DE2166070A1 - Heterocyclic polymers. Elimination from: 2165757 - Google Patents

Description

dr. W.Schalk dipl.-ing. P. Wirth · dipl.-ing.G. Dannenberg DR. V. SCHMIED-ICOWARZIK · DR. P. WEl N HOLD · DR. D. GUDEL

6 FRANKFURTAM MAIN CR.ESCHENHEIMER STRASSE 39

HORIZONS RESEARCH INCORPORATED 23800 Mercantile Road

Ohio 44122 / USA

Heterocyclic polymers

The present invention relates to heterocyclic polymers which. derived from 2, 3, 5, 6-tetraaminopyridine, optionally in combination with another aromatic! tetraamino compound and a polybasic acid.

The 2,6-diamino-3j5-dinitropyridine and its derivatives can can be represented by the following formula:

in the R., and R respectively

0 0 0 0

H, -COCH ₃ , -COC ₂ H ₅ , -CCH ₃ , -CCF ₃ , -SO ₂ CH ₃ and the like can represent monovalent groups and R .. and R ₂ need not be identical. The 2,3,5,6-tetraaminopyridine. has the formula; -

2 O 9 8 5 O / 1 α 1 O

SAD ORIGINAL

The diaminodinitropyridines represented by the formula I comprises are useful precursors of tetraaminopyridine of formula II above. Bis-o-diamines, of which 2,3,5,6-tetraaminopyridine represents an example, are again the starting products for the production of Polybenzimadazoles Poly-.imidazopyrrolonen (or pyrrons), polybenzimidazobenzophenanthrolines and polyquinoxalines. Polyquinoxaline can through Implementation of bis- ^ o-diamines with either 2,5-dihydroxy-p ~ benzoquinone or bis-glyoxalene are produced. Lots of materials These types of polymer have excellent resistance to heat and radiation, which makes them particularly useful for space travel Makes suitable .. Such polymers can often be used for the production of films and fibers with excellent chemical and physical properties are used and are used in the manufacture of protective coatings, laminate manufacture and adhesive compositions, composites, and the like are valuable. ". Derived from 2,3,5,6-tetraaminopyridine. Polymers have im Compared to bis-o-diamine-derived benzenzoid polymers, improved thermal stability in air.

Recently 2,3,4,6-tetraaminopyridine is mentioned in the literature been. However, since it is not a bis-o-diamine, it is for manufacture the above-mentioned polymers are unsuitable.

The 2,3,5,6-tetraaminopyridine as the free base (II) is amenable to oxidation and is generally produced and used as its acid salt. Preferred acids for converting the free base into its acid salt include hydrogen chloride, hydrogen bromide, sulfuric acid and trifluoroacetic acid , Trichloroacetic acid and methanesulfonic acid, but many other acids known to those skilled in the art are also suitable. The 2,3,5,6-tetraaminopyridine as the free base is preferably obtained by reducing 2 _r 6-diamino-3,5-dinitropyridine, the compound (I) in which "both R ₁ and R ₂ - The compound 2,6-diamino-3,5-dinitropyridine - (ie the compound I in which both R 1 and R ₂ = -H) is preferably prepared by direct nitration of 2,6-diaminopyridine This is in stark contrast to the production of the corresponding diaminodinitrobenzene precursor also 1,2,4,5, —benzene-

BAD ORiGiNAL

tetrarain, eggs in pure form directly from a diaminobenzene are not can be easily manufactured. The compound 2,6-diamino-3,5-dinitropyridine know also from a derivative of 2,6-diaminopyri-.din produced by nitration with subsequent hydrolysis will. Suitable derivatives of 2,6-diaminopyridine can be obtained "by acetylation, p-nitrobenzoylation, sulfonamide or urethane formation obtained from 2,6-diamonopyridine. Such reactions and derivatives are well known to those skilled in the art and therefore are not described in detail.

Dinitro-diaminopyridine of the formula (I) in which neither IL. or Rp = -H can be converted to the 2,3 »5,6-tetraaminopyridine by reaction with ammonia (or an ammonia precursor) or with hot aqueous acid with subsequent hydrogenation. The first method is preferred. When R ₁ or R _P =

-SOpCH ₇ or -CCF-, ammonolysis is not expedient, therefore acid hydrolysis is chosen as the process. An alternative route, which is less preferred, involves the reduction of substituted diaminonitropyridines to a 3,5- · diamino-2,6-disubstituted pyridine, which can then be hydrolyzed to the tetraaminopyridine with hot aqueous acid. This route is preferred when using the amino nitrogen

COCH d C

-COCH, or -COC ₂ Hk is substituted.

The preferred preparation of 2,6-diamino-3,5-dinitropyridine by nitrating 2,6-diaminopyridine involves the addition of one Nitrating agent to a well-stirred solution of the 2,6-diaminopyridine in concentrated sulfuric acid or in a mixture of sulfuric acid and acetic acid. The nitrating agent can, but not necessarily, be around 90 to 100% Nitric acid, fuming nitric acid, sodium or potassium nitrate fiein. The amount of nitrating agent can be between stoichiometric amount and 100% excess. the Hitrierurigsterperatures can be between about -15 ° C and 35 ° C ' but are preferably in the range of about -15 "

ι -

209850/1 0-1 0

■ * "^ r ^mm ■

to + 5 ^° C. When the nitration is practically complete, the product is isolated simply by precipitation by pouring into cold water or another cold aqueous solvent or by diluting the nitration mixture. The product obtained by direct nitration of 2,6-diaminopyridine is usually subjected to purification prior to reduction, using methods known to those skilled in the art.

The nitration of (i). Is, in particular when both R ^ and R ₂ from the group: _ _{SQ CH} _nCF ^{& υ5} β ^{βν / ΰ1ι1ΐ,} are considerably slower than in the case when both R ^ and tR _o = - H or even when R ^ and R ₀ = JU _{n u} . Virtually the same nitration procedure is used for these less reactive substituents, except that higher temperatures, preferably of about 40-80 ° C, are used.

In relation to the reduction of 2,6-diamino-3> 5-dinitropyridine it is convenient to use a dinitro intermediate of high purity. Such a material is usually obtained by ammonolysis of substituted 2,6-diamino-3,5-dinitropyridines of the formula (I), or thorough purification of the product from the direct nitration of 2,6-diaminopyridines.

k The reduction can be carried out chemically or catalytically, but the latter is preferred. Chemical agents such as tin-II-chloride ^ often lead to contamination of the product. Catalytic reductions can be done with platinum, platinum oxide or Palladium catalysts are carried out and the catalysts can be on a carrier such as carbon or barium sulfate, are present. The amount of catalyst can vary widely, depending on the solvent and the reaction temperatures, but is generally in the range of about 0.5 to 10 wt .- ^, based on the Diaminodinitropyri'din, the preferred amount? . is about 1 to 5 wt .- 6. Inorganic or organic solvents or mixtures thereof can be used. For example, pyridine, alcohol, sulfuric acid are in

209850/1010

'Acetic acid, phosphoric acid, phosphoric acid in acetic or formic acid and phosphoric acid in alkanols are all suitable solvents for the reduction. - - · '.

If a non-acidic solvent is used, it can Tetramine can be isolated directly as the free base ("Experiment 8), Suitable non-acidic solvents include lower aliphatis.che Alcohols, methoxyethanol, bis (2-methoxyättiyl) ether ("Diglyme"), monomethyl ether of diethylene glycol, pyridine, 4-picoline and others of a similar nature. Organic amines such as pyridine are "particularly useful when used alone Solvent or in conjunction with one or more of the ■ solvents mentioned above can be used. Your use ... leads to a surprising increase in the rate of reduction, allowing for considerably shorter reaction times for a given number of conditions.

If acidic solvents are used, the tetramic acid salt expediently either as a mixture with the catalyst (Example 6) or as a "solution, which is then replaced by a corresponding Acid containing non-solvent medium can be precipitated. . ('Experiment 7) can be isolated. For example, the reduction leads in sulfuric acid / acetic acid to the sulfuric acid salt of (II) in a mixture with the catalyst. The salt can be obtained by extraction

-ffiit Jiasser and then failure through the addition of sulfuric acid from

'- - Acid catalyst can be freed. The sulfate can also be dissolved in aqueous salt and the hydrochloride of (II) can be isolated by saturation with hydrogen chloride. The hydrochloride salt can also be used directly isolated directly from the original reduction mixture - (experiment 7).

The reaction temperatures can vary from about 20 to 100 ⁰ C.

and initial hydrogen pressures of about 2.1 to 70 kg / cni can be used. Temperatures from about 40 to 8O ⁰ C and water

Fabric pressures of about 3.5 to 14 kg / cm are preferred.

2 0 9 8 5 0/1 0-1 Q _ÄAn

ßAC> ORIGINAL

As the color and purity of the 2,3,5,6-tetraaminopyridine product are often extremely important (especially for further processing into polymers) is the catalytic process for reduction therefore advantageous in acidic media because a lightly colored (white to slightly pink) acid salt of high purity of 2,3,5,6-tetraaminopyridine is obtained can be obtained directly in good yield.

The following experiments serve to explain the preparation of the starting materials for the heterocyclic polymers according to the invention. ·; Try 1 ■
2,6-diamino-3,5-dinitropyridine from 2,6-diaminopyridine

ψ 54.5 g (0.5 mol or 1.0 equivalent) of 2,6-diaminopyridine were added to 250 ecm of concentrated sulfuric acid with cooling and stirring so that the temperature did not rise above 25 ° C. A solution of 30 ecm of sulfuric acid and 76 g of nitric acid / prepared from 47 ecm (75 g) of fuming nitric acid and 12.9 ecm (18.3 g) of 70% nitric acid / was added to this solution for 2 hours, with the temperature was kept at 10 -5 ° C. The resulting dark solution \ rarde during 3/4 hour at 70 ⁰ C heated and maintained 1/2 hour at 70 ⁰ C "The reaction mixture was cooled and poured into 1.5 1 -. -Water poured, stirred -gründlich- The solid product was washed thoroughly and dried, giving __g_2_g- <$ 63 yield).

The elemental analysis confirms the assumed structure. Calculated for C ₅ H ₅ N ₅ O ₄ : C, 30.2; Ή 2.5; θ "32.2. * Found: C 31.7; H 2.5; O 32.3.

Major "peaks" are in the infrared (KBr) spectrum at about 2.9; 3.0; 6.2; 6.9; 7.3; 7.5; 7.8; 8.1; 9.6; 13.2 and 14.0. The purified product consists of a gold-yellow solid, the sinters at about 300 C and then decomposes at about 355 ° C.

The above product is also obtained by using potassium nitrate (1.2 Mol) is used instead of nitric acid solution and the reaction is carried out at 0 ± 10 ° C.

209850/1OtO

Attempt 2

Diethyl 2,6-pyridinedicarbamate

195 g (171 ecm or 1.8 Hol) of ethyl chloroformate gradually became a thoroughly stirred mixture of 81.7 g (0.75 mol * = 1.5 equiv.) Of 2,6-diaminopyridine, 207 g (1.5 mol ) anhydrous potassium carbonate and 450 ecm of a mixture of tetrahydrofuran and Ν, Ν-dimethylformamide (5 vol * 2 vol). The temperature during the addition was 22 to 40 ⁰ C. Additional 69 g carbonate and 50 cc chloroformate were added and the temperature was maintained at 45 to 50 ° C for 1 hour, whereby a substantial evolution of carbon dioxide occurred. The mixture was poured into 1 liter of cold water, and then 150 ecm of concentrated hydrochloric acid were added and the tetrahydrofuran was allowed to evaporate overnight from an open dish. Most of the water-clear plague present was removed by edging. The liquor was acidified to pH with hydrochloric acid, concentrated to half its volume and cooled. The product and salts were filtered off and reslurried twice with water and filtered off to remove most of the potassium chloride. The product was extracted from the remaining inorganic salts with acetone at 500 ecm. The product was reprecipitated by adding 750 ecm of water, combined with the previously removed ^ colored solid. And. Slurried with isopropyl alcohol, filtered off and dried, \ io- "Jbßl .man; 42. g. (-22Jo) of an easily -alassified solid -received, melting point 124-128 ° C. Recrystallization from ethanol and water (1 Vol.:1 VoI) raised the melting point to 130-132 ⁰ C..

Analysis'.

Calculated for C ₁₁ H ₁₅ M ₃ O ₄ : C, 52.2; H 5.9; N 16.6. (Mol.wt. = 253)
Found: C -51.6; H 5.8; N 16.5.

The above product can also be used in tetrahydrofuran as a solution?; - · medium using a tertiary amine (e.g. pyridine,

209850 / 10.10

Triethylamine) obtained as an acid acceptor. Dimethyl 2,6-pyridinedicarbamate obtained when using methyl chloroformate instead of ethyl chloroformate.

Attempt 3 '

Diethyl ester of'3,5-dinitro-2,6-pyridinedicarbamic acid, (I) in which R ₁ and R _{9 are} \\ '

¹ * -COC ₂ H _5,. ·.

To a solution of 25.3 g (0.1 mol) of diethyl-2,6-pyridindicarbamat in 125 cc of concentrated sulfuric acid at O to 5 ⁰ C was added over 1 hour, a solution of 100% strength nitric acid. acidic (0 ·, 4 mol. Or 100% excess) in acetic acid. The nitration solution was prepared by gradually adding 14 ecm acetic anhydride to 19 ecm fuming 90% nitric acid while the temperature was kept below ⁰ ° C. The nitration was terminated by 1 hour at 0 to 5 ° C and then stirred for 1 hour at 27 ⁰ C. The reaction solution was poured into 1 / 2.1 of cold water. The solid product was thoroughly washed and dried to obtain 25 g of the dried product. Recrystallization from ethanol gave 21.0 g (62%), melting point 160-164 ° C.

Dimethyl 2,6-pyridinedicarbamate can be nitrated in a similar manner to give (i) where R ₁ and R _{9 are} fl. '^ -COCH ₃

Attempt . 4 · ·

2,6-diamino-3,5-dinitropyridine

To a solution of 9.0 g of diethyl 3,5-dinitro-2,6-pyridinedicarbamate 10 ecm of concentrated ammonia were added in 30 ecm of N, N-dimethylformamide. Formed within about 5 minutes strong precipitation. Stirring was continued overnight at room temperature. 50 ecm isopropyl alcohol with thorough stirring, the product was filtered off, washed and dried to give 5.1 g (97%) of yellow solid received. The infrared spectrum showed no carbonyl absorption.

w-i 209 8 50 / 10-1 Q '

^"9 ~ 216607Q

analysis for C ₅ H ₅ N Ω · C * 30, 1; H 2, 5; N 35, 1. Calculated C. 30, 6 y H 2, 5; 'N 35, 7th Found:

The infrared spectrum of this product is the same as that of Attempt. 1 practically identical.

In a very similar way, one can do 2,6-diamino-3,5-dinitropyridine obtained from substituted amines (i) in which R. and Rp each from the group -H, | j ■ Ii

Il

selected. The compounds in which the substituents 0 0 '

Il Il ■

-CCFI, and -CCF-, are obtained from 2,6-diamiiiopyridine by

Reaction with acetic anhydride or trifluoroacetic anhydride. Compounds in which R ^ is hydrogen and Rp is not Hydrogen means are conveniently using a large excess of 2,6-diaminopyridine in the original Reaction with the anhydride produced.

,Attempt . 5

'' 2,6-diamino-3,5-dinitropyridine by acid hydrolysis -

9.5 g of diethyl-3,5-dinitro-2,6-pyridincarbamat were added in 48 g sulfuric acid -konzentrierter- g-elöst -20 cc "of water and the solution was heated at 110-115 ⁰ C for 4 hours The reaction mixture was cooled and poured into 250 ml of cold water while stirring, the solid precipitate was filtered off, washed thoroughly and dried to give a quantitative yield of 2,6-diamino-3,5-dinitropyridine.

Trial 6

2,3,5,6-tetraaminopyridine ~ bis (sulfuric acid salt)

3.75 g (0.0100 Hol) 2,6 - DiamLno-3, '3-d; initrOpyridni were partially in 60 ecm .; JQ% ~ i [ ^r , pv iSchwo folic acid in glacial acetic acid in a 250 ecm Parr- Bottle dissolved, Ws v / iirdu · at. weak application of

209850/1010

¥ poor thoroughly stirred, and. 2.1 g of 5% palladium on barium sulfate were added. The reduction with hydrogen (absorption of about 0.113 mol of water substance) "

was finished within 2 hours at room temperature. The resulting almost white mixture was diluted with acetic acid and tetrahydrofuran, the solids filtered off, washed and dried, giving 8.5 g of Iiel3-gray solid. Of this weight there was 1 g of catalyst and a very small proportion could be inorganic salt, since no precipitate was obtained from the filtrate after the addition of ether. The yield of tetra-amine bis (sulfuric acid) salt) was 6.4 g (10050 × ^the solid was extracted with 50 ecm under nitrogen previously boiled water. A rapid darkening of the liquor was observed. A small amount of dark insoluble solid was filtered off and 13 g concentrated sulfuric acid was added to the filtrate to precipitate the product - the latter was washed successively with 25% sulfuric acid, acetic acid and alcohol, after drying 1.2 g rust-colored solid Washing with alcohol (twice) and drying of the insoluble product gave 5-2 g of dark solid.The elemental analysis of the material (1.2 g) confirmed the tetramine-di (sulfuric acid salt) structure.

Calculated for C ₅ H ₉ H ₅ ..! H ₂ SO ₄ : C 17.9; H 3.9; N 20.9; S 19.1; 0 38.2. (MoI.Gew. = 335)

Found: C 17.8; H 4.9; N 20.4; S 19.0; 03: 7.9

(by difference),

The mixture of sulfate salt and catalyst can be from the catalyst freed and converted into the trihydrochloride as follows: The solid mixture (17 g) was with 100 ecm 5? otoffic acid, into which nitrogen has been blown under reflux vnr, stirred thoroughly, filtered off hot, cooled and sprinkled with Chlorwan-Florstoff saturated. The purple solid was filtered off, washed with alcoholic hydrogen chloride and in vacuo; ■ {> - dries, 5.8 g of tetraaminopyridiri-trihyrtrochloricL-

, 2 0 9 8 5 0 / 10-10 SAD OR ₁ GINAL

Received monohydrate,

Calculated for C ₅ H ₉ N ₅₄ 3HCl.H ₂ O: C 22.5; H '5.2; N 26; 2; Cl 39 _; '. Found: · C 22.5; H 5.3; ' N 26.5; Cl 40 _V

Using hydrogen bromide, one obtains in a much similar manner the hydrobromide salt.

Trial 7 . '

2,3 * 5,6-tetraaminopyridine hydrochloride salt by reduction in

H ₃ PO ₄ - HCO ₂ H. .

In a 500 cc Parr bottle was added 15 g of 2,6-diamino-3,5-dinitro · pyridine was dissolved in 100 cc of hot 85% phosphoric acid, the solution was cooled to 25 ⁰ C and ecm 135 formic acid saturated with hydrogen chloride and 15 ecm concentrated hydrochloric acid. 5% palladium on charcoal (2.88 g) was added and the mixture was placed under hydrogen pressure of 3.85 kg / cm at room temperature. The reduction was carried out at room temperature until no further hydrogen uptake was detected. The mixture was filtered off, the solid was washed with 50 ecm of formic acid, which contained several ecm of concentrated hydrochloric acid, and finally with ethanolic hydrogen chloride. After drying, a 4.0 black solid was recovered. The filtrate was added to a cold solution of 500 ecm -I-etrahydrofuran and 50 ecm concentrated hydrochloric acid to precipitate almost white 2,3,5,6-tetraaminopyridine hydrochloride salt.

A similar reduction carried out in 85% H ^ PO // methanol

was performed, runs easily at 75 C. After removing the Catalyst by filtration and addition of concentrated HCl, a high yield of hydrochloride salt is precipitated. That Product of this example can be used in hair coloring (see British Patent No. 995 870). Quite similar Way is 1,3-diamino-2,4-dinitropenzene reduced and used as Separated 1,2,4,5-benzene tetramine hydrochloride salt.

209850/1010

J er sy c h .. 8

2,3, i3,6-tetraaminopyridine (free base)

1.5 g of 5/6 strength palladium on charcoal were added to a hot suspension of 15 g of 2,6-diamino-3,5-dinitropyridine in 200 ecm of 95% ethanol and 40 ecm of pyridine. The mixture was subjected to hydrogenation at an initial pressure of 3.85 kg / cm at about 60.degree. After 9.07 kg of hydrogen was absorbed, the temperature was increased to about 75 ° C. . When there was no further uptake of hydrogen (total 0.49 mol), the reaction mixture was cooled and 50 ecm of benzene / heptane (1% by volume) were added. The mixture was filtered off in a dry box under nitrogen and worked up in the dry box as follows: The filter cake was extracted with 150 ecm of de-aerated Ν, Ν-dimethyl acetamide and filtered. To the filtrate was added 150 ecm of benzene / heptane (1 vol. 1 vol) to precipitate the product, which was washed and dried in vacuo to give 4.3 g (41? 0 green solid.

I -

Analysis'. '"

Calculated for C ₅ H ₉ N ₅ : C, 43.2; H 6.5; N 50.4. • Found: C, 42.3; H 6.1; N 48.9.

The product was extreme against atmospheric oxidation sensitive. ■ ■

When the hydrogenation is carried out in the absence of pyridine, a much slower reduction is observed.

The trichloroacetic acid salt of 2,3,5,6-tetraaminopyridine can be obtained if the free base is mixed with a cold solution treated by trichloroacetic acid in acetic acid.

Tersuc h. 9

2,3,5,6-tetraaminopyridine (free base)

To a hot suspension of 15 g of 2,6-diamino-3,5-dinitro ~

2098 50/1010

pyridine in 200 ecm 95 ° 4-strength ethanol and 40 ecm pyridine were added to 1.47 g of 3.5% platinum on charcoal. The mixture was subjected to hydrogenation at an initial pressure of 3.85 kg / cm "at about 65 ⁰ C. .As. No further hydrogen uptake (about 0.45 mol to 1 hr.) At this temperature., Occurred was the reaction mixture cooled to about -10 ⁰ C and rapidly filtered, the cake was washed with benzene / hexane. (1 VoI 1 by volume). washed and then placed in a large Sublimationsvorrichtung the system was evacuated and then for 6 hours at 185-210 ⁰ C. heated at 0.08-0.2 mmHg and 0.5 g of tetraamine pyridine obtained as a sublimate under nitrogen.

The residue (10.1 g) from the sublimation was stirred with 70 ecm of 85% phosphoric acid and filtered. 100 ml of concentrated hydrochloric acid were added to the filtrate. The mixture was cooled to -10 ⁰ C and filtered using vacuum. After washing and drying in vacuo, 8.0 g of the hydrochloride salt were obtained as the product. "'

If a stoichiometric amount of triethylamine instead of Pyridine is used in the above reduction, a considerably slower rate of reduction occurs.

Attempt 10

A thoroughly stirred solution at ~~ e "fcwä -1t) ° c) of" 54.5 g (0.5 mol = 1.0 equiv.) of 2,6-diaminopyridine in 300 ecm of pyridine yielded 115 g (1.0 mol ) Methanesulfonyl chloride given. After 1/2 hour at this temperature, the dark solution was allowed to warm to room temperature and kept at this temperature for 1 1/2 hours. The product and the hydrochloride salts were precipitated by adding tetrahydrofuran and washing with tetrahydrofuran (total volume about 1 liter). The insoluble resin was diluted with 250 ecm of water and neutralized with concentrated ammonia. Most of the water was removed from the mixture using a rotary evaporator and the wet solid was extracted with 1/2 l of warm ethanol. The ethanolic solution was concentrated to 200 ecm, ^{cooled to -20 0} C and the crude product

209 8 50/1010

-U-

(24 g) filtered off. The removal of the inorganic salt and recrystallization from aqueous ethanol gave 2,6-Pyridiri- • dimethansulfonamid, melting point 190-194 ⁰ C. '

Analysis. .

Calculated for C ₇ H ₁₁ N ₅ O 1 S ₂ : N 15.9; S 24.2. (MoI.Gew.265)
Found: 'N 15.9; S 23.9.

5f0 g (0.019 mol) of the above 2,6-pyridinedimethanesulfonamide were dissolved in 20 ecm of concentrated sulfuric acid and a previously prepared mixture of 4 ecm of 90% nitric acid (100% molar excess) and 3 ecm of acetic anhydride was added so that the reaction temperature was within Range of 20-28 ⁰ C was maintained. The reaction was stirred at room temperature for 1 hour, becoming heterogeneous. Additional sulfuric acid (5 ecm) was added and the mixture was heated at 50-55 ° C. for 1 hour. After cooling to room temperature, it was poured onto 53 g of ice with stirring. The yellow solid was filtered, washed, reslurried with isopropyl alcohol, filtered off again and dried to give 4.7 g (7095), melting point 275-285 ⁰ C. The material was ir 15 ecm Ν, Ν-dimethylacetamide at 80 ⁰ Dissolved C and then added boiling isopropyl alcohol to kick in the precipitate. The mixture was cooled to ice temperature, the solid was filtered and dried to 3.0 to obtain g, melting point 282-286 ⁰ C.

analysis

Calculated for C ₇ H ₉ N ₅ OgS ₂ : N 19.7; S 18.0. (Mol. Weight 355)
Found: N 19.4; S 18.0.

Attempt 11

The monoinethanesulfonamide of 2,6-diaminopyridine can be used in a Reaction obtained., Which is similar to that of Example 10, if an excess of 2,6-diaminopyridine (54.4 g of 1 Equiv.), 100 ecm pyridine and 200 ecm tetrahydrofuran as solution

^209850/1010 "" OfG ₁ NAi.

solvent and 22.9 g (0.2 mol) methanesulfonyl chloride used. The product is separated by adding tetrahydrofuran and pyridine removed, the residue neutralized and the excess of 2,6-diaminopyridine is removed. -.

The above product gives after reaction with ethyl chloroformate, acetic anhydride (or acetyl chloride) and subsequent nitration (I), where R ₁ -SOoCH ,, and R ₉ «or R ₁ - -SOpCH,

0 -UUO ₂ H ₅

and R ₂ -. -CCH ₅ mean.

The following examples serve to explain the further

present invention without limiting it.

Heterocyclic polymers made from 2,3,5,6-tetraaminopyridine and Ί »4, 5,8-naphthalenetetracarboxylic acid

To a 500 ecm three-necked flask equipped with a Trubore stirrer and a nitrogen inlet tube was placed 333 g of 116% polyphosphoric acid. The polyphosphoric acid was freed from oxygen by heating overnight at HO ⁰ C while passing nitrogen through the stirred acid. At 75 ⁰ C

• were then 3.32 g (0.0133 mol) 2.3 »5» 6-tetraaminopyridine trihydrochloride added, and the solution was raised to 75 "80 ° C Heated overnight under nitrogen to drive off hydrogen chloride.

--To - this - solution - 4.05g - (- 0 * Ot33-Mol) A , -4, -5, -8-naphthalenetetracarboxylic acid were added, and the mixture slowly rose

-18O ⁰ C heated Tind "in addition: eT ^ temperature" held for 10 hours. The hot viscous solution was poured slowly xmter thorough stirring into 1.5 1 previously cooled (about -20 ⁰ C) methanol. The polymer was washed thoroughly with methanol and then with

. 190-200 ⁰ C dried under reduced pressure to give 3.4 g (76? 0 dark solid. The polymer was further

'Purified by dissolving 2 g in 50 ecm methanesulfonic acid and reprecipitating them in methanol. The precipitate was washed thoroughly with methanol and then methanol-halt ammonia and water, and finally for 6 hours at 230-250 ⁰ C at 0.05-0.1 mmHg dried to give 1.5 g of product (75% yield) obtain. > ·

209850 / 10-1 Q.

analysis

Calculated for G ₁₉ H ₅ N ₅ O ₂ : C, 68.0; H 1.5; N 20.9-

(Equiv. Weight 335)

Found: ' C, 66.2; H 2.2; N 19.3; Ash 0.3.

The extraordinary thermal stability of this polymer is illustrated by the following experiment. The polymer (0.12 g) was placed in an open 10 cc porcelain crucible and with a burner (the flame temperature just below the crucible was 1000 to 1100 ⁰ C.) '. It took over 2 hours to fully (98? O) burn.

Practically the same polymer is obtained if, instead of the naphthalenetetracarboxylic acid, an equivalent amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride is used used in the initial polymerization. The resulting product is also v / e. good thermal stability.

Examples 2-14 - ". '.

Repeat the procedure of Example 12 and each of the following Tetracarboxylic acids (or corresponding dianhydrides) or mixtures of tetracarboxylic acids instead of 1,4,5,8-naphthalenetetracarboxylic acid used or partially replaced the 2,3,5,6-tetraamino-pyridine-Tr-ih-hydrochloride, the corresponding ones are obtained Polyheterocycles.

The use of more than one tetramine or acid derivative in Examples 23-25, 38-43, 54-56 and 78-79 often has surprising properties in terms of improved solubility and processability result.

(2) 1,2,4,5-benzene tetracarboxylic acid

(3) 1,2,4,5-cyclohexanetetracarboxylic acid
(4) 2,3,6,7-naphthalenetetracarboxylic acid
(5) 3,3 ', 4,4'-benzophenone tetracarboxylic acid (6) bis (3,4-dicarboxyphenyl) sulfone

20985 0/1 010

(7) bis (3,4-dicarboxyphenyl) ether

(δ) 3 »6-dichloro-1,2,4,5-benzenetetracarboxylic acid (9) 2,3,6,7-Anthraquinone tetracarboxylic acid · (1O) 2,3,5,6-pyridine tetracarboxylic acid

dl) 2,3,5, δ-pyrazine tetracarboxylic acid

(12) Example 12, but instead of 0.06O moles of 2,3,5,6-tetraaminopyridine Ο, ΟΟβΟ mol 3,3 '~ diaminobenzicLine-tetra-

hydrochloride used v / earth
(15) 1 »^ 15,8-naphthalenetetracarboxylic acid (0.006? Mol) and 3.3 ',

4,4 '~ Benzophenonetetracarboxylic acid (0.0066 mol) (.14) 1,2,4,5-Benzoletetracarboxylic acid (0.0040, mol), bis (3,4-. Di-' carboxyphenyl) sulfone (0.0053 mol) and 2,3,6,7 ~ anthraquinone tetracarboxylic acid (0.0040 moles)

Example 15 '' ■

Polyheterocyclic material made from 2,3,5,6-tetraaminopyridine and 1,4,5,8-naphthalene etracarboxylic acid anhydride

Under an inert atmosphere, 1.07 g (4 millimoles) of 1,4,5,8-naphthalenetetracarboxylic acid dianhydride are added to a solution of 0.556 g (4 millimoles) of 2,3,5,6-tetraaminopyridine in 10 ^; Dry 'cc. N, N-dimethylacetamide (purified and de-aerated) given. The last 5% of the Bianhydride are added as a solution in the same solvent. The reaction at room temperature leads to the amine-substituted polyamic acid as an intermediate product which can be separated off by precipitation in aceto washing and drying at low temperatures. The polymer of Example 1 can be obtained, if one uses the above solution for casting a film which gives the cyclized polymer after drying at 150-400 ⁰ C.

Similarly, the corresponding dianhydrides of Examples 2-11 can be used.

Belsr> iel 16

Polybenzimidazole from 2,3,5,6 - tetraaminopyridine and isophthalic acid

209850 / i 0! 0

. A 500 ecm three-necked flask equipped with a Trubore stirrer, nitrogen inlet tube, and calcium chloride drying tube • was charged with 240 g of 116%. 'Polypho spho rs aur e charged. The acid was freed from air by 2 hours flushed with a strong nitrogen stream at 110-120 ° C: After cooling to 6O ⁰ C .wurden 4.96 g (0.020 mole) of 2,3,5,6-Tetraaminopyridin- trihydrochloride added in two portions, and the temperature was gradually increased to 120 ⁰ C in order to drive off hydrogen chloride. 3.32 g (0.020 'mol) of isophthalic acid was then added, and the polymerization was carried out at about 180 ^° C. for 20 hours. The hot, dark-brown solution was gradually dissolved in 1 liter of aqueous methanol (1 vol. iVol), which had been cooled to -10 C, poured. The polymer was thoroughly washed with water and aqueous methanol containing ammonia and dried at 200-22O ⁰ C in vacuo to give 4.4 g (94%) showed very dark solid. The polymer was redissolved in 75 ecm of warm 85% phosphoric acid, 100 ecm of acetic acid was added and the solution was poured into 500 ecm of water, washed and dried as above, which gave 3.5 g of solid. This polymer was treated again with fresh, hot phosphoric acid (100 g) under nitrogen at 220-225 ° C. for 4 1/2 hours. The polymer was dissolved in aqueous acetic acid.

- falls - UHdr as - above -au fg-oworks to gain 3.1g.

· "Analysis

Calculated for C ₁₅ H ₇ N ₅ : C, 66.9; H. 3.0; N 30.1. \ (Equiv-weight 223) '

Found: C, 64.9; H 3.3; N 28.5.

In a similar way, practically the same polymer can be obtained if one uses dimethyl isophthalate or the diamide of iso- ' phthalic acid used. ·.

209850/1010

Examples 17-32 - ■■ ".,

If the procedure of Example 16 is repeated and in each case the fol dibasic acids instead of isophthalic acid (as free acid or as diniethyl ester or diarnide) used, so the corresponding polybenzimidazole is produced.

(17) terephthalic acid

(18) 2,6-naphthalenedicarboxylic acid

(19) 4,4'-biphenyldicarboxylic acid

(20) 4.4 ^t -diphenyloxyddicarboxylic acid

(21) 4,4'-benzophenonedicarboxylic acid

(22) bis (4-carboxyphenyl) sulfone

(23) 3,5-pyridinedicarboxylic acid

(24) 2,5-pyrazinedicarboxylic acid

(25) 2,7-Anthraquinonedicarboxylic acid. "

(26) bis (5-carboxy-2-pyridyl) ether

(27) Example 16 except that 0.010 moles of 2,3,5,6-tetraaminopyridine trihydrochloride by 0.010 mole of 3,3′-diaminobenzidine tetrahydrochloride be replaced

(28) Example 16, wherein 0.010 moles of 2,3,5,6-tetraaminopyridine trihydrochloride by 0.010 moles of 3.3 '^ - ^' - tetraarainobenzophenone be replaced

209850/101 0

(29) Example 16, wherein 0.010 mole of 2,3,5,6-tetraaminopyridine trihydrochloride be replaced by 0.010 mol of bis (3,4-diaminophenyl) sulfide tetrabyrochloride

(30) Example x 16, wherein 0.010 mole of 2,3,5,6-tetraaminopyridiri trihydrochloride by 0.010 mol of bis (3,4-diaminophenyl) -

. sulfone replaces v / earth

(31) terephthalic acid (0.010 mol) and isophthalic acid (0.010 mol)

(32) Isophthalic acid (0.007 mol), 4,4'-diphenyloxydicarboxylic acid (0.007 mol) and 2,7-anthraquinonedicarboxylic acid (0.006 mol)

Example 33 '

Polyheterocyclic material made from 2,3-5,6-tetraaminopyridine trihydrochloride and trimellium anhydride acid chloride

To a solution of 0.01 mol of 2,3,5,6-tetraaminopyridine trihydrochloride in 200 g of de-aerated polyphosphoric acid were added under an. Atmosphere added 2.10 g (0.01 mol) of trimellitic anhydride monoacid chloride. The addition took place at about 100 ° C, and then the reaction temperature was gradually increased to 180 ⁰ C ER- "höht and held for 15 hours at this temperature. The polymer was ice in good yield in a ¥ to that of Example 1 _ir is similar separated. Its infrared spectrum showed imide band at about 5.7 / U and 13.9 YU and Imidazolbande at etv / a 6.2 ax on.

A similar polymer is obtained if trimellitic acid or trimellitic anhydride is used instead of trimellitic dianhydride monoacid chloride as in Example 33.

Examples 34-4 5

The procedure of Example 33 is repeated using trimellitic anhydride acid chloride by the anhydride acid chlorido, which differ from tribasic acids of the following general formula

209850/1010 ₆ a0 OWSWAL

HOOG-R

derive, is replaced, in the Rg a trivalent organic Group represents, or also partially the 2,3,5,6-tetraaminopyridine trihydrochloride is replaced, the corresponding polyheterocyclic materials are obtained:

(34) 1 »4,5-naphthalenetricarboxylic acid

(35) 2,3 f6-naphthalenetricarboxylic acid

(36) 2,3,6-Anthraquinone tricarboxylic acid

(37) 3,3'j 4-tricarboxybiphenyl

(38) 3 »4-dicarboxyphenyl-4'-carboxy-phenyl ether (39 ^ 3,4-dicarboxyphenyl-3 ^! -Carboxyphenylsulfone (40) 3,3 'y4-tricarboxybenzoplienone

(41) 2,3,6-pyridine tricarboxylic acid

(42) 1,2,4-cyclohexane tricarboxylic acid

(43) Example 33 except that 0.005 moles of 2,3,5,6-tetraaminopyridine trihydrochloride by 0.005 moles of 3,3'-diaminobenzidine tetrahydrochloride be replaced

(.44) Tj .- 'imellitic acid CQ ^ OS mol) and 3,3', 4-tricarboxybenzo-

phenone (0.005 moles)

- (- 45) -T-rime-lithic acid (0.004 mol), 3,4-dicarboxyphenyl-3'-carboxyphenyl sulfone (0.003 mol) and 2,3,6-anthraquinone tricarboxylic acid (0.003 moles)

Example 46

Polyquinoxaline from 2,3,5, δ-tetraaminopyridine trihydrochloride and 2,5-dihydroxy-p-benzoquinone

A solution of 0.0133 mol of tetraaminopyridine in 300 g of polyphosphoric acid was prepared as in Example 12 from the trihydrochloride. To this solution 1.86 g (0.0133 mole) of 2,5-dihydroergotamine-droxy-p-benzoquinone is added, and the mixture was heated for 12 'hours at 150 ⁰ C. The polymer was obtained in high yield by precipitation, thorough washing with dilute ammonia and drying

■ ^Mw - ^ ^ 209 8 50/1010

OfHQlNAL IMSPECTiD ""

separated.

Example 47A

Polyquinoxaline from 2,3,5,6-tetraaminopyridine and 4,4'-diglyoxalyl-

diphenyl ether dihydrate -

To a solution of 6.36 g (0.020 mol) of 4,4'-diglyoxalyldiphenyl ether dihydrate, which was dissolved in 125 ecm of hexamethylphosphoramide, ■ 2.78 g (0.020 mol) of 2,3,5,6-tetraaminopyridine, which was dissolved in 75 ecm .Hexamethylphosphoramide was dissolved, given .. The phosphoramide solvent had been freshly distilled directly into the reaction vessel under nitrogen at reduced pressure. Weighing and additions were carried out under a nitrogen atmosphere in a dry box. After in the drying box 1 hour had been stirred at room temperature for, the reaction flask was heated for 3 hours at 100 ° C and then 15 hours at about 160 ⁰ C. The polymer was by the addition of 800 ecm of water

• Free methanol precipitated, washed and dried in vacuo. The polymer was subjected to post-heating to complete the cyclization to the polyquinoxaline structure. Included the dry polymer was finely ground and placed in a small rotating flask with several small balls made of stainless, contained in steel, and gradually heated to 375 ° C while rotating

'Is heated under "high vacuum" and then at that temperature (- 5 ° C) held for 2 hours. An analysis of the polymer confirmed a polyquinoxaline structure.

\ .. * Example 473B

Another method for preparing the above polymer used m-cresol as the solvent. In a 100 cc three-necked flask equipped with a stirrer, condenser, and nitrogen inlet tube, 50 cc m-cresol was placed. The system was de-aired and 1.39 g (0.010 mol) of 2,3,5,6-tetraaminopyridine was added with a strong nitrogen purge. To this slurry at room temperature, the polymer solution was added 3.18 "g (0.010 mol) of 4,4'-Diglyoxalyldiphenyläther dihydrate. After 2 hours at 25-35 ⁰ C, the polymer was precipitated in methanol and re-dissolved in m-cresol.

209850/1010

was heated for several hours at 75 ° C, gradually heated to 200 C and the solvent removed in vacuo. The resulting polymer was hitzt 2 hours at 300-375 ⁰ C, yield the Polychinoxalin.zu.

Polymer was for 2 hours at 300-375 ⁰ C under nitrogen

Examples 48-59 . . ■

The procedure of Example 47B is repeated using each of the following diglyoxal dihydrates or mixtures of the bis-glyoxal compounds can be used instead of 4,4'-diglyoxaldiphenyl ether dihydrate, or in some cases the 2,3-, "5,6-tetraaminopyridine trihydrochloride is replaced, one receives .the corresponding polyquinoxalines.

(48) 1,3-diglyoxalylbenzene

(49) 1,4-diglyoxalylbenzene

(50) 4,4 ^f -Diglyoxalyldiphenylsulfid

(51) 4.4 ^! -Diglyoxalyldipheiiylsulfon

(52) 4,4'-diglyoxalyldiphenyl

(53) 4,4 ^I -Diglyoxalylbenzophenone

(54) 2,6-diglyoxalylnaphthalene. .

(55) 2,8-diglyoxalyldibenzofuran

(56) 5,5 ^f -Diglyoxalyl- (2,2 «-dipyridyl) ether

'"(57th) Example 47B, except that 0.005 moles of 2,3,5,6-tetraaminopyridine "by 0.005 moles of 172,4,5-tetraaminobenzene is replaced

(58) 1,4-diglyoxalylbenzene (0.005 mol) and 4,4-diglyoxalyldiphenyl sulfide (0.005 mol)

(59) 4,4'-diglyoxalyl diphenyl ether (0.004 moles), 4,4'-diglyoxalyl benzophenone (0.003 mol) and 4,4'-diglyoxalyldiphenyl '(0.003 mol) ■

Example e 60-68

The procedure of Example 44 is repeated using each the following bisbenzil compounds or mixtures of bisbenzil compounds instead of 4,4'-diglyoxalyldiphenyl ether dihydrate The 2,3,5,6-tetraaminopyridine is either consumed or partially used up is replaced, the corresponding ones are obtained

209850/1010

phenylated polyquinoxalines.

(60) 1,3-Di (phenylglyoxalyl) t> enzene

(61) 1,4-Di (phenylglyoxalyl) benzene

(62) 4,4'-Di (phenylglyoxalyl) diphenyl

(63) 4,4'-Di (phenylglyoxalyl) diphenyl ether

(64) 4,4'-Di (phenylglyoxalyl) diphenyl sulfone

(65) 4,4'-Di (phenylglyoxalyl) benzophenone '

(66) Pyrene-4,5,9,10-tetron

(67) Example 47B, with the exception that 0.00.5 mol 2,3,5,6- • Tetraaminopyridine by 0.005 mol of T, 2,4,5-tetraaminobenzene be replaced

(68) 4,4'-Di (phenylglyoxalyl) diphenyl ether (0.005 mol) and 1,4-di (phenylglyoxalyl) benzene (0.005 mol)

2098 5 0/1010

Claims (1)

Claims Heterocyclic polymers, characterized in that they differ from 2,3,5,6-tetraaminopyridine, optionally in combination with another aromatic tetraamino compound and a polybasic acid. Heterocyclic polymers according to claim 7, characterized in that that the aromatic tetraamino compounds from the group: 1,2,4,5-tetraaminobenzene, 3,3-diaminobensidine, Bis (3,4-diaminophenyl) sulfide, bis (3> 4-diaminophenyl) sulfone and 3,3'j4,4'-tetraaminobenzophenone are selected. Heterocyclic polymers according to claims 7-8, characterized in that that they are derived from tetrabasic acids or their derivatives and essentially as repeating units are those of the structural formula III III Contained, in which R- * is a tetravalent group containing at least carbon atoms, which is substituted in pairs by carbon atoms, the pairs bonded to carbon ens toffatoin.e of the group FU being in the 1,2- or 1,3-position hz \ r. in the ortho or para position, if R ^ is an aromatic group, 'and R ^ is a 2,3,5,6-substituted pyridine group 209850/1010 represents, where R »partially replaced by 1 or 2 R ^ groups can be, and the symbol> the different isomeric structures indicates. 4. Heterocyclic polymers according to claim 3, characterized ge-r 'indicates that as a tetravalent group containing at least carbon atoms, an optionally halogen-substituted, preferably chlorine-substituted aryl radical, preferably benzene or naphthalene radical, cycloalkyl radical, preferably cyclohexane radical, several optionally with oxygen, or the group π or \! interrupted -C- -S- Aryl, preferably phenyl groups, an aryldichinone radical, preferably anthraquinone, or one or more Heterocyclic radical containing nitrogen atoms, before. preferably the pyridine or pyrazine radical contains. 5. Heterocyclic polymers according to claim 2-3 »characterized in that that they are made by condensation with 2,3,5,6-tetraaminopyridine, optionally in combination with another aromatic tetraamino compound and the tetrabasic acid in the form of its anhydride, halide, amide, or esters. 6 .. Heterocyclic polymers according to claims 1-3, characterized characterized in that they are essentially recurring Units of the formula IY O O j. 1 ■ · • c c. \ / ν IV 209850/1010 contain,. where R, R ^, and the symbol> have the meaning defined above and R, in part by 1 or 2 R ^ - Groups can be replaced. 7. Heterocyclic polymers according to claim 3, characterized in that the group R _{3 is} a 2,3,5,6-tetrasubstituted pyridine group. 8. Heterocyclic polymers according to claim 1-2, characterized in that that they are derived from dibasic acids and essentially as repeating units of the structural formula V. .... AA V V -C-, EX C-Pv ₅ - H H wherein R _{5 is} a divalent Group and R ,, "R ^ and the symbol -—— ^ the., Defined above Have meanings, where R ^ 'partially replaced by R ^ and R ^ can be partially replaced by 1 or 2 other R ^ groups. . Heterocyclic polymers according to claim 8> characterized in that they contain an optionally halogen-substituted, preferably chlorine-substituted aryl radical, preferably benzene or naphthalene radical, cycloalkyl radical, preferably cyclohexane radical, several optionally through oxygen, or the Group n or u interrupted Aryl groups, preferably phenyl groups, an aryldichinone radical, preferably anthraquinone radical, or one or more Heterocyclic radical containing nitrogen atoms, preferably the pyridine or pyrazine radical. 20985 0/1010 10. Heterocyclic polymers according to claim §L, characterized in that that they are made by condensation with 2,3,5,6-tetraaminopyridine, optionally in combination with another aromatic tetraamino compound with the dibasic "see acid in the form of its anhydride, halide, amide or Esters. · · . Partially condensed precursors of heterocyclic polymers according to claim 8 ,. ' 12- ,. Heterocyclic polymers according to claim 1 _r 2., characterized in that they differ from tribasic acids and de- | ren derivatives and essentially as repeating units those of the structural formulas VI and VII / χ / V VII contain, wherein Rg is a trivalent, at least 2 carbon atoms represents containing group, wherein 2 carbon atoms on carbon atoms of the group Rg in 1,2- or 1,3-positions; or in the ortho or para position, if Rg is an aromatic group, are substituted, and the third carbon 209 8.50 / 10.10 Substituent substituent not in 1,2- or 1,3- _t ortho or para-position, to the two other carbon substituents, R ,, R ^ and the symbol> are as defined above and R ^ partly by R ,, and Rg can be partially replaced by 1 or 2 other trivalent Rβ groups. 13. Partially condensed precursors of heterocyclic polymers according to claim 12. 14. Heterocyclic polymers according to claim. 1-2, characterized in that they are derived from bis (glyoxal) bonds and / or bis (phenylglyoxal) compounds and essentially as repeating units of those of the structural Formula VIII ^vm contain, in which Ry is hydrogen and / or phenyl, and R ^, R. and the symbol ^ have the meanings defined above, where R ^ is partly through R ^ and -R ₁ - part-. may be replaced by 1 or 2 other R ^ groups. 15. Heterocyclic polymers according to claim ^, characterized in that that they are used as bis (glyoxal) or bis (phenylglyoxal) groups may contain those which are an aryl radical, preferably benzene or naphthalene, several optionally by oxygen or the group O O. Il Il -C- or -S- interrupted aryl, preferably phenyl groups, may contain a dibenzofuran or dipyridyl ether residue. 16 .. Heterocyclic polymers according to claim 1-2, characterized in that 209850/1010 indicates that it differs from pyrene ~ 4,5,9,10-tetron of the formula IX . or other tetracarbonyl compounds. 17. Partially condensed precursors of heterocyclic polymers according to claim 14-16. 18th Heterocyclic polymers according to claims 1-2, dadiirch 'characterized in that they are derived from 2,5-dihydroxy-p-benzoquinone. The patent attorney 209850/1010