DE2407309C3 - Polycondensates containing hydroxyquinoline end groups - Google Patents

Description

(2 B)

R ⁴ R ³ R ⁴
ι / \ ι ( 7th - C χ / I. R ⁵ R ⁵ R ⁴ R- '

R ⁵ CR ⁴

is where

R ⁵ , R ^{3 are} identical or different alkyl radicals having 1 to 5 carbon atoms, and

M is a polycarbanate segment or a polyester segment.

2. polycondensates of the general formula 10 according to claim 1, characterized in that M a poly carbonate segment represented by the following general formula Mi

ii l · C-O

is where D is chlorine, bromine, hydrogen or Ci-Ct-alkyl, L is a single bond Q-C5-alkylene, C ₂ -C5-alkylidene, C ₅ -Ci5-cycloalkylene, C ₅ -Ci5-cycloalkylidene or a radical of the following formula

CH ₃ CHj

CH ₃ CH ₃

4ο and ρ is an integer between 2 and 50.

In US-PS 36 97 481 chromans are incorporated as chain terminators in polycarbonates. Compared to the functional 8-hydroxyquinolines according to the invention, which are also used as chain terminators for polycarbonates and polyesters are used, the above-mentioned chromans have a completely different structure and no complexing properties, so the polycarbonates described in US Pat. No. 3,697,481 also not in comparison to the 8-hydroxychiriol-n-containing according to the invention Polycondensates as complexes

HO

R ¹

\ R ²

funds. Stabilizers for polymers with metallic Impurities used or converted to metal-containing or metal-bridged polycondensates can be, which also as described a wide field of application z. B. as finishing, weatherproof

and solvent-resistant coatings, polymerization accelerators etc. own.

The present invention relates to polycondensates of the general formula 10

and R ^{2 are} identical or different, and hydrogen, (Ci -C ^ alkyl, phenyl or halogen (beispieis * R ¹

> C) H
N

(10)

Way chlorine or bromine) mean And
CH ₂ , CH-GHj, an isoalkylidene radical with 3 to 5 carbon atoms, a cycloalkylene * or cycloalkylidene radical with 5 to 15 carbon atoms, or a radical of the general formula 2a

or 2b

8-hydroxyquinolines of the general formula I

ί R ⁴
ι R ⁴
I. R ¹
I. R ⁴
I. I.
C.
ι I.
c— <
I. -O I.
- C
I. R> R ⁵ R ^s ΐ R ³ Ö ι R ⁵ -C n * I is in those

(2 a)

(2 B)

R ⁵ , R ^{3 are} identical or different alkyl radicals with 1 to 5

Carbon atoms are, and
M is a polycarbonate segment, preferably the _ό

general formula

M ₁

or a polyester segment, preferably the general one formula

IO O I O O

!! Ii ι Il Il

M ₂ OjCRCO-R'-O-frC-RCO

ISL

pie_Polycarbonate segments have molecular weights Mn in the range between 1000 and 30,000; the polyester segments have molecular weights Mn in the range between 800 and 25,000.

In the polycarbonate segments Mi, D is chlorine, bromine, hydrogen or Ci-Gt-alkyl, L is a single bond, Ci-C ₅ -alkylene, C ₂ -Cv-alkylidene, C ^ -C \ y cycloalkylene, Cs-Cis-cycloalkylidene or a radical of the following general formula

CH, C ^- H ₃

c · / Vc

CH,

CH ₃

and ρ is an integer between 2 and 50; in the polyester segments M? R and R 'are identical or different and are C _{2 -C 2} -alkylene, which can be interrupted by -O- or cyclohexylene, Cs- Cis-cycloalkylene, Cg-Cu-arylene-dialkylene, for =, for example C ₈ - Ciz-Phenylenedialkylen, - Ce ^ -Cii'Afylen,

'For example phenylene, naphthylene, diphenylene, and Cn — Cis ^ alkylidene diphenylene, and ρ is an integer

between 2 and 50,

A process for the preparation of the 8-Hydroxychiriölinendgfüppen-containing polycondensates according to the invention of the general formula 10 consists in

in the

X stands for OH,

R>

and R ^{2 are} identical or different, and are hydrogen, (C, -O-alkyl, phenyl or halogen (for example chlorine or bromine) and

Z CH ₂ , CH-CH ₃ , an isoalkylidene radical with 3 to 5 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 15 carbon atoms, or a radical of the formulas 2a or 2b

R ^J

i0 C -

R ⁵

R ⁴

I. c

R *

R ⁵

(2a)

R ³

(2 B)

R ⁵ C ^- R ⁴

is, and filed in on the same day

r> German patent application P 24 07 3083 are described to cocondense directly with the starting compounds, which is required to build up the polycondensate segments M of the formula 10 according to known processes will.

It was surprisingly found that, for. B. in the production of polycarbonates with 8-hydroxyquinoline end groups according to the processes customary for polycarbonate syntheses, which are added during the condensation functional 8-hydroxyquinolines of the formula 1 (X = OH) are condensed at the chain end and on in this way react specifically as a chain terminator.

so that the complexing center of the 8-hydroxyquinolyl radical preserved.

The effect of the functional 8-hydroxyquinolines as chain terminators was determined by means of end group analysis and by comparing the molecular weights determined in this way with the measured values more independently Molecular weight determinations confirmed.

Through targeted addition of the functional 8-hydroxyquinolines of the general formula 1 in amounts of 2 Mol% to 50 mol%, based on the sum of the remaining starting compounds, as chain terminators polycondensates with 8-hydroxyquinoline end groups of the general formula 10 ir · the desired

Chain length can be set, the polymer units ρ of the polycarbonate or polyester, such as ooen for

,. , Formula 10 defines * available two to fifty times ' 'can.

The preparation of compounds of general

Formula 10 takes place depending on the type of polycode segments desired for the Representation of common polycondensate variants, where the radical X is the functional hydroxyquinolines

4er general formula 1 for the synthesis of polycarbonates and polyesters is OH.

A preferred method for the preparation of the polycarbonates with 8-HydroxychinoIin-endgruppen according to the general formula 10 (M = Mi) consists, for. B. therein, bisphenol components together with the functional 8-hydroxyquinolines of the general formula 1 (X = OH) under the conditions of the interfacial reaction with phosgene or the bischlorocarbonic acid esters of bisphenol components in a mixture of an aprotic, water-immiscible solvent such as. B. dichloroethane, methylene chloride, chloroform, mono- and dichlorobenzene, and aqueous alkali metal hydroxide solution in the presence of suitable catalysts, such as triethylamine, to implement π. Here, at temperatures around 20 ^° C., a little more than the equimolar amount of phosgene is used

To control the molecular weight, up to 50 mol%, based on the sum of the remaining 2η, are used Starting substances, the functional 8-hydroxychitiolines of the general formula 1 (X = OH) as a chain terminator.

The work-up of the polycarbonates can be carried out by customary methods, such as. B. by felling or by Evaporation of the solvent take place, expediently beforehand the polycarbonate-containing Phase is washed electrolyte-free. (Literature on the production of polycarbonates: H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, jo London 1964.)

Suitable diphenols for the production of polycarbonates according to the general formula 10 (M = Mi) are t. B.

4,4'-dihydroxydiphenyl. ⁿ

Bis (4-hydroxyphenyl) propane-2,2

(Bisphenol A),
Bis- (4-hydroxy-3,5-dichloro-phenyI) -propane-2,2

(Tetrachlorobisphenol),
Bis - ('/ - hydroxy-3,5-dibromophenyl) -propane-2,2 ⁴ⁿ

(Tetrabromobisphenol A),
Bis (4-hydroxy-3,5-dimethylphenyl) propane-2,2

(Tetramethylbispheno! A),
Bis- (4-hydroxy-3-methyl-phenyl) -propane-2,2, bis- (4-hydroxyphenyl) -cyclohexane-1.1 ^4>

(Bisphenol Z).

Further diphenols suitable for the production of polycarbonates are given in the US patents 30 28 365, 29 99 835, 3148 172, 32 71368, 29 70 137, 29 91 273. 32 71367, 32 80 078, 30 14 891, 19 99 846 towie in German Offenlegungsschriften 20 63 050 (Le A 13 359), 20 63 052 (Le A 13 425), 22 11 957 (Le A 14 240) and 22 11 956 (Le A 14 249).

Several processes are available for the production of polyesters with 8-hydroxyquinoline end groups according to the general formula 10 fM = M _2). A common process that is preferably suitable for the preparation of polyesters from glycols and aromatic dicarboxylic acid esters is the transesterification process. As is known, the diacid esters are easily volatile. TerephthaisäU; | _{t; Li} redimethylesterlmit corresponding'Glykolen, such as z / B / Äthylenglykoi, at temperatures of 120-300 ⁰ C ₁ optionally using reduced pressure Ufid presence of acidic or basic Katäly- »atoreri, z. B. MineraM, uren or alkali and alkaline earth oils, together "with the functional 8-Hydro 'xychinolinen of the general formula 1 (X = OH) condensed, the dicarboxylic acid ester depending on the desired degree of polymerization of the polyester in an excess of up to 50 mol%, based on the glycol component, can be added.

(Literature on the transesterification process: W. H. Carothers and F. J. van Natta, J. Amer. Chem. Soc. 52,31 <t [1930]; A. P. 25 34 028 [1948], Du Pont, inventor: E. F: Izard.)

If you want polyester of the general formula 10 (M = Mj) based on diphenols and aromatic dicarboxylic acids, the process of solution polycondensation with dicarboxylic acid chlorides, eg. B. isophthalic acid chloride and bisphenols, e.g. B. bisphenol A, as starting compounds, the reaction with the functional 8-hydroxyquinolines of the formula 1 (X = OH) preferably carried out according to the variant of interfacial condensation around 20 ° C and the sum of the phenolic components in a slight excess, based on the bifunctional acid chloride is used. Geppbenenfalls it is advisable to use a wetting agent such. fa. Add sodium lauryl sulfate. Suitable solvents are CH _{2 Cl 2} , CHCl ₃ , dichloroethane, mono- and dichlorobenzene. This has the advantage that the reactivity of the functional groups of the 8-hydroxyquinones is graded according to formula 1 (X = OH), and almost quantitatively only the functional center X is involved in the condensation.

(Literature on solution polycondensation:

H. Batzer, H. Holtschmidt. F. W. Wiloth and B. Mohr, Makromolekulare Chemie 7, 82 [1951]; W. R. Sorenson, T. W. Campbell: Preparative Methods of Polymer Chemistry S. 118, Verlag Chemie, Weinheim 1962.)

One of the processes mentioned also gives the polyesters of the general formula 10 (M = M ₂ ) based on aliphatic or cycloaliphatic carboxylic acids and glycols or on aliphatic or cycloaliphatic carboxylic acids and diphenols.

Suitable dicarboxylic acids or their esters, anhydrides and chlorides for the production of polyesters pemäß the general formula 10 (M = M ₂ ) are, for. B.

Terephthalic acid. Isophthalic acid,
Phthalic acid, methyl terephthalic acid,
Naphthalenedicarboxylic acid,
Diphenyldicarboxylic acid,
Diphenylmethanedicarboxylic acid, adipic acid,
Succinic acid, glutaric acid, sebacic acid,
Pimelic acid. Suberic acid. Azelaic acid,
Diglycolic acid, cyclohexanedicarboxylic acid,
Cyclohexanediacetic acid.

The preferred lower aliphatic pus of such acids are dimethyl ester, diethyl ester and Dipropyl ester and mixtures thereof.

Examples of suitable glycols are:

Ethylene glycols,
Di- and triethylene glycol,
1,2 and 1,3-propanediol,
1,4-2,3-, 1,3 butanediol.
1,6-hexanediol,!, JO-DecandioI,
Cyclphexanedimethanpl.Cyclohexanediol,
⁷ 22DihIiaii (i)

ypp (
Glycerol monomethyl ether

as well as mixtures of dihydric alcohols.

Suitable diphenols can be used in the Synthesis of the polycarbonates listed use

Find.

The subject matter of the present invention includes thus also a process for the preparation of the compounds of the formula 1 O ^ which is characterized is that for the production of the polycondensates of the structural part M by known processes ^ Hydföxy * quinolines of formula 1 as reaction components used.

The 8-hydoxyquinoline hydride groups according to the invention Polycondensates according to general formula 10 can be used in a suitable form for separating ro From metal ions of the transition from the periodic table, d. H. of the elements Sc to Zn (ordinal numbers 21 to 30), Y to Cd (ordinal numbers 39-48), La to Hg (Ordinal numbers 57-80), Ac to U (ordinal numbers 89-92) as well as Mg, Ca, Al, Pb and Bi from solutions

E.

or industrial wastewater. the Absorption of the metal ions is reversible; so you can easily wash them out z. B. with acids or Separate the copier from the polycarbonate again.

The polycondensates according to the invention can also for corrugation of troublesome metallic ones Impurities in thermoplastic or duoplastic Plastics in amounts from 0.01% by weight to 10% by weight, based on the total mixture are set.

The polycondensates according to the invention of the formula 10 can also be used for the production of metal-containing polymers, such as those of the following general formula 11

R ¹
I. -M- R ¹ -O- V ¹ V. <|) R ² R ² V * v ~ < >

-0 — G — S

(11)

correspond, in which R ¹ , R ² , Z, M are defined according to formula IO, η is between 1 and 50 and G is the metal compounds of formula 12a

[Me-O—] _r Me
(S) _ra (S) _m

corresponds in which

rri is the number of anion bonds and / or ligands S on the metal atom, which is calculated from the difference between valency or coordination number minus two,

r is an integer between 0 and 20,

Me is a metal of the 1st to 8th subgroup or the 2nd to 5th main group, and

S Anions of inorganic mineral acids, organic carboxylic acids, complexing agents, Ci - Cm-alkoxy radicals, Ce-C | ₂ -aryloxy radicals and / or trialkylsiloxy radicals having 3 to 12 carbon atoms, and

E H or

Polyethylene, polypropylene, polyacrylate,
Copolymers of (meth) acrylates and
at least one further monomer,
Vinyl acetate polymers,

jo ethylene-vinyl acetate copolymers,
Polycarbonates, polysulfones,
Polyphenylene oxides, styrene copolymers,
ABS-type polymers (acrylonitrile-butadiene-styrene-graft polymer-thermoplastics),

Nylon-type polyamides or polycaprolactam,

Polyethylene terephthalates, polyacetals, etc.

In addition, the metal-containing polymers of general formula 11 can be used as catalysts and, for. Am ■ 40 form of cobalt compounds, as initiators for Reactions that take place via a radical mechanism. Find use.

The following examples describe the production of some polycondensates containing S-hydroxyquinoline end groups of the general formula 10 and some metal-containing polymers of the formula 11.

(S) _m
(Me-O-VMe (S) "

50

is.

These metal-containing polymers of the general formula 11 can be used by themselves or as part of a Polymer alloy for the production of weather, corrosion, solvent and heat resistant coatings, as a sizing agent and as an adhesion promoter between metals, metal oxides, glass surfaces and subsequently applied plastics and lacquers can be used.

The metal-containing polymers of the general formula 11 can be used as stabilizers for plastics can be used. Such plastics are polyvinyl chloride or their copolymers like it

Ethylene chloride or
Vinyl acetate-vinyl chloride copolymer,

example 1

456 g of bisphenol A and 559 g of 2- [4-hydroxyphenyl] -2- [5- (8-hydroxyquinolyl)] propane are dissolved in 4 kg of 9% sodium hydroxide solution and then 9 kg of methylene chloride are added. 562.8 g of phosgene are introduced with vigorous stirring and then 60 ml of a 4% strength triethylamine solution are added dropwise. The phases are separated and the aqueous phase is checked for complete conversion. The organic phase is extracted once with 5% H3PO4, washed neutral with water and then dried over sodium sulfate. The organic phase is concentrated and the short-chain polycarbonate with hydroxyquinoline end groups is obtained directly by precipitation in Methanol η _τ α: 1.038; Nitrogen analysis: 2.56% N _2; phenol. OH: 2.8%. The molecular weight determined from these values is Af _n = 1178.

24 OF 309

ίο

Example 2

456 g of bisphenol A and 7 g of 2-14 ⁱ hydroxyphehyl] -2- [5- (e ^ hydroxychinölvl ^ -propane are dissolved in 2.675 kg of 9% sodium hydroxide solution. Then 6 kg of methyl chloride are added and 280 g of phosgene are introduced with vigorous stirring 30 ml of a 4% strength triethylamine solution are then added and the mixture is left to run for 1 hour, the pH of the solution being kept at 13 by adding sodium hydroxide solution.
η, α: 1.517

Nitrogen analysis N ₂ : 0.04%
M _n = 17 800 (membrane osmometric in dioxane)

Example 3

114 g of bisphenol A, 9.30 g of 2- [4-hydroxyphenyl] -2- [5- (8-hydroxyquinolyl)] 'propane and 40 g of sodium hydroxide are dissolved in 3 l of water. Then 300 ml of a 10% strength sodium lauryl sulfal solution are added. The reaction solution is stirred vigorously and 101.6 g of isophthalic acid dichloride in 31 methylene chloride are then added. The emulsion formed is stirred for a further 5 minutes and then precipitated in acetone. It is filtered and the polymer containing hydroxyquinoline end groups is washed with water and acetone. The polyester purified in this way is dried in vacuo
%: 1.035
M /, (osmometric): 5500

Through the following experiments, the application ! possibility of the stressed substances proven.

^: Experiment 1

7.65 g (7 mmol) of the polycarbonate described in Example 1 with hydroxychirioline end groups (M _n = 1096) are absolute in 150 ml. GH ₂ Cl ₂ dissolved and successively with 10 ml of a solution of 3.4 g of titanium tetra-butoxide in 100 ml of absol. CH ₂ Cl ₂ added, the relative viscosity being determined as a measure of the increase in molecular weight in each case after adding 10 ml of the titanium tetrabutylate solution. In Table I below, the increasing viscosity is related to the amount of metal compound added in each case.

Table 1

template Encore relationship '' rel Polycondensate / Metal connection 7.65 g polycarbonate oxyquinoline 10 ml solution I *) 7: 1 1.055 end groups (M _n = 1096) the same 20 ml solution I *) 7: 2 1.066 the same 30 rhi solution I *) 7: 3 1.082 the same 40 ml solution I *) 7: 4 1.093 the same 50 rhi solution I *) 7: 5 1.142

*) Solution I: 3.4 g of titanium tetra-butoxide in 100 ml of CH ₂ GI ₂ .

Attempt 2

1.78 g of the hydroxyquinoline- ■ endgroup-containing polycarbonate (M _n = 17 800) prepared in Example 2 are absolute in 100 ml. CH ₂ Cl ₂ dissolved and submitted 10 ml of this solution. For this purpose, 1 ml of a solution of 3.83 g of zirconium tetra-butoxide in 1 liter of absol. CH ₂ Cl _{2 was added} dropwise and, as in Example 2, the relative viscosity was determined each time.

Table 2 I ml solution II *) relationship '/ rci template Polycondensate / 2 ml solution II *) Metal connection 3 ml solution II *) 10: 1 1.714 1.78 g polycarbonate with oxyquinoline 4 ml solution II *) end groups (M _n = 17800) 5 ml solution II *) 10: 2 1,844 desgi. υ ffii i ^ OSüng ii ) 10: 3 2.083 the same 10: 4 2,419 the same 10: 5 2.635 the same 10: 6 Z, / UJ the same

*) Solution II: 3.83 g of zirconium tetra-butoxide in 1 1 CH ₂ Cl.

Attempt 3

5 g of the polycarbonate produced in Example 2 (M _n = 17 800) are absolute in 180 ml. GH ₂ Cl ₂ dissolved and with 14 ml, 21 ml and 28 ml of a solution of 0.383 g of zirconium tetra-butoxide in ί00 ml of absol. CH ₂ CI _{2 added} dropwise, the resulting chain-lengthened,

Table 3

zirconium-containing polycarbonates were isolated and processed into foils. Table 3 shows the yield stress Os, the tear strength an, the elongation at break ε «and the modulus of elasticity of the foils and related to the metal content of the respective polycondensate

relationship
Polycondensate /
Mclall connection Attempt 4 o _s (kp / cm ² ) on (kp / cm ² ) 69.3 Modulus of elasticity
(kp / cm ² ) 1: 0.5 533 509 50.6 27,000 1: 0.75 500 500 50.8 28 400 1: 1 516 500 29 700

24 g of a polycarbonate prepared according to Example 2 with 8-hydroxyquinoline end groups and a molecular weight M _n = 11,980 are absolute in 200 ml. CH ₂ Cl ₂ dissolved and with 0.476 g of titanium tetrabutoxide in absolute. CH ₂ Cl ₂ added.

The metal-containing polycondensate was processed into a film and the modulus of elasticity and the Freezing temperature determined. In addition, the molecular weight was determined osmometrically.

, Table 4

g g g y

polymer in 20 ml CH ₂ Cl _{2 was} added. The resulting titanium-containing polycarbonate was examined by means of differential thermal analysis. Table 5 shows the glass transition temperature increased by incorporation of the metal.

Table 5

relationship
Polycondensate / metal compound

Ratio M _n ET modulus of elasticity

Polycondensate / osmometric

Metal starting substance

connection A / "11980 (" C) (kp / cm ² )

ET ET

Polycondensate metal poly with hydroxy condensate quinoline end groups

Thermal stability

35 1: 0.5

145 ° C

I62 ° C

from 350 ° C decomposition

S g 6ifi <5S
nats with M _n

18 800

154.5

22 700

• to attempt 6
the in example

Attempt 5

Example 2 Hergesieüieri Füiycarbo-16,000 were in 100 ml absol. CH ₂ Cl ₂ 1.78 g each of the polycarbonate prepared in Example 2 with 8-hydroxyquinoline end groups are reacted with the metal acetyiacetonates listed in Table 6 in a molar ratio of i: i by heating for two hours at 140 ° in dichlorobenzene.

, Table 6

template

Encore

Metal content calculated

found

, 1.78 g of oxyquinoline polycarbonate (M _n ■■

the same

the same

800) 26 mg cobalt acetylacetonate 0.33

mg nickel acetylacetonate 0.33
mg iron acetylacetonate 0.32

0.33 0.34 0.31

All metal-containing polycarbonates could be processed into foils with tear strength o _R (kp / cm ² ): 585. The cobalt-containing film had an elongation at break Br ⁰ Zo: 51

Tensile test tested: 60 Ε module (kp / cm ² ): 28 500

attempt

3 g each of the polyester described in Example 3 with S-hydroxychinolincndgruppcn (Af _n == 5500) are absolute in 100 ml. CH ₂ CI ₂ dissolved and mixed with the following metal alcoholate solutions:

1. 10 ml of a solution of 1.77 gtitanium tetra-butylate in iOOrnlabsoi. CH ₂ Cl ₂ ,

2. 10 ml of a solution of 2 g of zirconium tetra-butylate in 10OmUbSoLCH ₂ Cl ₂ -

; ■ 13 14

¹ table- 7

A ^ ' - ■ ■ ' ■ ——— ■ - ■ -

_{; j} ι template adding metal content

, calculated found

ι _-:; - ^ ■ ■ - ■ ~ - - ^ ^ ^^^^^^ -i-, --_. - ^^ ^

'' 3 g polyester with 8-hydroxyquinoline endguppen (M ,, 55Ö0) 0.177 g Ti (C ₄ H ₉ O) ₄ 0.83% 0.75%

the same 0.20OgZr (C ₄ H ₉ O) ₄ 1.6% 1.4%

Claims (1)

Claims: Polycondensates of the general formula 10 R ¹ R ¹ OH (10) wherein and R ^{2 are} identical or different, and are hydrogen, (Ci-O-Alky !, phenyl or halogen and Z CH ₂ , CH - CH ₃ , an isoalkylidene radical with 3 to 5 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 15 carbon atoms, or a radical of the general formulas 2a or 2b (2a)