distilled with 100 g of water and introduced with vigorous stirring a solution of 16.96 g (48 mmol) of bisphenol A chlorocarbonate and 10.1 g of a 1% aqueous triethylamine solution. was added and the mixture was further stirred at pH 13. After about 15 minutes, the polycarbonate precipitated as a jelly. The reaction was stopped and the polycarbonate was treated as described in Example 5. Yield: linear white copolycarbonate 22.3
Evening (93%) N content: calculated value 2.32%, analyzed value 2.2
8% COO daily amount: calculated value 1.87%, analyzed value 1.7%
This product was able to adsorb approximately 38 times its weight of CH2Cl2. Example 14 Bisphenol A and N-(4,6-dichloro-S triazinyl-2)-6-aminohexanoic acid (90:10
Similar to Example 13, 1.84 molar parts of cyanuric chloride (0.01 mol) were added to 1.8 molar parts of 6-aminohexanoic acid. N-(4,6-dichloro-S-triazinyl-2) by reacting with Madarayu (10.5 mmol)
) -6-aminohexanoic acid was prepared, the resulting white suspension was condensed with 9.6 mmol of bisphenol A (4.2 mmol), and in the dark the acetone resulting from the initial reaction was removed from the mixture. Then, after addition of a 1% triethylamine solution, a colorless solution of the dihydroxy compound was dissolved in bisphenol A bischlorocarbonate ester 16 in methylene chloride.
．． Polycondensation was carried out with a solution of 96 mmol (48 mmol) at 20-25° C. for 1 hour to pH 13T. The organic phase was separated, acidified with dilute phosphoric acid, washed until neutral and added dropwise to methanol. At this time, polycarbonate containing triazine was precipitated in the form of white lines. Yield: 21.4 days (87%) rel (CH2CI2100 [medium product 0.5 days,
25°C): 1.535N content: calculated value 2.27%, analytical value 2.12% COO day content: calculated value 1.62%, analytical value 1.59% Example 15 Bisphenol A and N-(4
Copolycarbonate from 6-dichloro-S-triazinyl-2)-2-aminobenzoic acid Analogously to Example 4,
Bisphenol A9.6 (42 mmol), NaOH
3.76 mmol and N-(4,6-dichloro-S triazinyl-2)-2-aminobenzoic acid 2.8
5 ml (10 mmol) in 180 ml of water (approximately 95 to 1 mol)
The reaction was carried out at 0 pO for 5 hours, and a solution of 16.96 molar bisphenol A bischlorocarbonate (48 mmol) of CH2C12170 was introduced into the resulting milky cloudy solution, and 10.1 m' of a 1% triethylamine aqueous solution was added. was added and the mixture was condensed at pH 13 for 1 hour. The viscous organic phase was then treated as shown in Example 14. Yield: linear white copolycarbonate 24.7 min (1
00%)
．． 5 evening, 25℃): 1.372N content: Calculated value 2.26
%, analysis value 2. Female COO content: calculated value 1.82%, analytical value 1.7% The N-(4,6-dichloro-S triazinyl-2)-2-aminobenzoic acid used was
Triethylamine 2 as an HCI receptor
Cyanuric chloride 3 in the presence of 0.3 moles (0.2 mol)
6.8 (0.2 mol) and 2-aminobenzoic acid 27.
4 (0.2 mol) at 0-2°C. The resulting reaction product was washed with diluted hydrochloric acid, then washed with water until chlorine was eliminated, and dried with acetone. Yield: 30.2 min (53%): Melting point > 330 k0 (
Decomposition) Analysis: Calculated value C42.1% Day 2.11% C
I24.95% Analysis value C42.4% Day 2.19%
CI24.9% Example 16 Bisphenol A and N-
Copolycarbonate from (4,6-dichloro-S-triazinyl-2)-2-aminoethanesulfonic acid (90:10 mole parts)
．． 84 units (10 mmol) to 2-aminoethane-1-sulfonic acid (taurine) 1.31 units (10.5 mmol)
The corresponding dichloro-S-triazine was prepared by reacting with Bisphenol A for 9.6 hours (42
mmol) at 60 to 95 oo. 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 g (48 mmol) of bisphenol A bischlorocarbonate in methylene chloride at pH 13 after the addition of 1% aqueous triethylamine. was polycondensed with a solution of After a further 30 minutes of lighting, the triazine-containing copolycarbonate precipitated out in the form of a jelly. This was then processed as described in Example 5. Yield: 23.8% (97%) N content: Calculated 2.27%, Analyzed 2.18% The product was able to adsorb about 36 times its weight of CH2CI2. Example 17 Bisphenol A and N-(4,6-dichloro-S-triazinyl-2)-5-aminoisophthalic acid (90:1
Copolycarbonate from Example 13 (Cyanuric chloride 1.0 molar parts) The shell (10 mmol) was first diluted with NaOHI in acetone/water. 24 evenings (31 mm IJ mole)
of 5-amino/isophthalic acid (10.9%) in the presence of
5 mmol) at 0-5°C, and the resulting yellow suspension was reacted with 9.6 mmol of bisphenol A (42 mmol) and 60 mmol of bisphenol A.
After condensation for 5 hours at ~90 qqo and finally adding 10.1 parts of a 1% triethylamine solution, the aqueous solution of the dihydroxy compound was combined with a solution of 16.96 parts (48 mmol) of bisphenol A bischlorocarbonate in methylene chloride.
Polycondensation was carried out at pH 13 for 1 hour at 0 to 2yo. After heating for about 10 more minutes, the precipitated copolycarbonate was treated as in Example 5. Yield: white, copolycarbonate 25% (99%) N capacity: calculated 2.22%, analyzed 2.20% COO daily capacity: calculated 3.58%, analyzed 3.33% This product was able to adsorb about 19 times its weight of CH2CI2. Example 18 Copolycarbonate from bisphenol A and (4,6-dichloro-S-triazinyl-2)-2-hydroxyacetic acid (90:10 molar parts) Similar to Example 4, 9.6 molar portions of bisphenol A (42 mmol), 3.6 molar portions of bisphenol A, 3.6 mmol of NaOH. 76
(94 mmol) and (4,6-dichloro-S triazinyl-2)-2-hydroxyacetic acid 2.24 mmol (10
mmol) was reacted for 4 hours at about 70-80 qC over 20 kg of water. After cooling to room temperature, a solution of 16.96 mmol (48 mmol) of bisphenol A bischlorocarbonate in CH2CI2200 was introduced, and 1% aqueous triethylamine solution was added.
0.1' was added and the mixture was allowed to condense at pH 13 for 1 hour. After stirring for an additional minute, the triazine-containing polycarbonate precipitated as a jelly and was treated as in Example 5. Yield: triazine-containing copolycarbonate 22.
9th grade (95%) N content: calculated value 1.74%, analyzed value 1.
70% COO daily amount: calculated value 1.87%, analyzed value 1.7
5% Example 19 Copolycarbonate 2-arylthio 4,6- from bisphenol and S-(4,6-dichloro-S-triazinyl-2)-mercaptobenzoic acid
Teachings for the preparation of dichloro-S triazine [J. D
ra 戊k and M. Sbobal. Chem. Zvest
i17, 482 (1963)], acetone/ratio ○
Medium cyanuric chloride 1. Masuyu (0.01 mol) and 4-mercaptobenzoic acid 1.54 (0.01 mol) were dissolved in NaOH
O. The reaction was carried out at about 0-5° C. while adding 800 mol (0.02 mol). A solution of 9.6 mmol of bisphenol A (42 mmol) and 3.36 mmol of NaOH was added and the mixture was heated to about 70-80°C, during which time the acetone was removed from the reaction solution. did. After cooling to room temperature, the product was reacted with 16.96 mmol (48 mmol) of bisphenol A chlorocarbonate as described in Example 13, and the polycarbonate product was treated as described in Example 5. Yield: triazine-containing copolycarbonate 2
4.6 (99%) N content: calculated value 1.69%, analytical value 1.55% Example 201.1-bis-(4-hydroxyphenyl)-cyclohexane, bisphenol A and N-(4.6 -dichloro-S-triazinyl-2)-p
Copolycarbonate from -aminobenzoic acid (42:48:10 mole parts) Analogously to Example 15, 1.1-bis-
(4-hydroxyphenyl)-cyclohexane 11.3
(42 mmol) of N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (2.85 mmol)
0 mmol), and the resulting mixture of dihydroxy compounds was reacted with bisphenol A bischlorocarbonate 1
9.96 min (48 mmol) was condensed. The resulting copolycarbonate was processed as described in Example 5. Yield: triazine-containing copolycarbonate 2
6 days (97%) N content: calculated value 2.08%, analytical value 2.
0% Example 212.2-bis-(3,5-dimethyl-
4-hydroxyphenyl)-propane and N-(4.6
Copolycarbonate from -dichloro-S-triazinyl-2)-p-aminobenzoic acid (90:10 molar parts) Analogously to Example 15, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) -Propane 11.95 evening (
42 mmol) of N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzoic acid (10 mmol) in 170 M of methylene chloride.
A solution of 19.2 mmol (48 mmol) of bis-chlorocarbonate of 2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane is introduced, and 1 mol of triethylamine is added.
．． After adding 36 mmol (13.5 mmol), the mixture was allowed to stand for a further 3 hours and then processed as described in Example 5. Yield: 31 units of triazine-containing copolycarbonate (9
4%) N content: calculated value 1.70%, analytical value 1.65% Example 22 Bisphenol A and N-(4,6-dichloro-S-triazinyl-2)-2-aminobenzamide (90:10 parts by mole) ) Bisphenol A9.6 (42 mmol) as in Example 4
, NaOH 3.36 mmol and N-(4.6 mmol)
-dichloro-S-triazinyl-2)-2-aminobenzamide2. The solution (10 mmol) was reacted for 5 hours at about 90-90% water over 170%. Next, I was furiously shouting at CH2CI2270 on my desk, bisphenol A bischlorocarbonate 16.96 pm (
48 mmol) was introduced, 10.1 mmol of 1% aqueous triethylamine solution were added and the mixture was condensed at pH 13 for 1 hour. The copolycarbonate precipitated as a jelly was treated as in Example 5. Yield: Copolycarbonate 21.6% (87%) N content: Calculated value 2.83%
, analysis value 2.75%.The IR spectrum (KBn method) clearly showed that the product was a polycarbonate containing amide groups. N-(4,6-dichloro-S-triazinyl-2)-p
-Aminobenzamide was prepared by adding cyanuric chloride (0.1 mol) to p-aminobenzamide 13 in acetone/water (1:1 parts by volume) with the addition of NaHC038.4 mol (0.1 mol). .6 evening (0.1 mole) and 0
It was produced by reacting at ~3°C. Yield: 51.6 min (91%), melting point > 30000 CI content: calculated value 25.1%, analytical value 24.9% Example 23
Copolycarbonate from bisphenol A and N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzenesulfonic acid amide (90:10 molar parts)) Bisphenol A9.6 as in Example 22 (42 mmol) was first mixed with N-(4,6-dichloro-S-triazinyl-2)-p-aminobenzenesulfonic acid amide 3.
2 mmol (10 mmol) and then the product was reacted with 16.96 mmol of bisphenol A bischlorocarbonate ester (4 mmol).
8 mmol). Approximately 20 minutes after the addition of triethylamine, the triazine-containing copolycarbonate precipitated as a jelly.
Yield: 25 yen (100%) N capacity: Calculated value 2.79%, analyzed value 2.7%N-(4.
6-Dichloro-S-triazinyl-2)-p-aminobenzenesulfonic acid amide was prepared by adding 18.4 mol of cyanuric chloride in acetone/water (1:1 parts by volume) with the addition of 0.1 mol of NaHC. Yu (0.1 mol)
to 4-aminobenzenesulfonic acid amide 17.2 days (0
．． 1 mol) at 0 to 3°C. Yield: 53.5 min (84%), melting point > 30000 CI content: calculated value 22.3%, analytical value 22.1% Example 24
Bisphenol A and 4,4-bis-[4-chloro-6
-diethanolamino-S-triazin-2-yl]-amino-2,2'-stilbendisulfonic acid (99:1
Similar to Example 4, copolycarbonate from molar parts)
Bisphenol A22.6 (99 mmol), NaO
H7.92 (198 mmol) and 4,4-bis-[
847 capes (1 mmol) of the disodium salt of 4-chloro-6-ditanol-amino-S-triazin-2-yl]-amino-2,2-stilbendisulfonic acid were added to 175 ml of water.
The reaction was carried out for 5 hours at a temperature of about 90 to 9,500 ℃. The mixture was cooled to 2000 °C, 9 (3 mmol) of p-ten-butylphenol 450 and CH2CI21
After adding 75% of the mixture, heat the mixture vigorously to C.
It was reacted with OC1214.9 (0.15 mol) at pH 12. Then 1% aqueous triethylamine solution 10.1
was added and the mixture was incubated for an additional hour at pll12. 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: 24.3 days (94%) sword rel (CH2CI2100 heart product 0.5 days, 2
5° C.): 1.245 N content: calculated 0.54%, analyzed 0.53% When irradiated with UV, the product showed a blue crab glow. Example 25 Bisphenol A and 4,4'-bis[4-chloro-6-diethanolamino-S-triazin-2-yl]
-amino-2,2-stilbendisulfonic acid (90:1
Similarly to Example 24, 20.5 moles of bisphenol A (0.09 moles) and 4,4'-bis(0.09 moles) in CH2CI2210
8.47 mol (0.01 mol) of 4-chloro-6-diethanolamino-S-triazin-2-yl)-amino-2,2-stilbendisulfonic acid was added to N in pine 0210.
The reaction was carried out while adding 7.2 moles (0.18 moles) of aOH, and then 0.75 moles (0.75 moles) of p-ten-butylphenol (
5 mmol) at room temperature and the mixture was then diluted with COC1
Phosgenation was carried out over 211.9 days (0.12 mol). After adding 10.1 cm of a 1% aqueous triethylamine solution, the mixture was heated for an additional hour at pH 12.5. After acidification, the polycarbonate with all the methylene chloride adsorbed precipitated out as a grainy product. After drying for 24 hours at 8000/15 side Hg, 30 g (99%) of the copolycarbonate remained. N storage amount: calculated value 4.61%, analyzed value 4.4% Example 2
6 bisphenol A and 4,4-bis-[4-chloro-
6-anilino-S-triazin-2-yl]-amino-
Copolycarbonate from 2.2-stilbenedisulfonic acid (99:1 molar parts) Similar to Example 24, bisphenol A22.6 molar (99 mmol) and 4.4-bis-[4-chloro-6-anilino-S] -Triazine-2-
yl]-amino-2,2-stilbenedisulfonic acid (0.824 g (1 mmol)) in 175 ml of water.
The product was phosgenated with COC 1214.9 (0.15 mol) and triethylamine (1% aqueous solution 10.1 ) was added and the mixture was allowed to stand for an additional hour. After acidification, the mixture was added dropwise to methanol. At this time the polycarbonate precipitated out as a white flocculent material.
Yield: 23.8 evenings (92%) sword rel (CH2CI21
00 upper middle product 0.5 night, 2500): 1.287N
Content: calculated value 0.54%, analyzed value 0.49% The product exhibited a green-blue crab glow upon UV irradiation. The aspects and related matters of the present invention are summarized as follows: 1 Contains polymerized divalent residues of at least one bisphenol and at least one S-triazine compound, in which each divalent S-triazine compound residues are present between two bisphenol residues, and two S-triazinyl ring carbon atoms of each S-triazinyl compound residue are each bonded to one oxygen atom of an adjacent bisphenol residue. and each S-triazinyl ring in the residue of the S-triazinyl compound has an organic group containing a functional group as a substituent, or is bonded to another S-triazinyl ring by the organic group and is bonded to another S-triazinyl ring by an oxygen, sulfur or nitrogen atom. A polycarbonate bonded to the carbon atom of the adjacent S-triazinyl ring. 2 From the structural unit of the general formula [in the above formula, B is a bisphenol residue, T is a S-triazinyl compound residue, and n is a number from 1 to 200, more preferably from 3 to 100] The polycarbonate mentioned in 1 above has become a hot topic. 3 The polycarbonate described in 2 above, wherein n is 3 to 100. 4 At least some of the S-triazinyl compound residues have the general formula [wherein Z is -○-, -S-, -NH-, or -NRI or -N-(R*)-(Q*)a] *, and 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, and a carbon number a heteroarylene group with up to 14 carbon atoms bonded to the groups X and Q and optionally with one or more substituents, or an alkalylene or aralkylene group with a total of up to 30 carbon atoms; RI is a group with a total carbon number of up to 20 an alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, a mononuclear or polynuclear aryl group, or an optionally substituted heteroaryl group having up to 14 carbon atoms, provided that the carbon atom is bonded to a nitrogen atom. , or 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 -COOday, -COOR2, -CONR3R4, -S03day, -S03day,
02NR3R4 or alcoholic hydroxyl group, provided that R2 represents an alkyl group having up to 4 carbon atoms, and R3
and R4 are hydrogen, which may be the same or different, and have 4 carbon atoms
represents a straight-chain or branched alkyl group and an optionally substituted phenyl group up to or together with the N atom form a 5- or 6-membered pseudosystem, and a and a* independently of each other The polycarbonate according to 1 above, which has an integer of 4]. 5 At least some of the residues of the S-triazinyl compound have the general formula [wherein R5 and R6 may be the same or different, H, or alkyl, hydroxyalkyl, carboxyalkyl, or alkoxycarbonylalkyl having up to 5 carbon atoms] a C5-C7 cycloalkyl group, or a C6-C,4 aryl group, or together with the N atom form a 5- or 6-membered ring system. 6. The polycarbonate of 4 or 5 above, in which any substituent present in R, R* and RI is selected from alkyl, alkoxy and alkylmercapto groups each having up to 4 carbon atoms, a halogen atom, a nitro group and a cyano group. 7 0.01 based on the S-triazinyl compound residue
Polycarbonate of the above embodiment crosslinked by introducing ~5 mol % of trivalent groups of S-triazinyl compounds. 8. The polycarbonate of 7 above, wherein the trivalent residue has the formula: 9 Bisphenyl is bis(hydroxyphenyl)-
The polycarbonate of the above embodiment which is Alcan. 10 Bisphenol has the general formula HO-×-OH OQ [
In the above formula, X optionally has one or more substituents o
-, m- or p-phenylene group], or a group having the general formula [In the above formula, R7 and R8 represent a hydrogen atom, an alkyl group having up to 4 carbon atoms, or a halogen atom, and may be the same or different. , and Y is a single bond, alkylene or alkylidene having up to 7 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 12 carbon atoms, 10-, 1S1, 1CO1, 1S○, 1S02- group ] or the general formula [in the above formula, R9, R1o and RII represent the same or different alkyl groups having up to 4 carbon atoms, and RII
may represent a hydrogen or halogen atom. The polycarbonate of 10 above, in which 11× is a base. 12 The polycarbonate of 1 above described in the Examples. 13 At least one monomer comprising the at least one divalent bisphenol residue and the at least one divalent S-triazinyl compound residue, by itself or together with bisphenol, is 1. The method for producing polycarbonate as described in 1 above, which comprises reacting with a polycarbonate-forming derivative. 14. The method of 13 above, wherein the derivative is phosgene. 15 The above 14, 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 molecular weight limiting compound. 17 The monomer is S of the general formula [in the above formula, X, Z, R and Q have the same meanings as above]
triazinyl bisphenol, produced by itself or mixed with bisphenol of general formula 10 from phosgene and/or bischlorocarbonate of bisphenol of general formula 10 and/or bisphenol of general formula 10; 4 above, characterized in that it is reacted with a carbonate oligomer containing a terminal group.
The manufacturing method of polycarbonate according to the above 13 to 16. 18 Dihalo-S triazine of the general formula [in the above formula, Z, R, Q and a are the same as defined above] and 2 equivalents of the bisphenol of the general formula 10 of the above 10 in the presence of a proton acceptor, or 17. The method of 17 above, which comprises a pre-step of producing S-triazinylbiphenyl of general formula 11 by reacting 2 equivalents of the alkali metal salt of the bisphenol of 10. 19. The method of 18 above, characterized in that the reaction as in 17 above is carried out without isolating the S-triazinyl biphenyl after the preceding step or transferring it to a different reaction vessel. 20 The monomer is bis-S-triazinylbisphenol of the general formula [in the above formula, R5 and R6 have the same meanings as in 5 above], which is itself or mixed with the bisphenol of the general formula 10. The polycarbonate of the above 5, characterized in that it is reacted with a carbonate oligomer produced from phosgene and/or a bischlorocarbonate of a bisphenol of general formula 10 and/or a bisphenol of general formula 10 and containing a chlorocarbonate end group. Manufacturing methods according to 13 to 16 above. 21 Dichloro-S-triazine of the general formula [in the above formula, R5 and R6 have the same meanings as 5 above] and 2 equivalents of the bisphenol of the general formula 10 of the above 10 in the presence of a proton acceptor, or 20. The method of 20 above, comprising a pre-step of producing bis-S-triazinyl biphenyl of general formula 12 by reacting the bisphenol with 2 equivalents of an alkali metal salt. 22. The method of 21 above, characterized in that the reaction of 20 above is carried out without isolating the S-triazinyl biphenyl after the preceding step or transferring it to a different reaction vessel. 23 Bisphenol of general formula 10] Up to 99 equivalents are optionally mixed with 1 equivalent of S-triazinylbisphenol of general formula 11 and/or bis-S-triazinylbisphenol of general formula 12, provided that The total amount of equivalents of bisphenol of general formula 10 is 199 per equivalent of said S-triazinyl or bis-S-triazinylbisphenol.
23. The above-mentioned methods 17 to 22, characterized in that at least 1.05 equivalents of halogen (Hal) bonded through -CO- are used per equivalent of phenolic -OHI. 24. At least one of the monomers and the carbonic acid derivative forming the polycarbonate are reacted with S-triazinyltrisphenol of the general formula [wherein X has the same meaning as 8 above] The method for producing the branched polycarbonate described in 8 above according to 13 to 23 above. 25. A method for producing the polycarbonate of 1 above substantially as described in any of the Examples. 26 The above 1 produced by any of the methods 3 to 24 above
of polycarbonate. 27. A method for removing hydrocarbons from a mixture of the hydrocarbons and water or a salt aqueous solution, which comprises adsorbing the hydrocarbons and the halogenated hydrocarbons onto the polycarbonate according to any one of 1 to 12 and 26 above. 28. The method of 27 above, characterized in that a polycarbonate in which Q is -COO days or -S03 days is used. 29 The method of 28 above, wherein Q is -COO, Z is -NH, a is 1, and x is a group. 30. The method of 27 above substantially as described in any of the Examples.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the above formula, X is an o-, m- or p-phenylene group optionally having one or more substituents; Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R^7 and R^8 represent a hydrogen atom, an alkyl group having up to 4 carbon atoms, or a halogen atom, and may be the same or different, and Y is Single bond, alkylene or alkylidene having up to 7 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 12 carbon atoms, -O-, -S-, -C
O-, -SO-, -SO_2- group, or general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R^9, R^1^0 and R^1^1 have 4 carbon atoms
represents the same or different alkyl groups up to and R^1^1 may represent a hydrogen or halogen atom), and Z is -O-, -S-, -NH-
or -NR^1 or -N-(R*)-(Q*)_a*
R and R* are each independently an alkylene 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, and 14 carbon atoms. a hetero-arylene group, or an alkalylene or aralkylene group having up to 30 carbon atoms in total, in which carbon is bonded to a group X as defined above and a group Q as defined below and optionally carries one or more substituents; Yes, R^1 is an alkyl group with up to 20 carbon atoms, 5 to 5 carbon atoms
12 cycloalkyl group, mononuclear or polynuclear aryl group or optionally substituted heteroaryl group with up to 14 ring carbon atoms, provided that the carbon atom is bonded to the nitrogen atom;
or 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 -COOH, -COO
R^2, -CONR^3R^4, -SO_3H, -SO
_2NR^3R^4 or alcoholic hydroxyl group, where R^2 represents an alkyl group having up to 4 carbon atoms, and R^3 and R^4 may be the same or different hydrogen, up to 4 carbon atoms represents a straight-chain or branched alkyl group and an optionally substituted phenyl group or together with the N atom form a 5- or 6-membered ring system, and a and a*
represents an integer from 1 to 4 independently of each other] and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^5 and R^6 may be the same or different. may represent an alkyl, hydroxyalkyl, carboxyalkyl or alkoxycarbonylalkyl group having up to 5 carbon atoms, a C_5-C_7 cycloalkyl group, or a C_6-C_1_4 aryl group, or together with the N atom, a 5- or 6-membered Bis s forming a membered ring system
- at least one selected from triazinyl bisphenols;
Species monomer itself or said monomer with the formula HO-X-OH
(10) [In the above formula, X has the above meaning] The bisphenol of branched by the introduction of 0.01 to 5 mol% of a trivalent residue of the formula based on the residue of said s-triazinyl compound, characterized in that it is reacted with s-triazinyl-trisphenol having the meaning of A method for manufacturing polycarbonate.