JPS603410B2 - Method for producing metal-containing polymers containing hydroxyquinoline terminal groups - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, formula 10 [wherein RI and R2 can be the same or different, hydrogen, (C
,~C4)-alkyl, phenyl or halogen (e.g. chlorine or bromine), Z is C&, H-CH3, isoalkylidene having 3 to 5 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 15 carbon atoms; R4, R5, R3 can be the same or different and are an alkyl group having 1 to 5 carbon atoms, and M is a polycarbonate segment, preferably The basis of
or a polyester segment, preferably a group of the formula, or a polyamide segment, preferably a group of the formula] with a metal compound of the formula 12 {a} in an aprotic solvent.
At a temperature of 0° C., the molar ratio of the compound of formula 10 to the compound of formula 12 was 1:0.5 to 1:1, and the compound (1
0) and (12) in the solution at a concentration of 0.001 to 3% by weight, or [b-T is simply an anion of an inorganic mineral acid, an anion of an organic carboxyl acid, and/or a tsuba. *If the formula 1 corresponds to an aprotic solution,
A compound of formula 12 is dissolved in a polar protic solvent at a temperature of 200-220 pm.
The molar ratio of compound (10) to (12) is 1:0.5 to 1:1, and the concentration of the condensation polymer of formula 10 is 1 to 3% by weight.
, the concentration of the metal compound of formula 12 is from 0.001 to 3% by weight
Formula 11 [where Q in the formula is a melon group or T, R1, R2, Z, and M are as defined in formula 10, and n is a number from 1 to 50, G corresponds to the metal compound of formula 1, m is the number of anionic bonds and/or ligands T present on the metal atom, and the difference in valence or coordination is 2 is subtracted from the number, r is an integer from 0 to 20, Me is a metal from subgroups 1 to 8 of the periodic table, or from royal groups 2 to 5,
In particular, Sc~Zn (atomic number 21~30), Y~Cd (atomic number 39~48), La~Hg (atomic number 57~80)
), Ac~U (atomic number 89~92), N, Pb and B
i metal, T is an anion of an inorganic mineral acid, an anion of an organic carboxylic acid, a complexing agent, C, ~C,8 alkoxy group, C6 ~
corresponds to a C,2-aryloxy group and/or a trialkylsiloxy group having 3 to 12 carbon atoms] A method for producing a metal polymer is provided.

In formula 10, the polycarbonate segment has a molecular weight Mn ranging from 1000 to 30000, and the polyester segment and polyamide.

The segments have molecular weights ranging from 800 to 25,000. (Mn is measured by semi-permeable membrane osmometry at 20 oo in common solvent). In the polycarbonate segment M, D is chlorine, bromine, hydrogen or C. ~C
4-alkyl, L is a single bond, C, ~C5-alkylene, C2-C5-alkylidene, C5-C,5-cycloalkylene, C5-C,5-cycloalkylene, or a group, and p is 2-50 is an integer.

In the polyester segment M2, R and R can be the same or different, C2-C,2 alkylene, C5-G,5-cycloalkylene, in which 10- or cyclohexylene can be interposed C8-C,2-arylene-dialkylene such as C8-C,2-phenylene dialkylene, C6-C,2-arylene such as phenylene, naphthylene, diphenylene, and C,3-C
,5-alkylidene diphenylene, p is 2-5
It is an integer of 0. In polyamide segment M3, R'' is hydrogen and C, to C4-alkyl;
, R' and p are the same as defined in M2. A method for preparing a condensation product of formula 10 containing an 8-hydroxyquinoline end group is as follows:
)-alkyl group, RI and R2 are the same or different and mean hydrogen, (C, to C4)-alkyl, phenyl or halogen (e.g. chlorine * or bromine), Z is C, CH-CH3, isoalkylidene group having 3 to 5 carbon atoms,
Siku with 5 to 15 carbon atoms.

alkylene or cycloalkylidene radicals or radicals of the formula 2] are directly combined together with the raw materials necessary for the construction of the condensation polymer M of the formula 10 by known methods.

The above-mentioned 8-hydroxyquinoliso is described in the specification of the patent application of the same date based on German Patent No. 2407308. In this case, surprisingly, for example 8-
Polycarbonate with hydroxyquinoline end groups,
When prepared by methods commonly used for the synthesis of polycarbonates, the functional 8-hydroxyquinoline (X=OH) of formula 1 added during the condensation condenses to the ends of the polymeric chain and thus specifically terminates the chain. 8-hydroxyquinolyl group, thus retaining the complexing center of the 8-hydroxyquinolyl group.

The action of the functionalized 8-hydroxyquinoline as a chain terminator can be determined by analysis of the end groups and by the molecular weight obtained in this way and the measured value of a separate molecular weight determination (viscosity measurement or semipermeable membrane osmometry). It was determined by comparing the

By adding a functional 8-hydroxyquinoline of formula 1 as a chain terminator in an amount of 2 to 50 mol % with respect to the sum of other raw materials, a desired chain length can be obtained with an 8-hydroxyquinoline end group of formula 10. Polymers can be prepared in which the polymerized units p of polycarbonate, polyester or polyamide defined in formula 10 above can be present from 2 to 5 times. The production of the compound of formula 10 varies depending on the type of condensation polymerization segment desired, but is carried out by a conventional vertical polymer production method, in which the group X of the hydroxyquinoline of formula 1 is used in the synthesis of polycarbonate and polyester. is OH, and for the synthesis of polyamide, NH2 or NH-(C, ~
C4-alkyl). A preferred method for preparing a polycarbonate having 8-hydroxyquinoline end groups of formula 10 (M=M,) is to combine a bisphenol component with a functional 8-hydroxyquinoline of formula 1 (X=OH) and phosgene;
Alternatively, under conditions that cause an interfacial reaction between the bischlorocarbonate ester of the bisphenol component and an aprotic water-immiscible solvent such as dichloroethane, methylene chloride, coo-form, mono- or dichlorobenzene, and an alkali hydroxide. It consists of reacting in a mixture with an aqueous solution in the presence of a suitable catalyst, for example triethylamine.

In this case, the reaction is carried out with a slightly more than equimolar amount of phosgene at a temperature of about 20°C (ie oo~40q0). 8-Hydroxyquinoline of formula 1 as chain terminator (
x=OH) in an amount up to 50 mol % with respect to the sum of other raw materials to control the molecular weight. Recovery of the polycarbonate is carried out in the usual manner, for example by precipitation or evaporation of the solvent, in which case the polycarbonate-containing phase is preferably washed free of electrolyte. (References regarding the manufacturing method of polycarbonate are available from H. Schnell (N.Sc.
``Chemistry and Physics of Polycarbonates (C
Hemistry and Phys;csof Pol
ycarboMtes), Interscience Publishers
e Dai), London, 1964).

Suitable diphenols for the production of polycarbonates of the formula 10 (M=M, Hydroxy-3,5-dichlorophenyl)-propane-2,2 (tetrachlorbisphenol), bis-(4-hydroxy-3,5-dibromophenyl)-propane-2,2 (tetrabromopisphenol-A), bis( 4-hydroxy-3,5-dimethylphenyl)-propane-2,2(
Tetramethylbisphenol-A), bis-(4-hydroxy-3-methyl-phenyl)-propane-2.2,
It is bis(4-hydroxyphenyl)-cyclohexane-1.1 (pisphenol Z).

Other examples of diphenols used in the production of polycarbonates are U.S. Pat. No. 3,028,365;
No. 3148172, No. 3271368, No. 2970
No. 131, No. 2991273, No. 3271367,
No. 3280078, No. 3014891, No. 2999
No. 846, as well as German Published Patent Application No. 2063050
No. 2063052, No. 2211957, and No. 2211956. Equation 10 (M=M2
) Many methods can be used for the production of polyesters with 8-hydroxyquinoline end groups.

A preferred conventional method for making polyesters from glycols and aromatic dicarboxylic acid esters is transesterification. In this case, as is known, an easily volatile dicarboxylic acid ester of an alcohol, such as dimethyl terephthalate, is mixed with a corresponding glycol, such as ethylene glycol, at a temperature of 120 to 300° C., optionally using reduced pressure, and acidic or basic. a functional 8-hydroxyquinoline of formula 1 (X=OH) in the presence of a catalyst such as hydric acid or alkali and alkali metal alcoholates.
The dicarboxylic acid ester is condensed with the glycol component, depending on the degree of polymerization of the desired polyester.
It can be added in an excess of 0 mol%. (Literature on Esther Exchange: Davreu H. Carosas (W
．． Day. Carothers) and F.J. Juan. F.J. VanNatta, Journal of American Chemical Society (J.Ame
r. Chem. Soc. ) 52 萱 314 pages (1930
US Pat. No. 2,534,028 (1948), Du Pont Company, inventor E.F.
lzard)]. If a polyester of formula 10 (M=base) based on a diphenol and an aromatic dicarboxylic acid is desired, a solution condensation polymerization method using dicarboxylic acid chloride, e.g. isophthalic acid dichloride, and bisphenol, e.g. bisphenol A, is recommended. In this case, the reaction with 8-hydroxyquinoline (x = OH) of formula 1 is preferably carried out in about 20 qo by a variant of the interfacial polycondensation method, the total amount of phenolic component being in slight excess with respect to the difunctional acid chloride. Use quantity. It is preferred to optionally add a wetting agent, such as sodium lauryl sulfate. Suitable solvents are CH2CI2, CHC13 dichloroethane, mono- and dichlorobenzene. In this case, the plurality of functional groups in 8-hydroxyquinoline (X═OH) of Formula 1 have reactivity levels, and only the center X of the functional group participates almost quantitatively in the condensation. [Literatures related to the solution condensation polymerization method; J. Batzer, J. Holtschmidt, F.W. Wiloth, and B. Mohr Macromolecules - Shi・Heko
- (Kromolekulare Chemie) Vol. 7, p. 82 (1951): W.R. Sorensen, "T.W. Campbell;・Polymere Hemy (Pr a
Parative Method der Pol
ymere-Chemie) 118 pages, Welllag
Verlag Chemie, Weinheim 1962]. According to the above method, polyesters of the formula 10 (M=M2) based on aliphatic or cycloaliphatic carboxylic acids and glycols or aliphatic or cycloaliphatic carboxylic acids and diphenols can also be obtained.

Suitable dicarboxylic acids or their esters, anhydrides and chlorides suitable for the preparation of polyesters of the formula 10 (M=M2) are, for example, terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylmethanedicarboxylic acid,
These are adipic acid, tartaric acid, glutaric acid, sebacic acid, pimelic acid, corkic acid, azelaic acid, diglycolic acid, cyclohexane dicarboxylic acid, and cyclohexane diacetic acid. Suitable lower aliphatic esters of such acids are dimethyl ester, diethyl ester, dipropylester, and mixtures thereof. Examples of glycols include the following:

Ethylene glycol, di- and triethylene glycol, 1,2- and 1,3-propanediol, 1,4-,
2,3-,1,3-butanediol, 1,6-hexanediol, 1110-decanediol, cyclohexanedimethanol, cyclohexanediol, 212-dimethylpropanediol (1,3), glycerin monomethyl ether, and 2 mixture of alcohols. As suitable diphenols it is possible to use those already mentioned for the synthesis of polycarbonates.

Preferably an aliphatic diamine and an aliphatic or aromatic dicarboxylic acid as well as 8-hydroxyquinoline of formula 1 (X=NH
A number of methods can be used for the preparation of polyamides with 8-hydroxyquinoline end groups of formula 10 based on 2- or NH-(C, -C4)-alkyl).

A common method involves combining a difunctional acid chloride, such as sebacyl chloride, a suitable diamine, such as hexamethylene diamine, and the corresponding 8-hydroxyquinoline of formula 1 (X:N
H2 or NH-(C, -C4)-alkyl), in which a solution of the bisacyl chloride in a water-immiscible organic solvent, such as tetrachloroethylene, is added to the aqueous solution of the diamine and the compound of formula 1 used. An interfacial vertical polymerization reaction is carried out with an aqueous hydroxyquinoline solution.

This method can use reaction components that are difficult to undergo thermal condensation polymerization. The reaction is carried out at less than about 20 qo, in which case the sum of both amiso components can generally be added in slight excess with respect to the difunctional acid chloride. [Reference: E.
E. L Wittker
and P. Morgan, Journal of Polymer Science (J. Polymer
Sci. ) Magazine 4, 289 pages (195 balls), and P.W. Mor and S.L. Kwolek, Journal of Chemical・Education (J.Ch.
em. Educ. ) Magazine Volume 36, Pages 182, 530 (1
95g King)]. Other methods include diamines, dicarboxylic acids, 8-hydroxyquinoline of formula 1 (X=NH2 or NH-(
C, -C4-alkyl))), in which the water evolved during the reaction must be continuously removed from the reaction chamber, for example by vacuum. This is because this is a reaction factor that essentially influences the rate of polyamide production. At this time, the reaction is carried out without a solvent or in an inert solvent such as xylene at a temperature of 180 to 250 pm. Since salt is mainly produced during the reaction, a salt obtained from the corresponding diamine and dicarboxylic acid can also be used in advance. [Reference: German Patent No. 74
No. 9747 (i933 King), DuPont
): W. Hmann Laboratory Report, Bayer;
Methoden der Organitz (Methoden der Pig.)
Chemie) Volume XW, 2, page i36 (King 1963),
Thieme Uerlag
, Schuttgart (S■ttga 9)]. Suitable dicarboxylic acids or their modest conductors are the difunctional acids already mentioned for the preparation of polyesters with 8-hydroxyquinoline end groups.

For example, the following diamines are suitable as the amino component.
Ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 4,4'-diaminodicyclohexylmethane, and m- and p-phenylene diamine, diphenyl diamine. Of course diamine,
The dicarboxylic acid and the dicarboxylic acid can optionally be subjected to condensation polymerization with a suitable aminocarboxylic acid, such as 6-aminocaproic acid, 11-aminoundecanoic acid, or a lactam thereof, in a molten state while excluding oxygen.

[Literature: M.R.Akilim
) Anal Do Shimmy (Anal Do Shimmy)
mie) Magazine (12) Volume 3, Page 5 (1948)]. The striped polymer of formula 10 with 8-hydroxyquinoline end groups may in suitable form contain transition elements of the periodic table, i.e. Sc to Z
Element n (atomic number 21-30), Y-Cd (atomic number 39-48), Hg (atomic number 57-80), Ac
~U (atomic number 89-92) elements, as well as Mg, Ca
, AI, Pb and Bi metal ions from solutions or industrial wastes.

Adsorption of metal ions is reversible. That is, these metal ions can be easily separated from the polycarbonate by, for example, washing with an acid or a softening agent. The condensation polymer of formula 10 can be used to reduce harmful metal impurities in thermoplastic or thermosetting resins by 0.01 to 10% by weight, based on the total amount of the mixture.

Condensation polymers of Formula 10 can also be used to make metal-containing polymers. The above uses of the condensation polymer of formula 10 are based on the same principle that whether the vertical polymer is polycarbonate, polyester or polyamide, a metal absorption reaction takes place to form a metal-containing condensation polymer, in other words. It is based on the chelate-forming ability of the novel longitudinal polymer of formula 10.

In formula 12, the inorganic mineral acid that forms the anion T is especially HC.
1, 2S04, 3P04, and HN03, and the organic carboxylic acids for the generation of anion T are particularly C, ~C
, 8 saturated fatty acids, such as HCOOH, (COOH)2
, CH3-COOday, and CH3-(CH2),6-C
Among these, aliphatic diketones (eg acetylacetone), ethylenediaminetetraacetic acid, nitrilotriacetic acid, and cyclobentadiene are suitable as sulfurizing agents.

According to the present invention, there is also provided a metal-containing polymer of formula 11 produced using the vertical polymer of formula 10 by the above-described method. In the metal-containing compound of formula 11 of the present invention produced during the reaction of the condensation polymer of formula 10 and the metal compound of formula 12,
Generally, the 8-hydroxyquinoline group-containing condensation polymer is bonded to the metal or metal oxide through a linear chain bond.

In this case, a stable internal structure of the 8-hydroxyquinoline group and the metal is formed. [Comparative literature: L. Berg (R.B.
Oxyquinoline (Oxin)
Die anal ischeVeMend skin gUon o-○xychi
nolin gu0Mn”)undseinerDeri
vate], 2nd edition, Stuttgart (1938)
, and El Bock (R. Sectionck), Angevante
Chemie (AnhokowandteChemie) magazine volume 67,
420 pages (1953 balls)]. However, partial branching or cross-linking of the linear metallized polymer of formula 11 may later be applied to the linear metallized polymer of formula 1.
It can be obtained by bonding to the metal compound of 2 or reacting with Gund T.

Therefore, if titanium tetrabutyrate, for example, is used as a metal compound for bonding with the condensation polymer of formula 10, the butoxy groups remaining on titanium after the chain extension reaction will separate when water is added, forming different polymer chains. Nochi. The tan atoms are connected to each other by oxygen bridges.

Linear chain bonds are verified by determination of relative viscosity and number average molecular weight Mn, which is blocked by osmometry.

By varying the molar ratio of metal compound to condensation polymer of formula 10, the desired polymer chain length can be adjusted. In this case, if the molar ratio of condensation polymer 1 to metal compound is 1:1, a linear polymer is obtained, and if this ratio is 1:0.5, a dimer is obtained. The metal content of the formula 11 polymer can also be varied depending on the amount of metal compound used, and up to 3% by weight with respect to the formula 11 polymer can be used.

Examples of metal compounds suitable for producing the metal alloy polymer of formula 11 include the following compounds of the 1st to 8th subgroups and the 2nd to 5th royal groups. [a} Inorganic salts and their hydrated bodies "For example, FeC13, FeC13 - mother's day 20, CuS04, CuS04-9 days 20, C℃13.8 days 20, CoC12, MnS04.7 ratio○ , NiS〇4・
Mother's Day 20, AIC13・QH20'b} Organic acid salt,
For example, Cu (C2 day 302) 2, Ni (C2 day 302)
2, Co (C2 day 302) 2, Zn (C2 ratio 02) 2,
Cu(C7day502)2, AgC7&02, ZnC20
4, CrC204 "CoC204 2 days 20'c' alcoholates and phenolates, such as Zr (C4 days 90
) 4, Ti (C4 ratio ○) 4, Zr (C, 8 days 370) 4
, Ti (C, 8 days 04) 4, Ti (CQC 6 days 40)
4, B (C2 days 50) 3, B (C4 days 90) 3'd}
Metal complexes such as acetylacetonate, Co(C5day702)2, Ni(C5day702)2, Fe(C5day702)2
02) 3, Mn (C5 day 702) 2, Zr (C5 day 70
2) 4 and bis(cyclobentadienyl)-titanium dichloride.

[c - Aggregated metal compounds, such as n-butyl titanate polymers, cresyl-titanate polymers, and (trimethylsiloxy)-titanate polymers.

In this case, the degree of polymerization can be from 1 to 20 (see the corresponding newsletter of Dynamite Nobel).

The reaction between the metal compound and the condensation polymer of formula 10 can be carried out in a homogeneous solution or as an interfacial reaction.

Homogeneous solution reactions are performed using aprotic solvents such as acetone,
Acetonitrile, nitromethane, benzene, toluene,
It is carried out in xylene, mono- and dichlorobenzene, dimethylformamide, and dimethylacetamide, dichloroethane, methylene chloride, chloroform, diethyl ether of ethylene glycol, and the like.

The raw material is directly used, preferably in the form of a solution with a predetermined composition prepared to a raw material concentration of 0.001 to 3% by weight, and is a mixture of 8-hydroxyquinoline condensation polymer and metal compound of 1:0.5 to 1:1.
It is advantageous to prepare an equivalent dissolved amount of 1 at a temperature of 20 DEG to 16,000 DEG C., adding the metal compound to the 8-hydroxyquinoline end group-containing longitudinal polymer of formula 10. During the interfacial reaction, the longitudinal polymer of formula 10 is dissolved in nonionic water-immiscible solvents such as benzene, toluene, xylene, mono- and dichlorobesozene, and chlorinated hydrocarbons such as dichloroethane, methylene chloride, chloroform, etc. .

The metal compound of formula 12 in which T is simply an anion of an inorganic mineral acid, an anion of an organic carboxylic acid and/or a lead-forming agent is a metal compound of formula 12. It is used after being dissolved in a tonic solvent, preferably water. In the case of interfacial reactions, metal compounds of formula 12 can be used in large overload. This is because unreacted metal compounds remain in the protic solvent. Reaction is 20-220q
1 to 3% by weight for condensates of formula 10 and 0.001 to 3% by weight for metal compounds of formula 12 at temperatures between
It is carried out at a concentration of 0% by weight. The metal-containing polymer of formula 11 has a high thermal stability (DIN 53
735), high chemical resistance (DIN 5
3476), higher solidification temperatures and lower stress cracks (measured from DIN 5344y') compared to the corresponding metal-free condensation polymers with 8-hydroxyquinoline end groups of formula 10.

Both condensation polymers, having the metal-free type of formula 10 and the metal-containing type of formula 11, can be used industrially and are commercially useful, depending on the underlying polymerized segment M. .

That is, they correspond to formulas 10 and 11 based on M, which have a conventional terminal group (for example, a pt-butylphenyl terminal group) instead of the terminal group derived from 8-hydroxyquinoline of formula 1 of the present invention. polycarbonate; 8 of formula 1 of the present invention
- instead of a terminal group derived from hydroxyquinoline,
Formulas 10 and 11 based on M2 with normal end groups
Polyesters corresponding to the formulas 10 and 11 based on M3 with the usual end groups in the polycarbonate of 11 instead of the end groups derived from the 8-hydroxyquinoline of the formula 1 according to the invention. By using 8-hydroxyquinoline of formula 1 as a chain terminator for condensation polymers of the type M, M2 and M3 of formula 10,
These polymers additionally have the property of forming a body as described above.

Conversion to metal-containing striped polymers of formula 11 according to the invention provides improvements in the properties mentioned above. The present invention also includes novel metal-containing polymers of Formula 11.

According to the present invention, formula 11 [wherein Q is a group of formula 1 or T, and R1, R
2, Z, and M are as defined in formula 10, and n is 1 to 50
The number of , G is the formula 12 days [Me--.

- mountain] rMe smaller ÷) m <10> m 12a Corresponds to a metal compound, where m is the anionic bond and/or ligand T in the metal atom.
is the number obtained by subtracting 2 from the valence or coordination number, r is an integer from 0 to 20, and Me is a metal from the Liu group 1 to 8 or the royal group 2 to 5 of the periodic table. ,
In particular, Sc~Zn (atomic number 21~30), Y~Cd (atomic number 39~48), La~Hg (atomic number 57~80)
), Ac~U (atomic number 89~92), N, Pb and B
i is a metal, T is an anion of an inorganic mineral acid, an anion of an organic carboxylic acid, a galvanizing agent, C. ~C,6 Arkokishester
Corresponds to C6-C,2-aryloxester and/or trialkylsiloxy group having 3 to 12 carbon atoms]
A metal alloy polymer is provided.

The inventive metallized polymers of formula 11, alone or as part of a mixed polymer, can be used as sizing agents and adhesion aids between metals, metal oxides, glass surfaces, and later applied synthetic resins and lacquers. It can be used to form film-resistant, corrosion-resistant, solvent-resistant and heat-resistant coatings.

The metal-containing polymer 11 can of course also be used in its entirety in applications where the conventional corresponding polycarbonates, corresponding polyesters and polyamides are used. The inventive metal-containing polymer of formula 11 can also be used as a stabilizer for synthetic resins.

Such synthetic resins include polyvinyl chloride or a copolymer thereof, such as ethylene-vinyl chloride, or vinyl acetate-vinyl chloride copolymer, polyethylene, polypropylene, polyacrylate, (meth)acrylate, and at least one other monomer. polymers with polymers, vinyl acetate polymers, ethylene-vinyl acetate copolymers, polycarbonates, polysulfones, polyphenylene oxides, styrene copolymers,
These include A-speckled polymer (acrylonitrile-butadiene-styrene graft thermoplastic polymer), nylon-type polyamide or polycaprolactam, polyethylene terephthalate, polyacetal, and the like. In particular, the metal-containing polymers of the formula 11 can be used as catalysts, for example in the form of cobalt compounds, as initiators for reactions of the radical type.

The description of the raw material for the longitudinal polymer of formula 10, ie the novel functional 8-hydroxyquinoline of formula 1 below, was taken from the patent application specification of the same date under German Patent No. 2407308.

[However, in the formula, X is day, or N ratio, or NH (1C, ~4)
-alkyl, RI and R2 can be the same or different and mean hydrogen, (C,~C4)-alkyl, phenyl or halogen (for example chlorine or bromine), Z
H2, CH-CH3, isoalkylidene group having 3 to 5 carbon atoms, cycloalkylene or cycloalkylidene group having 5 to 15 carbon atoms, or a group of formula 2, and R4, R5,
R3 are the same or different alkyl groups having 1 to 5 carbon atoms].

The isoalkylidene group Z in Formula 1 is a group.

The method followed for the preparation of 8-hydroxyquinoline of formula 1 is 8
- Compounds capable of producing carponium ions by reacting hydroxyquinolines with (cyclo)alkenyl-substituted phenols or (cyclo)alkenyl-substituted anilines or under the influence of acidic catalysts, i.e. halogenalkyl-substituted phenols or anilines, or hydroxyalkyl This is a method of alkylating a hydroxyaryl compound by reacting it with a substituted phenol or aniline in a manner known per se; in this case, the component passed through the alkylation of 8-hydroxyquinoline, such as a hydroxyalkyl-substituted phenol, is Quinolines can be generated during in situ alkylation, for example from the corresponding phenol and the corresponding aldehyde.

A compound of formula 1 in which Z=C is a compound of formula 3 [where ×, R1,
R2 has the same definition as Formula 1, Y is hydroxymethyl or halogenmethyl group] and 8-hydroxyquinoline are reacted, and the molar ratio of the reaction raw materials (the ratio of 8-hydroxyquinoline to compound 3 is preferably 1:1~10:1
It is created by

In the case of compounds of formula 3 in which Y is the same halogenmethyl, preferably chloro and bromomethyl groups, only a Lewis acid such as aluminum (m) chloride or sheratrifluoride is used as a catalyst in the case of compounds of formula 3. 10 to 100 mol%
It can be used in an amount of

Preference is given to using compounds of formula 3 in which Y has the same hydroxymethyl, which is easily obtained from formaldehyde and the corresponding phenol and aniline.

As alkylation catalysts in this case Lewis acids, hydrosilicates of the montmorillonite type, as well as stannic acids and carboxylic acids, such as acetic acid used directly as solvent, are used in amounts of 10 to 500 mol %, based on the compound of formula 3. . Depending on the type of raw materials and the catalyst, the reaction is carried out neat or in solution at a temperature of 10 to 15 degrees, the choice of solvent being carried out according to the solubility of the raw materials, the reaction temperature and especially the catalyst.

A solvent is chosen which does not alkylate under the given reaction conditions and which does not itself act as an alkylating agent, such as carbon disulfide, nitromethane, nitrobenzene, optionally a carboxylic acid such as formic acid or acetic acid, and a Lewis acid, optionally as a catalyst. The reaction is carried out in the presence of a chlorinated aliphatic hydrocarbon, such as methylene chloride or dichloroethane.

[Literature: Huben-Weil, Methoden der Organitschen Hemie, Vol. The compound of formula 1, in which Z is CH-CH3, an isoalkylidene group having 3 to 5 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or a group of formula 2, is a compound of formula 2 with 8-hydroxyquinoline and formula 3 [however, formula X, R1, and R2 have the same meanings as in formula 1, and Y is vinyl, alkene [1}-yru[2] having 3 to 5 carbon atoms;
', Alkene-[21-yl-■ group having 4 to 5 carbon atoms, Alkene-[21-yl-'3} group having 5 carbon atoms, 5 carbon atoms
~15 cycloalkene-{1}-Y-{1} group, or formula 4 (R3, R4, R5 and R7 are the same or different alkyl groups having 1 to 5 carbon atoms in the nucleus, R6 is H or C, ~ C4
represents an alkyl group).

] can be obtained by reacting with the compound.

The alkenyl to cycloalkenyl groups in the compounds of formula 3 can be present capped with HCI or HCl adducts. When using ratio ○ adduct,
A protic acid, such as hydrofluoric acid or sulfuric acid, is added as a catalyst, in which case alkylation is carried out before the alcohol is dehydrated to the olefin. Lewis acids can also be used as catalysts. [Reference: G.A.01ah
), “Friedel Krach and its related reactions (Fri
edeICraftsand Related Rea
ction), Vol. 0, p. 477, InterScience Publishers (InteRclencePa)
Blishe Dai), New York, 1964]. Alkylation using the corresponding halides can also be carried out with Lewis acid catalysis. For alkylation involving alcohols and halides, 1
The reaction is carried out at as low a temperature as possible in the range from 0.00 to 15000 to avoid excessive isomerization, in which case the solvents mentioned above can be used. Suitable alkylation of 8-hydroxyquinolines with (cyclo)alkenyl compounds of formula 3 is carried out under the action of acidic catalysts of Lewis acids, hydrosilicate and protic acids, with or without solvent, from 50 to 250 qC,
It is preferably carried out at a temperature of 100 to 250q0.

The catalyst is added in an amount of 10 to 200 mol% depending on the type of feedstock, and the molar ratio of olefinic alkylating agent to 8-hydroxyquinoline reactant feedstock is generally preferably 1:1 to 1:10; It can also be out of range. Suitable catalysts include Lewis acids such as aluminum chloride (dish), iron chloride (m), zinc chloride, titanium tetrachloride, sheratrifluoride, and AIC12.HS04 or AIBr2.
A mixed catalyst of the type 2P04, a protic acid, such as hydrochloric acid,
Hydrofluoric acid, concentrated phosphoric acid, 96% or more sulfuric acid, Hakama acid, and toluenesulfonic acid are used. Also advantageous are acidic activated clays, such as pentonites, zeolites and other hydrosilicates, and ion exchange resins, such as polystyrenes with sulfonic acid groups or phenolic resins with sulfonic acid groups which are insoluble in the reaction mixture. The alkylation of 8-hydroxyquinolines with (cyclo)alkenyl compounds is carried out with or without solvents. Suitable solvents are, for example, nitrobenzene, nitromethane, carbon disulfide.

[Literature on catalysts: V. Enu Ipateyev (V.
．． N. latieff) and El Shymelling (
L. Schmerling), Adv Associations Iso.
Advances mCaplysis
, Volume 1, pp. 27-64, Academic Press (Ac
Academic Press, New York, 195th; References on alkylation with olefins: G.
E. Oler, supra, “Friedel Krach and related reactions” 1963; Asingel et al., Erd 61, Kohle 2, pp. 786, 852 (1967). Z has 5 or more carbon atoms
The compound of formula 1 which is a cycloalkylene group of 15 is 8-hydro. Although it is obtained by reacting xyquinoline with a compound of formula 3 in which Y is the corresponding hydroxycycloalkyl group having 5 to 15 carbon atoms, isomerization of the cycloalkyl group is not completely avoided. German patent application P240730
In the patent application dated the same date based on No. 8, in formula 3,
alkene-tl}-yl-[2}, alkene-[2)-yl-[2} group having 4 to 5 carbon atoms, alkene-[2}-yl-[3}] group having 5 to 5 carbon atoms, cycloalkene-[2]-yl-[3} having 5 to 15 carbon atoms] [8-hydroxyquinoline with a compound that is a 11-yl-m group, a group of formula 4, or a hydroxycycloalkyl group having 5 to 15 carbon atoms, in the presence of an acidic catalyst, and a known method for alkylating hydroxyaryl compounds. In this case, the 8-hydroxyquinoline pair of formula 3 is alkylated by
A method for producing a compound of formula 1 is described in which the reaction raw material ratio of the compound is 1:1 to 10:1.

In place of the (cyclo)alkenyl-substituted phenol or aniline of formula 3, a compound of formula la (wherein X, R1, R2 and Z
has the same meaning as formula 1),
It is also possible to use corresponding compounds which can be formed under the influence of acidic catalysts.

For the alkylation of 8-hydroxyquinoline in the present invention, suitable compounds are the phenolic type obtained in German Patent No. 1235894, the phenolic type obtained in German Patent No. 1191363
The following aniline-type compounds are described in German Unexamined Patent Publication No. 2064305. 4-isoprobenylphenol, 2-methyl-4-isoprobenylphenol, 2,6-dimethyl-4-isoprobenylphenol, 2-propyl-4-isoprobenylphenol, 2-phenyl-4-isoprobenylphenol, 2-chloro-4-isoprobenylphenol, 3-methyl-4-isoprobenylphenol, 2-(p-hydroxyphenyl)-12-butene, 2-(p-hydroxyphenyl)-12-bentene, 4-cyclohexenyl Phenol, 21 (p-hyde).

xyphenyl)-121 (p-improbenyl phenyl)
-propane, p-isof. Robenylaniline, aryl on the phenyl nucleus, e.g. phenyl, alkyl, e.g. C,
p-isoprobenylaniline substituted with ~C4-alkyl or halogen, such as chlorine or bromine. Instead of monomeric alkenylphenols and alkenylanilines, dimeric forms of these compounds can also be used.

This is because these dimers decompose into monomers under the reaction conditions. For example, an isoprobenyl-phenol duplex of the formula can be used.

For the alkylation of 8-hydroxyquinoline, other suitable compounds capable of producing carbonium ions under the action of acidic catalysts are, for example:

4-hydroxybenzyl alcohol, 2-bromo-4-hydroxybenzyl alcohol, 3,5-dibromo4
-Hydroxybenzyl alcohol, 4-hydroxy-3
・5-dimethylbenzyl alcohol, 4-hydroxy-2,6-dimethylbenzyl alcohol, 4-hydroxy-2-isopropyl-5-methylbenzyl alcohol,
2-phenylbenzyl alcohol, 3-phenylbenzyl alcohol, 2-[4-hydroxyphenyl]-propanol, 1-[4-hydroxyphenyl]-ethanol, 2-[4-hydroxyphenyl]-ethanol, 2-
1[4-Hydroxyphenyl]121[41(1-hydroxypropyl-(shaphenyl)-propane, 4-amino-benzyl alcohol, 2-chloro-4-amino/penzyl alcohol).

Recovery of the reaction mixture is carried out as follows.

Initially, the catalyst is optionally neutralized, and then the optionally present solvent and 8-hydroxyquinoline are removed in known manner, such as extraction, distillation, vacuum distillation, and steam distillation. By recrystallizing the residual residue from a suitable solvent such as benzene, toluene, ethanol, diethyl ether, acetone, or a mixture of these solvents, 8-hydroxyquinoline with the desired functional group is obtained. This is used directly in the next reaction. The following Reference Examples A, B, and C illustrate the method for producing the compound of Formula 1.

Reference example A 2-[4-hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane 8-hydroxyquinoline at 1508 m, p-isoprobenylphenol at 483 m, and pentate at 150 m night (acidic catalyst K20 manufactured by Sudchemie, Munich)
were combined and heated under nitrogen atmosphere at reflux for 24 hours.
Heat to 80°C.

The reaction mixture is then filtered in a suction furnace to separate the solid crystals. After adding the methylene chloride/water mixture, 2
A portion of the -[4-hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane precipitates as crystals.

The remaining mixture is steam distilled to recover the excess 8-hydroxyquinoline. Additional methylene chloride is added to crystallize the other portion of the functionalized hydroxyquinoline. Both crystallized parts were combined and the total yield was 460
evening (46% of the theoretical value).

Soxhlet extraction with benzene gives colorless crystals with a melting point of 139 qo. Reference example B 2-[4-aminophenyl]-12-[5-(8-hydroxyquinoline)]-propane 8-hydroxyquinoline at 2180 m, p-improbenylaniline at 400 m,
and 300 h of pentonite (acidic catalyst K20 from Jude Chemie, Munich) are heated under reflux under a nitrogen atmosphere for 2 h of 16,000 h.

The reaction mixture is filtered in a suction furnace and then subjected to successive first vacuum distillation and then steam distillation. In this case, the excessive amount of 8
-Hydroxyquinoline is recovered almost quantitatively. Methylene chloride is then added to the reaction mixture and the organic phase is separated. The organic phase was concentrated and the remaining residue was extracted with a methylene chloride/petroleum ether mixture to obtain 2-[4-aminophenyl]-121[5-(8-hydroxyquinolyl)]-propane 3822 with a melting point of 105-107°C. (46% of theoretical value)
I got it. Recrystallization from ethanol gave colorless crystals with a melting point of 109°C. Reference example C [4-hydroxy-3,5-dimethyl-phenyl]-[
5-(8-Hydroxyquinolyl)]-methane Dissolve 36.2 parts of 8-hydroxyquinoline in 200 parts of acetic acid,
Boil for less than 1 hour and add 7.6 ml of acetic acid to 50 ml of acetic acid.
- Drop a solution containing 6-dimethyl-4-hydroxymethylphenol.

Heat at reflux for 5 hours and remove acetic acid by vacuum and azeotropic distillation. Excess 8-hydroxyquinoline is separated off by steam distillation. Take the remaining groove in methylene chloride,
Pass through the oven. Methylene chloride was concentrated and colorless crystals were obtained in 7.1 hours, corresponding to a yield of 47%.Production of a condensation polymer having a terminal group of 8-hydroxyquinoline of formula 10 according to Reference Examples 1 to 3 below. Reference example 1 456 bisphenol A and 559 bisphenol A and 2-[4-
Hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane is dissolved in 4k9 of 9% caustic soda solution and then 9k9 of methylene chloride is added.

Under vigorous lighting, 562.8 m of phosgene is introduced and then 60 m of a 4% solution of triethylamine is added dropwise. It is then concentrated for 1 hour, adding from time to time enough caustic soda to keep the pH of the solution constant at 13. Separate the phases and ensure that the aqueous phase has reacted completely. The organic phase is extracted once with 5% 3P04, washed with water until neutral and then dried over sodium sulfate. Short chain polycarbonates with hydroxy end groups were obtained by concentrating the organic phase and precipitating with methanol. 1.0 cycles of ribata [re, measured in CH2CI2 at 20 qo on a solution of 0.5 ml dissolved in 100 ta]. Nitrogen analysis value N2 = 2.56% phenol OH 2.8%. Molecular weight estimated from this value Mn = 117 & Reference example 2 456 parts of bisphenol A and 7 parts of 21[4-hydroxyphenyl]-21[5-(8-hydroxyquinolyl)]-propane 9 parts caustic soda Dissolves in 2675k9.

Next, 6 kg of methylene chloride is added and 280 g of phosgene is introduced while stirring vigorously. Then, 30 minutes of 4% triethylamine solution was added and incubated for 1 hour. In this case, the pH of the solution is maintained at 13 by adding caustic soda. Recovery follows Reference Example 1. Re, = 1.517 (0.5 ml of CH2CI2 solution was dissolved in 100 ml of solution and measured at 20 ml). Nitrogen analysis value N2 = 0.04%. Mn=17800
(osmotic method in dioxane). Reference example 3 Bisphenol A of 114 days, 21[4-hydroxyphenyl]-12-[5-(8-hydroxyquinolyl)]-propane of 9.30 days and sodium hydroxide of 409 times were added to the water. dissolve.

Then add 300 ml of 10% Na2S04 solution. The reaction solution was stirred vigorously and 101.6 cm of isophthalic acid chloride contained in methylene chloride was added. The resulting emulsion is incubated for another 5 minutes and precipitated in acetone. The resulting polymer with hydroxyquinoline end groups is filtered, washed with water, and washed with acetone. The polyester purified by this method is vacuum dried. rel=1.03
5 (measured in the same manner as in Reference Example 1) Mn=5500 (measured by semipermeable membrane osmotic pressure method in dioxane). Example 1 below
7 exemplifies the method for producing the metal-containing polymer of formula 11 of the present invention.

Example 1 7.65 mmol (7 mmol) of the polycarbonate described in reference example 1 with hydroxyquinoline end groups (Mn=1096) are dissolved in 150 M anhydrous CH2C12.

3. Then dissolved in 100' of anhydrous CH2CI2.
Add 10' of a solution of titanium tetrabutyrate for 4 nights;
At this time, after adding 10% of the tetraptylate solution, the relative viscosity is determined as a measure of molecular weight increase. Table 1 below shows the increase in viscosity with respect to the amount of metal compound added. The increase in viscosity indicates that the metal-containing polycarbonate of Formula 11 has been formed. 1 solution lost 7:1 1,Q
5520 required 〃 7:2 1-〇6
630 Necessary 〃 7:3 1-08240
〃 7:4 1-09350ゑ 〃 7:5 1.142 Reference example Standard according to IK 1.038 solution 1 = 100 odd O
Example 2 Solution containing 3.4 μm of titanium tetrabutyrate in H2012 Polycarbonate (Mn=17800) with hydroxyquinoline end groups described in Reference Example 2 1.78 μm to 100 μm
Dissolve 10' of this solution in anhydrous CH2CI2 and take out 10' of this solution.

To this, a solution 1' containing 3.83 g of zirconium tetrabutyrate in anhydrous CQC12 was added dropwise, and the relative viscosity was determined in the same manner as in Example 1. An increase in viscosity indicates that a metal-containing polycarbonate of Formula 11 has been formed. Table 2 Vertical Polymer Raw Material Added Heavy Metal Compound Equivalent Ratio of Polycarbonate with Terminated Polycarbonate 1.78 (Mn = 178oo) 1. Microsolution 0* 10:1 1.
714 condensation polymer/raw material Added amount Metal compound Re equivalent ratio of 2〃 10:2
1.8443 Autumn 〃 10:3 2083
4 Of course 〃 10:4 2-4195 Ushio
〃 10:5 2.6356 NazuZ 〃
10:6 2-705 Reference example 2K standard 1.517*Solution 0 = 1 O OH201
A solution containing 3.83 g of zirconium tetrabutyrate in 2.

Example 3 Polycarbonate (Mnco178) produced in Reference Example 2
00) Dissolve 5 esters in CH2CI2 above 180, 10
Solutions 14', 21' and 28' containing 0.383 g of zirconium-tetrabutyrate in anhydrous CH2CI2 are added dropwise.

The resulting metal-containing polycarbonate of formula il with increased chain length containing zirconium is separated and made into a film.
Table 3 shows Fulm's yield stress os and tensile strength. R, tensile elongation R, and elastic modulus are listed to indicate the metal content of each striped polymer. Table 3 Yield pressure, tensile strength, and tensile elongation are according to D Nagi No. 53455, elastic modulus is DN 5
Measured according to No. 3457.

Example 4 Polycarbonate 24 with 8-hydroxyquinoline end groups and molecular weight Mn = 11980 (measured by semipermeable membrane osmosis method in dioxane) prepared according to Reference Example 2 was
It contains 0.476% titanium tetrabutyrate dissolved in 0% hot water CH2CI2 and dissolved in anhydrous CQC12.

This metal-containing striped polymer of formula 11 is made into a film and its elastic modulus (according to DW53457 method) and solidification temperature (ET) are determined. The molecular weight was also determined by osmotic pressure method. Table 4 Condensation polymer/metal compound Osmotic pressure ET Elastic modulus equivalence ratio in dioxane
Mn measured from K ■
(kp i) ■ Summer fee Mn = 11980) 2:
1.4 Mn 18800
154.5 22.700
Reference Example 5 Polycarbonate of Mn=16000 (determined in dioxane by semipermeable membrane osmotic pressure method) prepared in Reference Example 2 was dissolved in 100' of anhydrous CQC12 and 0.32' of Mn was dissolved in 20' of CH2CI2. Add the solution containing the titanium tetrabutyrate polymer.

The resulting titanium-containing polycarbonate of formula 11 is subjected to differential thermal analysis. Table 5 shows that the inclusion of metal increases the solidification temperature (ET).

Table 5 Condensation polymer / Convex T ET DIN metal compound Hydroquinolite Alloy metal striped wheel Equivalent ratio of 53 735 Condensation product No. K Yorutsu condensate
Thermal stability 1:0.5 145℃ 162℃ 3
Decomposition above 50°C Example 6 1.78% of the polycarbonate prepared in Reference Example 2 having 8-hydroxyquinoline end groups was dichloromethane with metal acetylacetonate of notation 6 in a 1:1 molar ratio. React for 2 hours at 140oo in benzene.

Table 6 Raw materials Additives Metal content (weight%) calculated value
Detection value hydroxy cobalt acequinoline botylacetone 0.33 0.3
3 recarbonate 26 substances (Mn = 17800) 1.78 nickel acetyl acetone 0.33 0.3
4-27 Phosphorous iron acetyl acetate 0.32 0.3
135 Phosphorus All formula 11 metal alloy polycarbonates can be made into films.

The cobalt-containing film was subjected to a Dm 53455 tensile test. Tensile strength oR (kp Igomi) 585 Tensile elongation sR * 51 Elastic modulus (kp Igomi) 28500 Example 7
The polyester (Mn=5500) described in Reference Example 3 having 8-hydroxyquinoline end groups is dissolved in 100% of anhydrous CQC12 and reacted with the following metal alcoholate solution in equivalent amounts (1:1).

An alloy metal polyester of formula 11 is obtained.

A solution containing 1.77 g of titanium tetrabutyrate in 100 g of anhydrous CH2C12.

A solution containing 2 hours of zirconium tetrabutyrate in 100' of anhydrous CH2CI2'.

Table 7 Raw materials Additives Calculated metal content Detected value 8 - Hydroquine Ti (90 on 04) 4 083%
0.75 *Polyester with quinoline terminal group 0.177 (Mn = 5500) 3 days 〃 Zr 4 days 9○) 4 1.6% 1
- 4% 0200 yen reference example 4 Polyester with aliphatic dicarboxylic acid 7.87 yen adipoyl chloride, 4.28 yen hydroquinoline, and 1.32 yen 2-[4-hydroxyphenyl]-2 A mixture of 5-(8-hydroxyquinolyl)-propane and 20' of nitrobenzene is heated to 150 qo within 21 hours with exclusion of moisture and kept at this temperature for 6 hours.

A stream of nitrogen is passed through the mixture during the entire reaction time. Remove the nitrobenzene under high vacuum and thoroughly dry the solid residue. Molecular weight Mn760 determined by semipermeable membrane osmotic pressure method in dioxane
0 white striped polymer remained. Reference example 5 Polyamide 55 and N-N'-diethylethylenediamine and 6.9
5 mixture of 2-[4-aminophenyl]-2-[5-(8-hydroxyquinolyl)]-propane and 2.5
During the same day, a solution containing 106 ml of NaO3 was fully irrigated and reacted within 10 minutes with a solution containing 101 ml of terephthaloyl chloride in 800 ml of dry chloroform.

The chloroform is removed from the reaction mixture, and the precipitated bran polymer is filtered. Rel = 1.9 after washing several times and drying
5 (determined in cresol as a 1% by weight solution at 25° C.) a colorless condensation polymer matrix was obtained. The following Examples 8 and 9 also illustrate the preparation of metal-containing polymers of Formula 10 of the present invention. Example 8 Production of metal-containing polycarbonate of formula 11 from the polycarbonate described in Reference Example 1 5 parts of the polycarbonate described in Reference Example 1 were dissolved in 100 parts of CQC12, and 2.0 parts of the polycarbonate part was dissolved in 100 days of 20 days. Shake at 20 qo with the containing solution.

The phases are then separated and the organic phase is dried. The remaining polymer is 0
．． It is a metal alloy polycarbonate of formula 11 containing 99 g of Hg. This is 19. Corresponds to the Hg content in box weight %.
This experiment also proved that the condensation polymer of formula 10 has a great ability to absorb heavy metal ions. Example 9 Production of metal-containing polyamide of formula 11 from polyamide described in Reference Example 5 Polyamide 5 described in Reference Example 5 in the same manner as Example 8
I took the evening as chloroform, and it was 8.1 in 20 on the 100th day.
A solution containing Hg(○-C-CH3)2 and 2oqo
Shake for 2 hours at g.

The aqueous phase was then separated, the CHC13 was separated, and the remaining polymer was tested for Hg content. Hg amount 5.1% by weight. This example also showed that the vertical polymer 10 has a high ability to absorb heavy metal ions.

The Hg-containing condensate obtained corresponds to the structure of the product of formula 11 and can therefore also be considered as an example for the production of metal-containing polyamides of formula 11. The main embodiments of the present invention are as follows. 1 Formula 10 [However, the formulas RI and R2 are the same or different and are hydrogen, (C, to C4)-alkyl, phenyl or halogen, and Z is a C ratio, a CH-C ratio, an isoisomer having 3 to 5 carbon atoms. alkylidene, cycloalkylene or cycloalkylidene having 5 to 15 carbon atoms, or a group of formula 2 (wherein R4, R5
and R3 are the same or different and are an alkyl group having 1 to 5 carbon atoms), and M is a polycarbonate segment M
, , representing a polyester segment M2 or a polyamide segment M3], the method comprises producing a condensation polymer of the formula 1 [wherein X is OH, N ratio or NH--(C, to C4
)-alkyl group, 8 and RI, R2 and Z are as above], together with the starting compounds required to synthesize the polycarbonate segment M, polyester segment, or polyamide segment M3. A method characterized by condensation.

2 M in Equation 10 is expressed as Equation M. [Wherein, D is chlorine, bromine, hydrogen or C, ~C4-alkyl, and L is a single bond, C, ~C5-alkylene, C2
~C5-alkylidene, C5-C,5-cycloalkylene, C5-C,5-alkylidene, or a group of the following formula, where P is a number from 2 to 50] or a polycarbonate segment of formula M2 [formula R and R' are the same or different, and C2 can be interposed with 1○- or cyclohexylene;
~C,2-alkylene, C5~C,5-cycloalkylene, C8~C,2arylene-dialkylene, C6~C
, 2arylene, or C,3-C,5-alkylidene-
diphenylene, p is a number from 2 to 50] or a polyester segment of formula M3, where R'' is hydrogen or C, to C4-alkyl,
The method of 1 above, wherein R' and p are polyamide segments as defined above.

3. The method of 1 above, wherein the amount of 8-hydroxyquinoline is 2 to 50 mol% with respect to the total amount of other starting compounds.

4. Mixing a bisphenol component with 8-hydroxyquinoline of formula 1 in which X is OH, a pis-chlorocarboxylic acid ester of phosgene or a bisphenol component, an aprotic water-immiscible solvent and an alkali metal hydroxide aqueous solution. 3. The method of 3 above, which comprises reacting in a liquid in the presence of a catalyst. 5. The method of 4 above, wherein the water-immiscible solvent is dichloroethane, methylene chloride, chloroform, monochlorobenzene, or dichlorobenzene, and the catalyst is triethylamine.

6. Method 4 above, wherein the reaction temperature is 0 to 40 do.

7 The starting material compounds for producing polycarbonate of formula 10 (M=M,) are bisphenol 4,4'-dihydroxyphenyl, bis(4-hydroxyphenyl)-propane-2,2 [bisphenol A], Bis(4-hydroxy-3,5-dichlorophenyl)-propane-2.
2 [tetrachlorobisphenol], bis(4-hydroxy-3,5-dibromophenyl)-bropan-2.
2 [tetrabromopisphenol A), bis(4-hydroxy-3,5-dimethylphenyl)-propane 2
・2 [tetratyrene bisphenol A], bis-(4
-Hydroxy-3-methylphenyl)-propane-2.
2 or pis-(4-hydroxyphenyl)-cyclohexane-1.1 [bisphenol Z].

8 The polyester of formula 10 (M=base) contains volatile alcohol ester of dicarboxylic acid together with glycol
Method 3 above, prepared by condensation with 8-hydroxyquinoline of formula 1, which is H.

9. The method of 8 above, wherein the reaction temperature is 120 to 300 pm.

10. The method of 9 above, which is carried out under reduced pressure in the presence of an acidic or basic catalyst.

11. The method of 3 above, wherein the polyester of formula 10 is produced by condensing a dicarboxylic acid chloride and the bisphenol of 7 above with 8-hydroxyquinoline of formula 1, wherein X is OH.

12 The dicarboxylic acid, Ustel, acid anhydride or acid chloride for producing the polyester of formula 10 is terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid,
diphenylmethane dicarboxylic acid, adipic acid, succinic acid, glutaric acid, sebacic acid, pimelic acid, suberic acid,
Azelaic acid, diglycolic acid, cyclohexane dicarboxylic acid or cyclohexane diacetic acid; esters are dimethyl esters, diethyl esters or dipropyl esters of the above acids; glycols are ethylene glycol, diethylene glycol, triethylene glycol,
1,2-pro/gundiol, 1,3-propanediol, 1,4-, 2,3- or 1,3-butanediol, 1,6-hexanediol, 1,10-decanediol, cyclohexanedimethanol, cyclohexanediol, 2・2-dimethylpropanediol (1.3
), glycerin monomethyl ether or a mixture of dihydric alcohols.

13. The method of 3 above, wherein a polyamide of formula 10 (M=M3) is made by reacting this functional acid chloride with a diamine and an 8-hydroxyquinoline of formula 1, where X is NH2.

14 The difunctional acid chloride is the above-mentioned dicarboxylic acid chloride, and the diamine is ethylene diamiso,
The method of 13 above, which is trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 4,4'-diaminodicyclohexylmethane, m- or p-phenylene diamine or diphenyl diamine.

15 A formula characterized by reacting the condensation polymer of formula 10 described in 1 above with a metal compound of formula 12 [wherein Q is the formula 1
G is a metal compound of the formula; E is H or; n is a number from 1 to 50; Me is a metal of the 1st to 8th subgroups or the 2nd to 5th royal groups; ,
T is an anion of an inorganic acid, an anion of an organic carboxylic acid, a converting agent, a C, to C,8-alkoxy group, a C6 to C-aryloxy group, and/or a trialkylsiloxy group having 3 to 12 carbon atoms; , m is the number of anionic bonds and/or ligands T on the metal atom, valence group < is the coordination number minus 2, r is a number from 0 to 20, R1, R2, Z and M are as described above.] A method for producing a metal-containing polymer.

16 The reaction was carried out in a homogeneous solution of an aprotic solvent from 20 to 6
and the molar ratio of the compound of formula 10 to the metal compound of formula 12 is from 1:0.5 to 1:1;
15. The method of 15 above, wherein the concentration of the compound of formula 10 and the compound of formula 12 in the solution is 0.001 to 3% by weight.

17 When T is an anion of an inorganic acid, an anion of an organic carboxylic acid and/or a leadifying agent, the reaction is between a compound of formula 10 in an aprotic solvent and a compound of formula 12 in a polar protic solvent.
It is a two-phase reaction with a compound of
and the molar ratio of the compound of formula 10 to the compound of formula 12 is 1
:0.5 to 1:1, the concentration of the compound of formula 10 in the solution is 1 to 30% by weight, and the concentration of the compound of formula 12 is 0.001 to 3% by weight. .

18 Formula 10 [wherein RI and R2 can be the same or different and mean hydrogen, (C, to C4)-alkyl, fenyl or halogen (e.g. chlorine or bromine), Z is the C string, CH
-C horse, isoalkylidene having 3 to 5 carbon atoms, 5 to 5 carbon atoms
15 cycloalkylene or cycloalkylidene group, or a group of formula 2-, R4, R5, and R3 on the strings are the same or different alkyl groups having 1 to 5 carbon atoms, and M is a polycarbonate segment. , polyester segment or polyamide segment].

19 M is the formula M, [wherein D is chlorine, bromine, hydrogen or C, ~C4-alkyl, L is a single bond, C, ~C5-alkylene, C2~
C5-alkylidene, C5-C,5-cycloalkylene, C5-C,5-cycloalkylidene, or a group of the following formula, p is a number from 2 to 50. Vertical polymer of formula 10.

,20 Formula 11 [However, in the formula, Q is the group of formula 1 melon or T, R1, R2, Z, and M are as defined in formula 10, n is a number from 1 to 50, and G is Corresponds to the metal compound of formula 12, where m is the number of metals present in the anion bond and/or T, and is the number obtained by subtracting 2 from the difference in valence or the coordination number, r is an integer from 0 to 20, Me is a metal from the 1st to 80th group of the periodic table or the 2nd to 5th royal group, especially Sc to Zn (atomic number 21 to 30), Y to Cd (
Atomic number 39-48), La-Hg (atomic number 57-8
0), Ac to U (atomic number 89 to 92), N, Pb and Bi metals, T is an anion of an inorganic mineral acid, an anion of an organic carboxylic acid, a sulfurizing agent, C, to C, 6 A metal-containing polymer corresponding to a C6-C,2-aryloxyester and/or a trialkylsiloxy group having 3 to 12 carbon atoms.

21 M is the formula M, [wherein D is chlorine, bromine, hydrogen or C, ~C4-alkyl, L is a single bond, C, ~C5-alkylene, C2~
C5-alkylidene, C5-C,5-cycloalkylene, C5-C,5-cycloalkylidene or a group, P
is an integer of 2 to 50.] The metal-containing polymer of formula 11 according to 3 above, which is a polycarbonate.

Claims (1)

[Claims] 1 Formula 10 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R^1 and R^2 are the same or different, hydrogen, (C
_1 to C_4)-alkyl, phenyl or halogen, Z is CH_2, CH-CH_3, isoalkylidene having 3 to 5 carbon atoms, cycloalkylene or cycloalkylidene having 5 to 15 carbon atoms, or a group of formula 2 ▲Math. There are chemical formulas, tables, etc. ▼ (where R^4, R^5 and R^3 are the same or different and are alkyl groups with 1 to 5 carbon atoms), M is polycarbonate segment M_1, polyester segment M_2 or polyamide segment M_3] with a metal compound of formula 12 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula 11 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Formula In, Q is a metal compound of the formula 10a ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or T, G is a metal compound of the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and E is H or ▲Mathematical formulas, chemical formulas, tables, etc. etc. ▼ where n is a number from 1 to 50, Me is a metal from the 1st to 8th subgroups or the 2nd to 5th main groups,
T is an inorganic acid anion, an organic carboxylic acid anion, a complexing agent, C_1-C_1_8-alkoxy group, C_6-C
_1_2-aryloxy group and/or carbon number 3-12
is a trialkylsiloxy group, m is the number of anion bonds and/or ligands T on the metal atom, is the difference in valence or the number of coordinations minus 2, and r is 0 to
20, and R^1, R^2, Z and M are as defined above].