DE1570699A1 - Process for the preparation of poly (2,6-dihalophenylene) ethers - Google Patents

Description

PATENT ADVOCATE DR. HANS-GUNTHER EGGERT, .DIPLOMA CHEMIST

5 koln-hndenthXl peter-kintgen-stbasse 2

Dr. Expl.

Cologne, X6.9.1965 Eg / Ax

General Electric Company,

1 River Road, Schenectady 5, N.Y. (v.St.A.).

Process for the production of poly (2,6-dihalophenylene) -

ether

The invention relates to the oxidation of 2,6-dihalosubstituted substances Phenols to poly (2,6-dihalophenylene) ethers in the presence of a dissolved copper amine complex.

The oxidative coupling of phenols in the presence of a copper

amine complex is the subject of German patents

(Patent application G 38 186 IVb / l2o) and (patent application G 38 266 IVb / 39c) of the applicant. In these processes, certain monohydric, monocyclic phenols are oxidized in the presence of a catalyst which contains a basic copper (II) salt and secondary or tertiary amines. While the process of these patents is feasible with 2,4-dihalophenols, it excludes phenols which contain halogen in both the 2- and 6-positions.

A modification of the general procedure is the subject of

German patents (patent application G 39 4-77 IVd / 39o) and

(Patent application G 39 4 * 98 IVd / 12p) by the applicant.

In this case, certain metal-aromatic heterocyclic amine complexes of 2,4,6-Trihalogenphenolen at temperatures decompose above 8O ⁰ C, said poly-2,6-dihalogenphenylenä * ther are formed from medium molecular weight. This procedure is

0098U / 1759

in the production τοη higher-aolekularen polymer · _{"i-transferable,} and is not AUOH for the polymerization of ~ ± 2.6 D-halogen phenols with Wasseret off ia the p-> 8fcelluagi

Poly (2,6-dihalophenylene) ethers were released from the Metal halide from Metallealaen (especially alkali ·· and Silver salts) of 2,4t6-trihalophenols * D $ ese Processes generally produce products of low "" "molecular weight, which have been recognized as being highly branched. Polymers of higher molecular weight were produced according to a known process in which an alkali "2,4" 6-trihalogenpheÄ © lat. in an aqueous two-phase system in the presence of an oxidizing agent or a free radical initiator is polymerized. The high molecular weight polymer formed turned out to be very branched, a confirmation of previous experiences.

The invention relates to a general, simple and economical process for the preparation of poly (2,6-di ~ halophenylene) ethers duroh oxidative coupling of 2,6-dihalogen-substituted, monohydric, monoolyolic phenols. ThatB Process is characterized in that one halophenols of the structural formula

X »9 ^H X»

where X * is iodine, bromine or chlorine and X has the same meaning as X * and can also be hydrogen, in the presence of oxygen and a catalytically active complex voa cuprophilic secondary and tertiary amines with a basic copper (II) salt at a Temperature of not more than 120 ⁰ Q or, if X is halogen, of not more than 8G ⁰ O in Q-egenwaB-fe of an ouprophilic aromatic heterocyclic amine.

In the reaction according to the invention, the hydrogen atom _'-, the hydroxyl group of the halophenol molecule, a hydrogen

0098U / 1758

-eier halogen substituent in the p-position of the haloplienol molecule and oxygen is involved with the formation of water or hydrogen halide. It is true that the reaction becomes oxidative Coupling or polymerization denotes, however, it is probable that the reaction is not directly an oxidation of the hemophenol molectile with molecular oxygen includes, but that it is rather an oxidation of the Eupfer amine catalyst, which is then used in both Condensation polymerizations as well as oxidation polymerizations of various halophenols is active.

The halophenols obtained by the process according to the invention can be coupled have the following formula

^. OH

Herein Z is hydrogen, iodine, bromine or chlorine and Z 'is each iodine, bromine or chlorine.

In the practice of the invention it has been found that the particular lain must be a strongly coordinating ligand, rather than not forms stable chelates with copper ions, i.e. "cuprophil" is · The complex of a basic copper (II) salt with a ouprophilen Aain is further defined here as "catalytically active" · Meβ indicates that the complex is in the presence ■ the halophenols used according to the invention functionally is stable.

The ouprophilen imine urnftssen secondary and tertiary Aminli- ligands, namely _r monodentate strongly co-ordinating ligands and strongly coordinating, weak ehelatbildende, mehrzähMge Idganden. It can be assumed that the choice of a cuprophilic, possibly strained, polyamine ligand depends on the number of carbon atoms separating a pair of nitrogen atoms and on the nature of the substituents on the nitrogen atoms. As a reference example for definition

0098 U / 1759. -

. ■ '■ J

Of the ouprophilic amines,! etraaetnyl ~ 1,2-ethylehtd ± aiala are considered amines that form complexes that have a higher stability than tetramethyl-1,2-ethyltBi4iaaia, measured by the association constant, the free energy of formation or the like, are generally unsuitable »while those which form complexes of lower stability suitable for the purposes of the invention, possibly under tension represent standing ligands.

♦ Typical examples τοη strongly coordinating, weakly ohelate-forming polyamines are NfHfN
ϊϊ, Ιί, Ν ·, N «-Tetraamyl-1,2-ethylenediamine, N» - 1 ^ -ethylenediamine, symmetrical dibenzyldimethylenediamine-1,2-ethylenediamine, 1,2-ethylene-N, N »-d: ün < i: rpholine, N, N, N ¹ , F'-fetramethyl-1,3-propanediamine, Ν, Ν, Ν », N'-tetramethyl-ijS-butanediamine and M, N, N *, li ^l " * 3 ? ^e ' ^fc ramethyl-1 | 4-butanediamine. Polyalkylenepolyamines, aminoalkyl-substituted aromatic heterocyclic amines and bifunctional heterooyelic amines can be used as further polyamines.

The term “secondary and tertiary aliphatic amines ^{11 used here} denotes both the strongly coordinating, potentially unstable multivalent aliphatic (and substituted aliphatic) polyamines and the strongly coordinating, secondary and tertiary monovalent aliphatic (and substituted aliphatic) monoamines. In the case of the monovalent ligands the ouprophilic property is related to the ability to form stable keerdinativbinduagea, measured by the dissociation constant and the free energy of formation, which is a function of the basicity of the amine. The more strongly coordinating ligands also prove to be stronger bases. The base strength is usually determined by the size pKg given, which is the negative logarithm of the IBaBPPedissosierungskonstante the amine In general, the strongly coordinating ligands that are suitable for the purposes of the invention have a pKg host τοη τοη greater than 6.0, with a few exceptions, the higher n values rarely exceed 13 »0

0098U / 1789 »

BAD OR (GINAi

For example, pyridine, which is unsuitable, has a • value of 5 »4, while the methylpyridines have a pKg value of ■ more than 6.0 and are strongly coordinating idgands for the purposes of the invention. · An obvious exception to this rule is pearylaniline , which has a pK _g value of 5.1, but forms a catalytically active complex and must also be regarded as a strongly coordinating ligand. As a pattern for heterocyclic and aliphatic (and substituted aliphatic) ligands pyridine or dimethylaniline can be viewed,

The preferred secondary and tertiary aliphatic monoamines according to the invention can be defined as derivatives of dirnethylamine according to the formula

H ₂₁ -IT-B ₂₂

^R 23

where E ₂₁ ^ ¹ * ³ - ^ 22 in ^{each case} O ^ -O ^ Q-alkyl, 0 ^ -ög «» represent hydroxyalkyl or aralkyl and Bg ^ for hydrogen, O | -O ^ Q-alkyl, O ^ ög- Hydroxyalkyl, aralkyl and aryl are, typical examples of strongly coordinating secondary and tertiary aliphatic monoamines are dimethylamine, diisopropylamine, di-n-butylamine, "methylethylamine, methylbenzylamine, dibenzylamine, diootylamine, fErimethylamine, iriethylamine, methylamethylbenzylamine, methylamethylbenzylamine, methylamethylbenzylamine, methylamethylbenzylamine, methylamethylbenzylamine, methylamethylbenzylamine, diisopropylamine, di-n-butylamine." , Dimethylaniline and diethylamine «

Another class of singular, ouprophilic ligands, that are suitable for the purposes of the invention are those that are strong coordinating saturated and aromatic heterocyclic ... amines, e.g. 2-methylpyridine, 2,4-dimethylpyridine, 2,4 »6-! Dri- * methylpyridine, 2-propylpyridine, 2-benzylpyridine, 2- (5-iTonyl) -pyridine, 2- (2 "-Methoxyethyl) -6-methylpyridine, 2-" aminopyridine and 2- (2-pyridyl) pyridine

• Secondary and tertiary saturated heterooyolic amines are

009814/1769 _BAD Sä!

the hydrogenation and partial hydrogenation products of the aromatic heterocyclic compounds and di ·% tut'ated derivatives of these products. Those of this group, in turn, have a pKg value t more valid and form catalytically active complexes with copper _. Ä-alkylpyrrolidines and pyrroles, imidazolidines, quinolidines ^ 'JF- ^ AHfI **' quinolidines, thiazolidines, morpholines, N-alkylmorpfiuolio ·,! Thiomorpholines, morpholine, N-methylmorpheline, V-BentfUier ^ liö »lin, ir-urethyl- 2-pyrrolidine and 1,4-diazabioycle- (2 _t t _t a) © otaa

The reaction conditions, such as the berorzugte reioh and the choice of particular preferred örupp · ren amines, depend on the type of according to formula I the substituents obtained from · In general, it is convenient to the reaction at a temperature of nioht more ale 120 ⁰ O, or Wenji the p-substituent is of the formula X · I and halo is rerwtttöet as jmin a ouprophiles aromatic heterocyclic amine s at a temperature of not more than 80 ⁰ O durchsöfUha? _#

The halophenols can be polymerized with up to 99 hol ~ £ a of several other phenol compounds Phenolic oomonomers have the formula

wherein X is hydrogen, iodine, bromine or chlorine. Qu is a; monovalent substituents namely hydrogen, a hydrocarbon residue that does not contain a tertiary α-carbon atom? a * halogenated hydrocarbon radical, the at least two G-atoms * zwisohen the halogen atom and the phenol ring and keia, tertiary α-carbon atom contains a OxykohlenwasserstoffJreirfj 3 ^f no aliphatic tertiary α-Kohlenet of fatoe enti>El-t> or ~ · a Halogenoxykohlenwasserstoffrestf · - who at least «knows

0098H / 1759

"Between the halogen atom and the piienol ring and no '" liphatieehes tertiary α "carbon atom! Q * and Q "have the same meaning as Q and can additionally halogen •• la with the proviso that X must be halogen, if Q and Q * are both substituents from the group of aryl radicals, haloaryi radicals, oxy-carbon hydrogen radicals and halogenoocycarbon-hydrogen radicals bind, Preferably Q * is hydrogen "" No tertiary "α" carbon atom containing ¹¹ means t "that to - the terminal carbon atom of the aliphatic hydrocarbon - ■ ubstituent bonded to the phenol ring (either directly" if the substituent is hydrocarbon or halogenated hydrocarbon) let, or via the oxygen atom, if the substituent is orycarbons or halooxy hydrocarbons) "at least one hydrogen atom is bonded" The called phenols have the structure

)H 111

in which Q and Q * have the meanings already mentioned and are preferably not hydrogen. Q and Q * are preferably lower (O ₁ WJ ₊ ) alkyl radicals.

Q ₁ Q * and Q "can be monovalent hydrocarbon radicals in all formulas shown in the table. Isobutyl, Cyolobutyl, Jyeyl »Oyolopentyl, Hexyl, Cyclohexyl, Ifethyloyolohexyl, Äthyleyolohexyl, Ootyl, Deoyl, Ootadeeyl etc.j alkenyl including-IiOh Cyoloalkenyl, ε.B. Vinyl, Allyl» Butenyl, Cyclobutenyl,. ; Alkynyl, e.g. Prop * rgyl | Aryl einsohliefilioh Alkaryl, ζ · Β. Phenyl, TοIyI, Ethylphenyl, ^ fIyI »Haphthyl, Hethylnaphthyl etc .; Aralkyl, eg Lensyl, Phenyläthyl, Phenylpropyl and Tolofylenkohol. As already mentioned, can the monovalent halohydrocarbons be the same as the hydrocarbon radicals with the exception of 4-methyl · »and a-haloalkyl radicals, in which one or more

ÖÖ98U / 1759

■. ■■■■■ BAD ORIGINAL

Hydrogen atoms are replaced by halogen, with halogenated hydrocarbon radicals are formed, the least · two carbon atoms between the halogen and the free Contain valence. Examples are 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 2,2-diohloroethyl, 2- and 3-bromopropyl, 2,2-DIfIuOr-S-JOdPrOPyI, 2-, 3- and 4-bromobutyl, 2-, 3- »4- and 5 ~: fluoramyl, 2-chlorovinyl, 2- and 3-bromallJrl, 2- and 3-fluoropropargyl, Mono-, di-, tri-, tetra- and pentaehlorphenyl, Mono-, di-, tri- and tetrabromotolyl, Ohloräthylphenyl, Äthylohlorphenyl, Fluoroxylyl, chloronaphthyl, bromobenzyl, iodophenylethyl, Phenylohloroethyl and bromotolylethyl. .

Typical examples of monovalent oxyhydrocarbon radicals are methoxy, ethoxy, propoxy, isopropoxy, butexy, sec-butoxy, tert-butoxy, amoxy, hexoxy, octoxy, decoxy, vinoxy, alloxy, Butenoxy, propargoxy, phenyloxy, toloxy, xthylphenoxy, toloxy, Naphthoxy, methylnaphthoxy, beneoxy, phenylethoxy, phenylpropoxy, Tolyläthoxy uew · The monovalent halooxy hydrocarbon radicals can be the same as the standing ones named oxyhydrocarbons with the exception of the methexy and a-Haloalkoxy radicals in which one or more hydrogen atoms by a halogen, e.g. fluorine, chlorine, bromine or iodine, be replaced, with Halogenoxykohlenwaaserstofüseste with at least two carbon atoms can be obtained between the halogen and the free valence. Some typical examples for this are 2-chloroeth »xy, 2-bromoethoxy, 2-fluorothoxy, 2,2-dichloroethoxy, 2- and 3-bromopropoxy, 2,2-difluor-3-chloropropoxy, 2-, 3- and 4-iodobutoxy, 2-, 3-, 4- and 5-fluoramoxy, 2-Ghlorvinoxy, 2- and 3-Bromoaltoxy, 2- and 3-PluorpfsBparg © xy, Monq-, Di-, Tri-, Tetra- and Pentachlorophenoxy, MonoS, Di-, Tri- and Tetrabromtoloxy, Ohloräthylphenoxy, Xthylohlorphenoxy, Iodoxyloxy, chloronaphthoxy, bromobenzoxy, chlorophenylethoxy, Phenylchloroethoxy and bromotolylethoxy

Examples of preferred phenols are 2-methylphenol, 2,6-dimethylphenol, 2-methyl-6-fluorophenol, 2,6-diethylphenol, 2-ethyl-6-propylphenol, 2,6-diisopropylphenol, 2,6-dibutylphenol,

0098U / 1759

2,6-pimethoxyphenol, 2 _and 6-diphenylphosphol, 2 "" methyl-6-phenylphenol and 2,4 "bichloro-6" methylphenol.

When preparing the catalyst from a "basic Copper (II) salt and an ouprophilic amine each have that When using copper eel in general, there was little influence on the character of the product Run out of copper (II) salt or a copper (I) salt * The only one The prerequisite is that when using a copper (l) salt this must be able to exist in the divalent form and form a complex with the ouprophilic amine must, which is soluble in the reaction medium ", The necessity that the copper (I) salt must be capable in the divalent Form is based on the assumption that the oxidation of the phenol takes place by the fact that the oxygen with the complex from euprophilic amine and copper (I) - »salt reacts, whereby as an intermediate compound an activated complex of ouprophilem Amine and basic copper (II) -aalζ is formed with the Phenol reacts to form an unstable intermediate compound, the sioh with the formation of the self-condensation product of phenol and decomposed by water and the amine-copper (l) salt complex regenerated «This activated complex can also be formed if one looks at the formation of the copper-amine complex a copper (II) salt is assumed from the outset, for example by adding a reducing agent, e.g. copper metal, used the sioh with what has become free. Anion combined and the copper (I) salt forms in situ. It can however, simpler methods can also be used. For example the activated complex can be formed by adding cupric hydroxide to a cupric salt, for Copper (II) salt is a base, a copper (II) salt Alkali salt of phenol (which could be the phenoxide of phenol) or a copper (II) salt with an ion from eh.- treated with resin containing interchangeable hydroxyl groups. These reactions are preferably carried out in the presence of the ouprophilic amine to prevent precipitation of the basic To prevent copper (II) salt, however, it is possible that

.; ■ 009SU / 1769 ^ -

_8A D

euprophilic amine to be added later, the basic copper (II) salt also being dissolved as a precipitate. Typical examples of suitable basic copper (II) salts that do not amines according to the invention can be converted into complexes, are copper (II) oxychloride, copper (II) oxybroad.A and basieohee Copper (II) sulfate.

The copper-amine complex serving as a catalyst for the process according to the invention is preferably and most extensively formed in situ by the components, ie. there· Copper (I) as and the amine, added to the reaction mixture · Bas copper (I) salt must be soluble in the amine »d» h » it must form a complex with the amine (which is still soluble in the reaction medium) and also be capable of bivalent form to be present · For the method according to Copper (I) salts suitable for the invention are, for example, copper (I) chloride, copper (I) bromide, copper (I) sulfate, Copper (I) -uid, copper (I) -tetramine sulphate, copper (l) -e> oet at, Copper (I) propienate, copper (I) palmitate and copper (I) «» «« naoate.

The polymerization is only a small catalytic amount

of the copper-amine complex necessary · In general, proved a lot of the copper-amin complexes are found to be suitable which the molar ratio of the monomer to copper in the range of 1-150, with values outside the range optionally used and a ratio of 8 to 25 µm is generally preferred.

In the polymerization of monomers which are substituted with halogen in the p-position, a must in the reaction system The presence of a hydrogen halide acceptor "In these tales it is often sufficient if at least an essentially heterogeneous amount of the amine or the copper-amine complex is present." Use the amount of the copper-amine complex bu, b.B »» norganieeh · Alkali compounds »* .B. Vatriunhydrexyd, Kftliuahy * «acy * and * Oaloium hydroxide, organic bases, «· Β. Benzyltrimetliylftamenl

0098U / 1769

'- Bethoxyd, and organic and inorganic anions resin · · The addition of bases to Eeaktionsgemisoh must be careful to avoid a surplus of eo high IRFC, AAQ is zarstört the catalyst system "used In polymerization Sound 2 _i 4F6-Trihalogenphenol®n is frequently ^v Tor * ug * w "ie" d excess "h _e least one stöohi ©» metric amount of either the amine or the copper "" amine complex as a hydrogen halide acceptor "

Molecular oxygen must be present in the reaction mixture, even if the monomer is a p-halophenol. In this pail it was found that the oxygen absorption is proportional to the amount of oxygen present and is independent of the phenolic concentration to be polymerized. The introduction of oxygen or a suitable oxygen-containing gas must be continued throughout the course of the reaction, but in certain recognizable cases it can be terminated after the saturation of the copper-amine complex Stoehiemetric amount of oxygen required for its removal.

The method according to the invention is preferably carried out in a% xl substantially homogeneous solution which contains the copper · Astin complex »the monomer or the monomers, the product polymers and a relatively inert, non-aqueous Iöeungsmittel; Particularly preferred solvents are aromatic hydrocarbons, e.g. benzene, toluene, xflol, etc., and halogenated hydrocarbons, such as chloro-bejurol, dichlorobenzene, chloroform, trichlorethylene and tetra-

'ohlor & thylen. Other solvents, e.g. alcohols, ketones, aliphatic hydrocarbons, nitro hydrocarbons, ethers, Beterι anides, sulfoxides, etc., can also be used provided that they do not interfere or take part in the oxy-

'Dationreaktlon participate, and so long the product in it Remains soluble until the copper-amine complex decomposes.

009814/1759 ' _eAD

~ 12 -

to prevent by water, it is often convenient to remove the water physically or for the The presence of a desiccant. Any relatively inert, and preferably inexpensive, desiccant can be used. The physical methods used are the aeotropic Distillation and stripping with an inert gas are preferred *

The temperature at which the reaction is carried out lor <3> eollte depending on the type _f of the abovementioned amines uad halophenols between ambient temperature (about 25-35 C) and 12O ⁰ O are. At ambient temperature, the JJolymerisations- is, speed is too low, and temperatures over 100 C eind usually undesirable · The "optimum temperature range is 65 to 80 ⁰ C.

During the copolymerization, the non-halogenated comonomer generally a much lower optimum polymerization temperature. The copolymerization is conveniently accomplished by carrying out the reaction in two stages, viz first a certain time at the lower temperature which is optimal for the comonomer, and then and abeohliee— send a certain time at the higher temperature which is optimal for the halophenol. As by fractionating the product was found to be the halophenylene oxide radicals evenly distributed over the fractions of different molecular weights. In this process, the addition • a hydrogen halide acceptor to the system during the second stage preferred when circumstances call for a great addition.

If * the halophenols of the formula I according to the method according to polymerized according to the invention, they form which essentially consist of several bonded oxyphenylene units, namely

IV

- units and

0098U / 1759 »

branched units

Here, X * has the meaning already mentioned; R ¹ and R "are iodine, bromine, chlorine or a branching 2,6-disubstituted 1-phenoxy radical, and n ^ and n ₂ are integers from 1 upwards, where at least one of the radicals R 'and R" has the branching 2, Represents 6-disubstituted 1-phenoxy radical, which, since it is derived from the reacting phenols, is contained in the sum tt-j + n ₂ * If at the oxidative. Polymerisatiansreaktion an Oomonomeres of the formula II is involved, the poly (halophenylene ether) still contains

n-

Q "

Q »

copolymeric units

where Q, Q ¹ , Q "and η have the meanings already mentioned. To a certain extent, the o-position in the halophenols of the formula I _1, if it is substituted by halogen, is oxidatively coupled with other types of phenol, which are involved in the overall reaction of the polymerization The consequence of this is that the poly (halophenylene ether) obtained by this process additionally comprises a minimum number of polymeric units according to the formula III, in which Ζ »can furthermore represent a monovalent or divalent, branching o-phenoxy radical, that of any monomeric halophenols or oomonomerea

009814/1759 bad original

. u - 157 ^ 699 · ί

Phenols can be derived, which in daa Beaktionegemisoh can be included. As most of these phenolftytes preferably at least 2,6-diubetituler * sin *, wtf * this branching o-phenoxy radicals hereinafter referred to as branching ones 2,6-disubstituted 1-phenoxy radical is awarded, provided that it is derived from any pheno! which have been mentioned above

The process according to the invention enables the production of poly (halophenylene ethers) of low, medium or higher molecular weight. The molecular weight of a certain polymer naturally depends on the halophenol and other phenols used as starting material, the 1min used in the analyzer system, the temperature and the reaction conditions in general which is known to be a function of the molecular weight of each polymer 1βΊ | was determined in each case by extrapolation of the specific viscosities, which were determined for the polymers in chloroform solution at 30 ⁰ O n & eh standard methods, to the nail concentration «unless otherwise stated, understand M ± 9h the specified (residual viscosities in dl / g

According to the method according to the invention, it is possible to produce slightly curved, higher molecular weight poly (2,6-dihalogenophenylene leather with a Grenja viscosity of at least 0.09) defines that the ratio of n ^ to the sum n ^ + n _{2 is} greater than «SuIl and less than 0.25. Within this definition, the polymer produced according to the invention is considered to be minimally branched.

Further minimally branched, high molecular weight duroh polymerization of halogenated phenols are prepared with the phenols of the -formula "II or III · This QopQtjmx ** consist essentially of a plurality of bound oxy oovalent

0098U / 1758 bath

.phenylene units, namelyι

TII η,

-Units

branched units copolymeric units

Here X, Σ ¹ , S ^f , B ^H _S Q and Q »the meaning already mentioned] 4er £ _$ -6 <" ddlsu.bsti ^ sd.e? Te I-Phenos ^ ncest is in Summ «η« φ η », 4 * n ^" © labe so-called s EJ »n _o and n ^ are gaaa © from 1 upwards ι .das" ferliältnia. from n ₂ ^3ur Buasae n ^ ψ n ₂ ii larger aXs O and smaller than @ ₉ 23 _g imß. Äao ratio of ssur sum xl * + n * +

is zero him 0 _f 99 _e

example 1

A 1000 ml three-neck flask was fitted with a sealed mechanical stirrer, an IC thermometer, an oxygen inlet, a gas outlet and an external heating mantle. In the flask, 10 g of 2.6% chlorophenol, 0.5 g of copper (I) chloride and 3 ml of HtÄiH ^ N'-tetraiaethyl-IIS-butanediamine were dissolved in 100 ml of chlorobenzene. »Carried 12 _t 3 and the molar ratio of imine to copper 3.3. 20 g of anhydrous magnesium sulfate were added as a drying agent. Oxygen gas was passed through the rapidly stirred mixture while the temperature was slowly increased. Each time the temperature reached 50 ° C, the reaction became so rapid that external cooling with a water bath was required to prevent the temperature from rising above 70 ° C.

0098U / 1759 ^

"■" ■ '■ -. BATH ORIGINAL

The temperature was held at 65 ° C for 1.5 hours Oxygen was passed through continuously · The reaction mixture was filtered to remove the desiccant. The 'filtrate was added to 750 ml of methanol, the 10 ml of 38% contained aqueous hydrochloric acid. The precipitate formed was filtered off, washed well with methanol and dried. The yield was 7.0 g (70 $ of theory) of product one Intrinsic viscosity of 0.16 dl / g (at 30 ° 0 in chloroform). Of the The chlorine content of the product was 40.4% by weight.

Example 2

In the manner described in Example 1, 2,6-dichlorophenol was polymerized in the presence of copper (I) chloride and!, HjN'jiP-tetramethyl-1,3-propanediamine, the molar ratio of monomer to copper being 9.1 and the molar ratio of amine to copper was 3 | 0. The reaction was carried out ^{at 70 ° C. for 2 hours.} The yield was $ 97 of a polymer which had an intrinsic viscosity of 0.17 and a chlorine content of 40.6% by weight. In a repetition of the reaction at 9O ⁰ C the yield was only 31 $ · In a repeat with a molar ratio of monomer to copper of 1.8, the yield only. 17 $ and the limit viscosity 0.06.

Example 3

In the manner described in Example 1, 2,6-dichlorophenol was obtained in the presence of copper (I) bromide and Ν, Ν, Κ ', Ι ^ -ΤβΐΓβ-methyl-T, 3-propanediamine polymerized, the molar ratio of monomer to copper being 8, t and the molar ratio of amine to copper was 2.8 · The reaction was 2 hours at 75 ° C carried out. The yield was 96 $ of a polymer, dae one Intrinsic viscosity of 0.11 and a chlorine content of 38.9 wt. would have.

Example 4

2,6-dichlorophenol was prepared in the manner described in Example 1 _v in the presence of copper (I) chloride and !!, ",! ', N'-fetra- *

0098U / 1759 - ¹ ^

methyl ~ 1,3-butanediaiEin polymerized. Daa haul ratio of. Monomers! to copper was 2.0 and the Mo ratio of 1 minute to copper 2.90 The reaction was carried out at 80 ° C. for 2 hours. The yield was $ 47 of a polymer that was a limit had a viscosity of Oj14 and a chlorine content of $ 41.5,

Example 5

In the manner described in Example 1, 2,6-dichlorophenol was obtained in the presence of copper (I) chloride, but using polymerized by N-methylmorpholine, read molar ratio monomer to copper was 9.1 and the amine to copper molar ratio was 5.0. The reaction was continued for 2 hours at 90 ° G carried out «The yield was $ 93 of a polymer that an intrinsic viscosity of Oj16 and a chlorine content of $ 42.5 hattec

Example 6

The reaction described in Example 5 was carried out using repeated by m-xylene as a solvent, the yield was about $ 30 of a polymer that had an intrinsic viscosity of 0.15 and a chlorine content of $ 40.5.

Example 7

In the apparatus described in Example 1, 15 g of 2,4,6-triohlophenol, 30 ml of H, nr, N ', N ^ -! Retramethyl-1,3-butanediamine, 8.5 g of copper (i) chloride and 20 g of anhydrous magnesium sulfate dispersed in 200 ml of chlorobenzene. The temperature was ^{kept at 80 0} O for 2 hours. During this time, oxygen was passed through. The reaction mixture was filtered. The filtrate was added to 1000 ml of methanol containing 25 ml of aqueous 38% hydrochloric acid. The precipitate formed was filtered off. The product was dissolved in 100 ml of chloroform and the solution was added to 500 ml of methanol containing 5 ml of hydrochloric acid. The precipitate was filtered off, washed with methanol and dried. The yield was 10.5 g ($ 86 of theory),

0098U / 1759 -

BATH

The polymer had an intrinsic viscosity of O _t 11 dl / g, measured in chloroform at 3O ⁰ O.

In Versuohen, which Durohführung in the manner described above were found to be borderline viscosities of less than 0.09 can be obtained when nitrobenzene ale Solvent is used or the desiccant is omitted. If only a catalytic amount of the copper amine complex was used and a stoichiometric amount of a strong base was added, a polymer of lower intrinsic viscosity was also obtained.

Example 8

In the manner described in Example 7, 15 g of 2,4,6-trichlorophenol, 13.5 g of copper (I) bromide, 30 ml of diisopropylamine and 60 g of 4A molecular sieve were dispersed in 200 ml of chlorobenzene. The temperature was ^{kept at 80 °} C. for 2.5 hours. During this time, oxygen was passed through. The product was worked up in the manner described in Example 2. The yield was 10.2 g (83% of theory) and the intrinsic viscosity was 0.09 dl / g.

In experiments carried out in the manner described in Example 7, polymers of average molecular weight were obtained obtained when N, N * -diethylethylenediamine, tri-N-butylamine or N-methyl-2-pyrrolidone were used as the amine

Example 9

A dispersion was made in the apparatus described in Example 1 of 15 g of 2,6-dichloro-4-bromophenol, 8.5 g of copper (Ij) chloride, 30 ml Ν, Ν, Ν », lP-tetramethyrbutane» 1,3-diamine and 200 g anhydrous magnesium sulfate reacted in 200 ml of chlorobenzene »The mixture was heated to 75 ° C, whereupon oxygen gas was passed through for 2 hours with vigorous stirring. The Heaktionegemisoh was then filtered and the filtrate added to 1000 ml of methanol given, which contained 25 ml of 38 # aqueous hydrochloric acid. The , Precipitation was filtered off, washed with methanol and dried

0098U / 1759. ~

net «The polymer yield was 7.8 g (78% of theory). The size & zviskosität was 0.10 in chloroform at 30 ⁰ G.

Example 10

In the apparatus described in Example 1, 1.5 g of 2 ₉ 6-dionlorophenol, 5 g of 2,6-dimethylphenol, 0.5 g of copper (I) bromide, 3 g of Ν, Ν, Ν *, N »« « Tetramethyl-1,3-butanediamine and 50 g of anhydrous magnesium sulfate are dispersed in 600 ml of chlorobenzene. The temperature of the mixture was increased from 24 ⁰ C to 70 ⁰ C, followed by 1 hour of oxygen was passed "The mixture wurdan worked up as described in Example 1. Di · · Auebeut was 6.4 g of a copolymer which had a Grenzviskoeität sound 0.09 dl / g (in chloroform at 3O ⁰ C) and a CBolorgehalt τοπ 14.2 G * w .-%.

Example 11

In the apparatus described in Example 1, 10 g of 2,4 * 6-trioßlcrphenol, 6 g of 2, S-dimethylphenol, 8.5 g of copper (I) - »hloxite, 30 al V, H, N *, B'- * 1 @ 3 ~ tetraethylbutanediamine and 50 g of Molakulftrsleb 41 are dispersed in 250 ml of chlorobenzene. Oxygen was passed through the fleeisoh with vigorous stirring. They B "" k * IONET "Äperatur was 1 hour at 40-45 ⁰ C and then 1.5 hrs. At 75 ° 0 · The Beaktionsgemisoh was filtered and ta" product by precipitation in 1000 ml of methanol 25 ml 3S ] ALg * contained aqueous salic acid, isolated. The copolymer was washed with methanol and dried. The yield was 11 _# 7 g (82.5 # of theory) and the chlorine content was 23.7 $ in the Tergleioa see below a theoretically expected chlorine content of 25.4 $. Di · GrenBTiskosität of the copolymer was 0.28 dl / g as measured in öhloroform * at 30 ° C The product obtained was # su pressed a light yellow, transparent film at 260 ⁰ C. If the pressed material was held in a match flame, it charred and melted, but it did not burn.

0098 U / 1759 bad ORIGINAL

Example 12

The apparatus described in Example 1 was modified by adding a funnel fitted with a tap to allow a potassium hydroxide solution to be added slowly to the reaction mixture. In this apparatus, 15 g of 2,6-dimethylphenol, 7.5 g of 2,4,6-trichlorophenol, 1.0 g of copper (I) chloride, 3.0 ml of Ιϊ, Ν, Ν ¹ , N'-tetramethyl -i ^ -butanediamine and 40 g of magnesium sulfate dispersed in 300 ml of chlorobenzene. Oxygen was bubbled through the mixture at room temperature for 1.5 hours with rapid stirring. The temperature was then raised to 70 ° C, which caused the color of the solution to change from dark brown to golden yellow. Potassium hydroxide (1.85 g as a solution in 25 ml of aqueous methanol) was then added dropwise over 1.5 hours, followed by a reaction continued for another hour. The reaction mixture was worked up in the manner described above, giving 19.5 g (93% of theory) of an copolymer which contained 13.0% by weight of chlorine and had an intrinsic viscosity of 0.31 dl / g. An advantageous temporary softening effect when using poly (2,6-dichlorophenylene) ether as a plasticizer when shaping in the heat, the disadvantageous effects that plasticizers usually cause, namely deterioration of the tensile strength and the tensile modulus due to the reduced viscosity, avoided. This unusual effect apparently results from a chemical interaction between the two polymers.

The polymers and cojolymers produced according to the invention ^ have excellent flame retardancy and can therefore replace * used where there is a risk of fire. In addition, Hie can be used as flame-retardant additives to otherwise less flame-resistant Polymers are used. Of special interest is the addition of dialog-substituted polyphenylene ethers to other polyphenylene ethers, e.g. poly (2,6 ~ dimethylTphenylene) ethers, because this is not just a connection from ernSliter Flammwiarigkeit is obtained, but the Halogeheubetituier-

0098U / 1759.; - ι

ÖAD ORIGINAL

«21 -

ten phenylene ether in this case a unique temporary Have a whitening effect and in this way greatly facilitate the shaping, e.g. by pressing or injection molding, without affecting the physical properties of the final product. Poly (halophenylene ethers) have been found to be particularly valuable plasticizers, including polycarbonates those made from bisphenols and phosgene or related carbonic acid derivatives impart resistance to contamination.

The great advantage of copolymers is their higher molecular weight and the relatively smaller number of branching o-bonds, which gives the beneficial physical properties including flexibility, impact resistance, etc., can be greatly improved.

The polymers and copolymers produced according to the invention have a particularly interesting combination of properties, making them advantageous materials for electrotechnical purposes or for use under extreme conditions of the Pressure, temperature, humidity and corrosion. They have excellent resistance to oxidative and hydrolytic conditions including heat, water vapor. Acids, alkalis and other reactive chemicals as well as good physical properties, e.g. high dimensional stability in the heat, high tensile strength, high tensile modulus and excellent impact resistance. They are true thermoplastic Materials and can be extruded, pressed, cast or by other methods into a wide variety of objects and materials are processed, e.g. into sheets, "foils, tapes, strips, rods, tubes, pipes, laminates, coated Products, etc. Coatings can be applied to any type of substrate by extrusion, calendering, casting, injection molding, etc. as well as by application from solutions in a volatile solvent or from aqueous dispersions. Furthermore, the materials can be used as such or in combination with inert fillers, modifying agents, etc., e.g. Dyes, pigments, stabilizers, plasticizers and others

0 0 98 U / 1759 bad ORIGINAL

commonly used for thermoplastic polymers. Sto £ fe use &.

0098U / 17S9

Claims (6)

Claims {1.) ^ experience for the production of poly (2,6-dihalogenophenylene) · —_ ^r ethers, characterized in that halophenols in which X 'iodine, bromine or chlorine, and X represents the same substituent as X ^J or hydrogen in the presence of oxygen and a catalytically active complex ouprophilen, secondary or tertiary amines and a basic cupric salt at a temperature not exceeding 120 ⁰ C converted from and that the reaction temperature is not higher than 80 ° C. when the substituent X is halogen and when the reaction is carried out in the presence of a cuprophilic aromatic heterocyclic amine. 2.) The method according to claim 1, characterized in that the reaction in the presence of 0 to 99 mol # of another Phenol of the formula BAD ORiGiNAL 0 0 98 U / 1759 is carried out in the Q of tertiary α-carbon atoms free hydrocarbon radicals, of tertiary «carbon atoms free halogenated hydrocarbon radicals with at least two carbon atoms between the halogen atom and the phenol nucleus, of aliphatic tertiary α-carbon atoms free hydrocarbonoxy radicals and of aliphatic tertiary carbon atoms free halogenated hydrocarbon radicals two carbon atoms between the halogen atom and the phenol nucleus means tod in which Q ¹ and Q ^{8 are} the same radicals as Q or halogen and X is hydrogen, iodine, bromine or chlorine. 3,) Method according to claim 2, characterized in that in a first stage the polymerization at the optimum Polymerization temperature of the additional phenol and then in a second stage at the optimum polymerisation temperature of the halophenol is carried out. 4.) Process according to claims 1 to 3, characterized in that 2,6-dichlorophenol is used as the halophenol. " 5.) Process according to claims 1 to 3, characterized in that 2,4,6-triehlorpherfol is used as the halophenol. 6.) Process according to claims 1 to 5 »characterized in that that the reaction in the presence of an inert solvent for the halophenol, the complex and * the poly (2,6 ~ dihalophenylene) ether is made.