DE2136931A1 - Linear polyamides, processes for their manufacture and their uses - Google Patents

Description

Linear polyamides, processes for their preparation and their

Use.

The present invention relates to linear polyamides with high molecular weight, which are characterized by high thermal stability and the following general formula

OC -

C - - C It Il N N

-CO-Y-

- (D

in which X is either O or S. The dicarbonyl stress of the repeating unit is derived from the 1 ₉ 2 ₉ 5 ° thiadiazole-3, J * -dicarboxylic acid (II a) or from the 1 _S 2 _S 5-oxadiazole-3,4-dicarboxylic acid (II b), while Y is the remainder of a primary aliphatic or secondary cyclic diamine or a diamine with cycloaliphatic

209819 / ΙΟβθ

see carbocyclic aromatic or heterocyclic Sing means.

- OC - G C-CO-

II a «X ■ S Hb = X = O

Besides the fact that the polymers of formula I represent an unusual example of polyamides that are derived from purely heterocyclic dicarboxylic acid monomers, they are also characterized in that they can easily be seen from their solutions in common organic solvents in films and fibers and by means of general Conventional pressing processes can be converted into molded pieces · In addition, the remainder II is missing C-H bonds, which are usually the points of least resistance to the thermal decomposition process represent·

All polyamides were made by polycondensation at low temperature using the interfacial method (interfacial method) or by polycondensation in solution, the dihalides (preferably Dichlorides) of acids and the various diamines were used as starting material.

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In particular, the present invention relates to polyamides of structure I, the halide by reacting a di- of l, 2,5-thiadiazole-3,4-dicarboxylic acid (III a) or l, 2,5-0xadiazol-3,4-dicarboxylic acid (III b), whose structure is given below, with primary aliphatic Diamineη, secondary cyclic diamines and slide mi NEN with cycloaliphatic, aromatic or aromatic heterocyclic rings car bocyclischen be obtained.

AIg-OC-C C-CO-AIg (III)

Il Il

IHa, X = S
IHb, X = O
AIg β halogen β Cl, Br.

The primary aliphatic diamines which can be used according to the invention have the following formula

(IV)

in which m is an integer from 2 to 12 and R and R, (the can be identical and different) can represent a hydrogen atom or an alkyl radical. Specific examples suitable diamines are 1,2-ethylenediamine

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and its homologues up to 1,12-dodecamethylenediamine, 1,2-propylenediamine, 2,2,4-trimethylhexamethylenediamine or its isomeric 2, / f, 4-trimethylhexamethylenediamine or their mixtures.

If the diamines have one or more optically active carbon atoms, they can except in the racemic Form can also be used in the optically active (clockwise or linked-rotating) form.

The secondary cyclic diamines which can be used according to the invention have the formula V or VI:

(VI)

in which η 0 or an integer from 1 to 8 and ß is an alkyl radical, in particular a methyl, ethyl or aryl radical mean.

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In the formula V, the various radicals R, if n> 1 is, with respect to the ring in any steric Position be arranged; it can be both the pure (cis and trans) stereoisomers and their Mixtures are used.

In formula VI, m denotes an integer from 0 to 3ι where the aliphatic bridges connecting the dipiperidyl units are arranged either in the ortho, meta or para position; R can be either a hydrogen atom or an alkyl radical, R ₂ either a hydrogen atom or a methyl radical.

Specific examples of suitable secondary cyclic diamines are piperazine, mono-, di-, tri- and Tetramethylpiperazine and its ethyl analogs. Other examples are the 2,3 »5-tri-n-butylpiperazine" the 2,5-ditolylpiperazine, phenylethylpiperazine, phenylmethylpiperazine and the phenylpiperazine.

In addition, 1,2-di (4-piperidyl) ethane, di (4-piperidyl) methane, 1, J-di (4-piperidyl) propane, ^, V-dipiperidine, 3,3 ^I -dipiperidine , 1,3-di (V-piperidyl) -2,2-diaethyl-propane, 1,2-di (3,3'-dimethyl-4-piperidyD-ethane and the 1,3-di (2-piperidyl ) -propane can also be used.

The diamines with cycloaliphatic rings which can be used according to the invention have the formulas VII and VIII:

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(VII)

J. "Γ

(VIII)

in which ρ and ρ '(which can be either identical or different) are 0 or an integer from 1 to 6, R has the meaning given above for formula IV and η is O or an integer from 1 to 10. In formula VIII, Z can be -CH ₂ -, - (CH ₂ ) ₂ -, -C (CHa) ₂ -I -0-, -SO ₂ - or -Si (CH,) ₂ -. Specific suitable diamines are 1, / f-cis- or trans-diaminocyclohexane, 1,3-cis- or trans-diaminocyclohexane, "1,2-cis- or trans-diaminocyclohexane, 1,4-cis- or trans-bis (Aminomethyl) cyclohexane, 1,3-cis- or trans-bis (aminomethyl) cyclohexane or 1,2-cis- or trans-bis (aminomethyl) cyclohexane and their analogous bis-aminoethyl compounds.

In addition, the mixtures of the corresponding cis-trans stereoisomers can also be used. Further Examples are bis (p-aminocyclohexyl) methane and the

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Bis (p-aminocyclohexyl) ethers in their various pure forms and impure stereoisomeric forms. If there is an even number of substituents, they are preferred arranged symmetrically on the cyclohexane core.

An example of a suitable one according to the invention substituted diamine is 3-aminomethyl-3,5> 5-trimethyl-cyclohexylamine- (isophoronediamine).

The aromatic carbocyclic ring diamines which can be used in the present invention have the following Formulas IX and X

(CH,

NH.

NH-

(IX)

H ₂ N

CH ₂ )

(X)

in which Ar is an aromatic carbocyclic radical, e.g. a phenylene, diphenylene or a naphthalene radical, p, p 'and Z have the meaning given above for formula VIII and R the above for For -

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2Ί36931

mel IV has the meaning mentioned, η is O or an integer between 1 and the number of hydrogen atoms bonded directly to the aromatic system.

Diamines specifically suitable for this purpose are p-phenylenediamine and the ortho- and meta-isomers, p-xylenediamine and the ortho- and meta-isomers, benzidine, naphthylenediamine, bis- (p-aminophenyl) methane, bis (paminophenyl) ether, Bis (m-aminophenyl) methane and bis (paminophenyl) sulfone

The diamines with aromatic heterocyclic rings which can be used according to the invention have the formulas XI, XII and XIII:

R _n -E

H ₂ N - Ar - E - Ar -

(XI)

R _n (XII)

ΓΛ-ζ. / 'V ^E f> ^ζ

(XIII) in which E is one or more aromatic heterocyclic

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Kinge represents with 5 to 6 atoms, the aromati see heterocyclic ine one or more heteroatoms such as 0, S, N and Se may contain R a Hydrogen atom, an alkyl or aryl radical and η 0 or an integer between 1 and the number of the aromatic heterocycle or the aromatic heterocycles mean bonded hydrogen atoms.

In formula XII Ar has the same meaning as in formula IX, and in Formula XIII has Z has the same meaning as in formula VIII 'from the diamines of type XI, in particular, the diaminopyridines, the 2 _J 5-diamino-l blank, 3, 4-thiadiazole, the 3 "5-diamino-1,2, if". triazole, the diaminopyrimidines, the 2, Zf-diamino-6-phenyl-S-triazine (benzoguanamine) and the 2, Zf-diamino-6-methyl-S-triazine (aceto-guanamine).

Of the diamines of the formula XII, the bis (p-amino phenyl J-l ^ i ^ f-thiadiazole and Use the bis (p »aminophenyl) -N-phenyl-1,2, Zf-triazole.

Of the diamines of the formula XIII, the Zf ₅ ^{Zf 1} -bis (p-amino phenoxy) -diphenyl-1,3 $ V-oxadiazole can be used.

The polymers according to the invention are produced by polycondensation at low temperature using the interface method or obtained by polycondensation in solution. This becomes common with the interface method Diamine dissolved in one liquid phase with one usually in a second phase, but not with the first phase. miscible, liquid phase dissolved dihalide of the

2 0 ¹ Y a IU / Ϊ Ü B ti

- ίο -

1,2,5-thiadiazole-3,4-dicarboxylic acid or 1,2,5-oxadiazole-3,4-dicarboxylic acid implemented.

In general, the diamine is dissolved or dispersed in an aqueous phase and the dihalide of the acid is dissolved in a water-immiscible organic solvent. The temperature of the polycondensation can range from the freezing point of the phase with the highest freezing point to the decomposition temperature of the | Respondents vary. However, temperatures between -10 ⁰ C and + 70 ⁰ C are preferred.

The organic solvents used for this purpose must be vis-à-vis the reactants However, they can be inert towards that in the other Phase contained reactants be reactive, although their reactivity must be less than the reactivity of the reactant they contain.

As a solvent for the dihalides of 1,2,5-thiadiazole-3 »* f-dicarboxylic acid and for the dihalides of l ^ j ^ -oxadiazole ^^ - dicarboxylic acid are particularly suitable Benzene, chlorobenzene, dichloromethane, chloroform, toluene, xylene, carbon tetrachloride, cyclohexanone, tetramethylene sulf one, 2, lf-dimethyl-tetramethylene sulfone, tetrahydrofuran and propylene oxide.

The reaction can be carried out without stirring or, better, with stirring such that fine dispersion the phases is guaranteed. The concentrations of the halide of the acid and of the diamine in the corresponding

2 (I ¹ JB lü / IUb b

r 11 -

the phases can vary over a very wide range, that of a 100% pure reactant can range up to very dilute solutions (0.001 mol / l).

Furthermore, it is not necessary to use the reactants in stoichioinetric equivalent amounts to use. In many cases, polymers were obtained with high molecular weight if the diamine is used in excess over the dihalide of the acid.

In general, the diamine-containing phase becomes an acceptor for that which forms during the reaction Hydrohalic acid added. This acceptor can be an inorganic base or the diamine itself. Sodium hydroxide is particularly suitable as acceptors, Potassium hydroxide, sodium carbonate, magnesium oxide and triethylamine.

However, the aqueous phase does not have to be basic. It can also be in a neutral or acidic medium to be worked. In order to accelerate the dispersion of the phases, it is sometimes very advantageous to use the to add an emulsifier to the aqueous phase.

When the polycondensation is carried out in solution, both for the diamine and for the dihalide the acid is related to the solvent. Both solutions are mixed with stirring and generally under implemented in an inert gas. As in interfacial polycondensation, the solvents must be compared to the Reactants be inert. For this purpose dichloromethane, chloroform, dimethylformamide,

19/100 II

N-methylpyrrolidone, hexamethylphosphoramide, acetonitrile, Tetramethylene sulfone and 2, Zf-dimethyltetramethylene sulfone related.

Although many of these solvents also contain the hydrohalic acid released during the reaction can block, you can use an organic tertiary base as an acceptor, e.g. triethylamine, dirnethylaniline, N-methylmorpholine, pyridine or the diamine itself, the | is used as a reactant in the polycondensation, add.

The concentration of the monomers can range from 100 % pure reactants to very dilute solutions (0.001 mol / l). The same applies to the temperature of the polycondensation as to the interfacial polycondensation.

The polymers obtained as described above are solids which generally do not melt or Have softening point range, but in general have well-defined glass transition or glass transition temperatures exhibit. These polymers, especially those- " genes with the 1,2,5-thiadiazole core, decompose at high temperature; the latter generally have ther

mix decomposition peaks that occur under a dynamic vacuum]

Vacuum higher than 330 G and in the air higher than

In general, the known heat-resistant polymers have high heat resistance with a low solubility in organic volatile solutions

2098 1 9/1066

connected by means of which it is particularly difficult to subject them to molding processes. In contrast, the polyamides according to the invention have high thermal stability combined with a ready solubility, as can be seen from the examples below.

For this reason, foils (film) and fibers from the solutions of the various polyamides can be easily removed produce. In addition, the polyamides according to the invention, their glass transition or glass transition temperatures be below the decomposition limit, through a suitable choice of temperature and viscoelasticity of the material are converted into molded pieces using the commonly used molding processes (pressing, injection molding, etc.) will.

The molecular weight of the polymers described here depends on the diamines used and on the individual synthesis conditions. The molecular weight of the polymer is expressed by the value for the intrinsic viscosity, which, unless otherwise stated, in a 99% strength by weight HpSO, solution in a concentration of 0.5 g of polymer per 100 ml of solvent at one temperature of 30 ⁰ C was determined. The polyamides according to the invention have an intrinsic viscosity of over 0.3 dl / g. As indicated in the examples, by thermal stability is meant the temperature up to which the polymer does not show any significant weight loss after gradual heating under dynamic vacuum (0.1 torr) or in static air (heating rate = about 3 ° C / min »).

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The following examples serve to illustrate the invention.

Example 1:

A solution of 800 ml of water, 3.10 g of trans-2,5-dimethylpiperazine and 6.92 g of Na ₂ CO _{1 was} poured into a glass reactor with a capacity of 1.9 l.

The solution was then stirred vigorously and a solution of 5.74 g of the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid in 200 ml of dichloromethane was poured in through a side funnel in about 10 seconds. An emulsion formed which was stirred for 10 minutes. The dichloromethane was then evaporated off and the polymer thus obtained was separated off in the form of a white solid. This solid was then ground, suspended in water and stirred vigorously. The polymer was then washed several times with water and then dried at 50 ° C. under reduced pressure. A yield of 95 % was achieved, the internal viscosity was 2.9, which corresponds to an M = 30,000 determined with a Perkin Elmer Mod. 115 osmometer.

The polymer was found to be soluble in a wide variety of solvents, including dichloromethane, chloroform, Dimethylformamide and dimethyl sulfoxide are the most important are. The solutions of the polymer then became transparent films by evaporation of the solvent obtain.

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The Warmebestandigkeit of the polyamide was under a dynamic vacuum and about 390 C in air for about 36O ⁰ C.

The glass transition or glass transition temperature of the polyamide, measured by thermal analysis, was 238 ^° C. and measured by thermo-mechanical methods,

As shown in Table 1 below, those obtained from the solutions of these polymers had Films have a number of excellent properties.

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Table 1:

Measure ASTM unit sample Remarks ! 23 ⁰ C Relative default example 1 ι humidity
j 65 % I. i Specific weight D'792 g / cnr 1.27-1.33 ; Water adsorption D 570 % 2-2f after Zh hours \ , Vapor permeability E 96 £ cm 0.04 Method B \ , m ² , mmHg 2i |. ^H : Tensile strenght D 882 kg / cm 950-1100 Samples that \ j extreme elongation D 882 % 8-10 2h Std.lang; i (Ultimate elongation) Dei cLy ^ Kj uno. \
a rela- \ I tear resistance D 77h kg / cm 1.3-1.5 tive air j i (Resistance to bur humidity i sting) from 65 % I. ■ folding resistance D 2176 number of : conditioned I. Double folds 8 000-10 00c WUx UcIl ι transparency D 1003 % ! 94-95 i
: with sun
"1 * 4 r * Vi 4" ViQ _- \
\ : shine Cloudiness D 1003 % 0.8 - 1
i

This polyamide has good hydrolysis resistance and good stability against strong bases, Salt solutions and organic solvents (alcohols, ketones, aliphatic and aromatic hydrocarbons) on. The polyamide obtained according to Example 1

was made tableted powder at 280-300 ⁰ C.

p pressing at specific pressures of 250-300 kg / cm in molded transparent plates with a thickness of 1-2 mm. These plates were used to climb-mill the samples obtained according to their physical-mechanical properties shown in Table 2 below Main characteristics are to be assessed.

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Table 2:

σ co cc

Measure

23 ° Relative humidity 65 %

ASTM standard

unit

sample
Example 1

Remarks

tensile strenght

extreme elongation

modulus of elasticity

Rockwell hardness

Resistance to creep under tensile stress)

Linear coefficient for thermal expansion

Distortion to heat

700-800
5-6

6O, OOO-7O _T OOO
100-120

1.5

6, ΙΟ-

235

After 1,000 minutes at

500 kg / cm ² in air, relative humidity 10 %

dilatome

tric

method

at

18.56 kg / cm ²

Oo

213693

Example 2;

A solution of 300 ml of water, 2.37 g of Ka ₂ CO, and 0.80 g of piperazine was poured into a 1 liter three-necked flask. The solution was vigorously stirred. Another solution of 300 ml of dichloromethane and 1.96 g of the dichloride of 1,2,5-thiadiazole -3-4-dicarboxylic acid was poured into this solution. A finely divided precipitate then formed which became more consistent after stirring for a further 10 minutes. The dichloromethane was removed under vacuum and the resulting polymer was then washed several times with water and finally dried. The yield was 88 %.

washed with water and finally at 50 ⁰ C under vacuum

The polyamide, which had an intrinsic viscosity of 0.77, was soluble in HCOOH ₉ m ~ cresol and the sttm-tetrachlora / phenol mixture (weight ratio 40/60) _{in addition to H ^ SO 1.} This polyamide started under a dynamic vacuum at about 36O ⁰ C and in the air to decompose at about 300 C.

Example 3;

A solution of 100 ml of water, 5.26 g of 4j4'-trimethylene dipiperidine and 6.36 g of Na 2 CO _{4 was poured into a 1 liter three-necked flask.} This solution was stirred vigorously while a solution of 100 ml of dichloromethane and 5.27 g of the dichloride of 1,2,5-thiadiazole-3-4-dicarboxylic acid was quickly added. A viscous emulsion formed which was stirred for 10 minutes became. The dichloromethane was then evaporated from this emulsion under vacuum, and the polymer thus obtained

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/ 138931

after being suspended in water, was milled with vigorous stirring. The polymer was then washed several times with water and then ^{dried at 50 °} C. under reduced pressure. The yield was 95 % and the intrinsic viscosity was 2.37. In addition to HpSO, the polymer was also soluble in HCOOH, chloroform and dichloromethane. Transparent sheets (films) were obtained from the solutions of the polymer by evaporating the solvent. The glass transition or glass transition temperature, measured by differential calorimetry, was 118 C, which made it possible to obtain | to form the polyamide at 1 ^ 0-200 C using commonly used molding processes in sheets or finished goods (manu factures articles). Under a dynamic vacuum, the loss begins at around 340 ^° C., while the polymer begins to decompose in the air at 260 ° C.

example k :

A solution of 250 ml of water, 6.30 g (0.085 mol) of 1,3-propylenediamine and Poured 3.48 g of NaOH.

A solution of 250 ml of benzene and 8.96 g (0.042 mol) of the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid was added rapidly with stirring. A fibrous, white precipitate formed immediately. After 10 minutes the stirring was stopped and the benzene was evaporated in vacuo. The polymer was then ground and, after being suspended in water, washed several times with vigorous stirring. Finally it was ^{dried at 50 °} C. under vacuum.

2U9bi9 / 1Ü86

The yield was 63%> the intrinsic viscosity was 0.56. It was found that the polyamide was soluble not only in H, but also in HCOOH, in a chloroform / methanol mixture (in a weight ratio of 80:20), in dimethyl formamide and in dimethyl sulfoxide C measured by differential calorimetry. Its thermal stability in the air was about 280 ^° C.

Example 5:

In a 1 liter three-necked flask equipped with a stirrer and kept under an atmosphere of dry nitrogen, a solution of 300 ml of chloroform and 8, kk S of the dichloride of 1 _s 2 _s 5-thiazol-3, * f -dicarboxylic acid initiated. This solution was admixed with a solution of 300 ml of chloroform and 9.14 g of trans-2,5-di-diethylpiperazine with stirring over the course of one hour at room temperature and under a nitrogen atmosphere.

The mixture was then stirred for a further 10 minutes, _s thereby obtaining a viscous solution of the chloroform was evaporated under vacuum. When the mixture was completely dry the product in almost ₉ 2 1 warm water was dissolved and then filtered "The filtrate was then abundantly washed with hot water and then dried under vacuum at 60 ⁰ C. The yield of the polyamide obtained in this way was based on 95% (based on the dichloride of the acid); it had an inherent viscosity of 1.95.

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Example 6;

In contrast to Example 1, the dichloride was used here related to lj2,5-oxadiazole-3,4-dicarboxylic acid.

The starting solutions contained the following components: 800 ml of water, 2.28 g of trans-2,5-dimethylpiperazine and 509 g of Na ₂ GO ^. A solution of 200 ml of dichloromethane and 3.90 g of the dichloride of ψ l ^ j ^ -oxadiazole ^ j ^ f-dicarboxylic acid _{was then added to this solution according to the method described in Example 1 &} the yield was 62 % , the intrinsic viscosity 3 »11 · The polyamide was found to be soluble in a variety of solvents; belong to the more important solvents; HCOOH, chloroform, dichloromethane and dimethylformamide.

Example 7 °

In a 1 liter three-necked flask fitted with a neck, kept under a nitrogen atmosphere, a solution consisting of 200 ml of chloroform, if, 00 g of 2-methylpiperazine and 11.6 g of triethylamine was then introduced this solution was quickly stirred with a

another solution containing 200 ml of chloroform and 8, Mt g of the dichloride of 1,2,5-thiadiazole-3 _f 4-dicarbonic acid added. The mixture was then stirred for 15 minutes and the resulting viscous solution poured into about 3-n-hexane, whereupon the polymer separated. The polymer was filtered off, washed several times with water and then dried at 50 ° C. under a vacuum.

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The polymer was obtained in a yield of 96 % . The polymer had an intrinsic viscosity of 2.2 and, in addition to being soluble in HoSO, also in HCOOH, chloroform, dichloromethane, dimethylformamide and dimethyl sulfoxide. Its thermal stability under dynamic vacuum was 36O ⁰ C and 35O ⁰ C. in the air This polyamide had a glass transition temperature or glass transition temperature of 210 C (measured by differential scanning calorimetry), whereby it was possible, at 21f0-260 C by means of generally common molding process in Forming panels and finished goods.

Example 8:

In a reactor with a capacity of 1.9 liters a solution of 100 ml of water, A-65 g of 1,6-hexamethylenediamine and 10.18 g Na-CO ^ poured. To this The solution was then another solution of 70 ml of dichloromethane and 8.4 g of dichloride while stirring more rapidly the 1,2,5-Tliiadiazol-3> ^ i - dicarboxylic acid mixes. This mixture was then stirred for 10 minutes, after which an emulsion was obtained from which the Polymer was separated after evaporation of the dichloromethane under vacuum. The polymer was filtered off, then Washed abundantly with water and then at 50 ° C dried under vacuum.

The polymer was obtained in a yield of 85% and had an inherent viscosity of 0.56.

It turned out that the polymer except in sulfur

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acid was also soluble in HCOOH, in a chloroform / methanol mixture (weight ratio 88:12), in dimethylformamide and in dimethyl sulfoxide. Its thermal stability in air was 3A-0 C. This polymer had a glass transition or glass transition temperature of 66 ⁰ G, which was measured by means of differential calorimetry.

example 9:

In contrast to the example given above, the dichloride of 1,2,5-0xaxliazol-3, V'dicarboxylic acid was used here. The starting solutions contained the following components: 400 ml of water, 2.32 g of 1,6-hexamethylenediamine and 509 g of Na ₂ CO ,,; a solution consisting of 70 ml of dichloromethane and 3 »90 g of the dichloride of the! ^, ^ - oxadiazole ^ j ^ f-dicarboxylic acid was added to this solution according to the method described in Example 8. The polymer was obtained in a yield of 63 % and had an inherent viscosity of 0.45. In addition to HpSO, it was also soluble in HCOOH, in a chloroform / methanol mixture (weight ratio 88:12), in dimethylformamide and in dimethyl sulfoxide.

Example 10:

A solution of 60 ml of dirnethylacetamide and 2.71 g of m-phenylenediamine was poured into a three-necked flask with a capacity of 250 ml provided with a stirrer and a thermometer. This solution was cooled with an ice and salt bath to keep the temperature of the solution at about ⁰ ° C. Thereupon 5 »27 g of the

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Dichloride of 1,2,5-thiadiazole-3,4 "dicarboxylic acid was added in three portions, the three portions being added every 5 minutes. After each addition, the temperature rose to 15 ^° C. and then fell again to ⁰ ° C.

The polymer separated from the solution during the third addition, which was another 9 hours at room temperature was stirred »

The mixture was then poured into water and ice, then filtered and washed several times with water. After the polymer ^{had been dried at 50 °} C. under vacuum, a yield of 95 % was obtained; the polymer had an intrinsic viscosity of 0.36%. In addition to HpSO, the polyamide was also soluble in dimethylformamide and in dimethyl sulfoxide. The thermal decomposition in the air occurred at a temperature above 300 ⁰ C «,

Example 11:

600 ml of a water / tetrahydrofuran mixture (volume ratio 1: 1), 2.5 g of k $ k '-diaminodiphenyl ether and 1.00 g of NaOH were introduced into a reactor with a capacity of 1.9 l.

Then, with rapid stirring, a solution containing 600 ml of dichloromethane and 2.64 g of the dichloride of 1,2,5-thiadiazole-3, ^ - dicarboxylic acid contained, mixed in. This immediately formed the polymer in the form of a very finely divided precipitate, which was stirred for 15 minutes.

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2T36937

The dichloromethane was then evaporated under vacuum abge and the polymer was filtered off, then washed several times with water and then dried at 50 ⁰ C under vacuum.

The polymer was obtained in a yield of 95 % ; the polyamide had an intrinsic viscosity of 0.34 and was SO _{except in H 2.} also soluble in dimethylformamide and dimethyl sulfoxide. Its thermal stability in the air was 35O ⁰ C.

Example 17 :

A solution of 400 ml of water, 18.59 g of 1,6-hexamethylenediamine and 20.35 g of Na ₂ CO ^ was poured into a reactor with a capacity of 1.9 l.

The solution was cooled to 0 C and, while stirring rapidly, a solution of 70 ml of dichloromethane and 16.87 g of the dichloride of I, Z ^ -thiadiazole-J ^ -dicarboxylic acid was added. The whole mixture was stirred for 10 minutes. After the dichloromethane was evaporated in vacuo, the polymer was obtained. This polymer was ground in water at 0 ° C. with vigorous stirring. After the polymer had been filtered off, it was washed several times with water and ^{dried at 50 °} C. under reduced pressure. A yield of 88 % was achieved. The intrinsic viscosity was 0.71.

Example 13:

In a reactor with a capacity of 1.9 l

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was a solution of 400 ml of water, 8.42 g of 4,4'-methylenebis (cyclohexylamine) and 10.18 g Ufa CO ^ poured With rapid stirring, this first solution was mixed with another solution of 70 ml of dichloromethane and 8.44 g of the dichloride of 1,2,5-thiadiazole-3,4-dicarbo acid offset. The whole mixture was stirred for 15 minutes to obtain an emulsion from which the Polymer was separated after evaporation of the dichloromethane under vacuum. After the polymer has been filtered off it was washed several times with water and 1 L of ethyl alcohol and dried at 50 ° C under vacuum.

The yield was 93 %. The intrinsic viscosity, measured in N, N'-dimethylformamide (concentration: 0.50 g / 100 ml, at 30 ^° C.), was 0.37.

It was found that the polymer, in addition to N, N'-methylformamide, was also soluble in a chloroform / methanol mixture (weight ratio 88:12) and in dichloromethane. Its thermal stability in air was 340 ^° C. This polyamide had a glass transition - or freezing temperature of 205 C (measured by differential calorimetry), which made it possible to transform it into plates by molding at 240-280 ° C at specific pressures below 2,000 kg / cm g / uii.

Example 14:

To a 1 liter flask was added dropwise a solution of 160 ml of water, 4.38 g of a mixture of the isomers of trimethylhexamethylenediamine and 2.27 g NaOH poured.

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A solution of ΙβΟ ml of dichloromethane and 3) Sk g of the dichloride of 1,2,5-thiadiazole-3 »4-dicarboxylic acid was then added with rapid stirring. The whole mixture was stirred for 10 minutes to obtain a white emulsion from which the polymer was separated after the dichloromethane was evaporated. After the polymer had been filtered off, it was washed several times with water and ^{dried at 50 °} C. under vacuum.

The yield was 87 % and the inherent viscosity of the polymer was 0.42.

The polymer is not only in HpSO, but also in formic acid, Chloroform, dichloromethane, dimethylformamide, dimethyl sulfoxide and in a chloroform / methanol mixture (Weight ratio 88:12) soluble. Its heat stability in air was 300 C. The polyamide had one Glass transition or glass transition temperature of 76 ° C as measured by differential calorimetry.

Example 15:

In a flask provided with a stirrer, a thermo- ψ thermometers and a ^ inleitungsrohr nitrogen, was added a suspension of 60 ml of dimethyl formamide, 5 »g of triethylamine and 06 ki73 S 2,5-diamino-1,3, if-thiadxazoldihydro chloride initiated.

The solution was cooled to -7 ° C. and, while stirring, with the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid mixed in three servings. The first portion weighed 2.0 g, the second 2.0 g and the third 1.27 g; the addition

20 9 8 19/1066

ν.

occurred every 5 minutes. The whole mixture then became new Stirred for hours and left to stand overnight.

The polymer precipitated after adding 2 liters of water at 0 ° C.

The precipitate was filtered off and the polymer was washed with water and then under vacuum at 50 C dried.

The yield was 85 % and the inherent viscosity of the polymer was 0.31.

209819/1066

Claims (1)

Claims; 1 * Linear polyamides with a high thermal stability and the general formula OC - Il -C - CO - Y in which X is 0 or S, Y is the radical of a primary aliphatic, secondary cyclic diamine or a diamine with cycloaliphatic, carbocyclic aromatic or heterocyclic aromatic rings mean. 2. Polyamides according to claim 1, characterized in that Y of the formula is the radical of a primary aliphatic Diamines of the general formula: R. 2098 19/1066 represents in which m is an integer from 2 to 12 and R and R ₁ , which can be identical or different, denote H or an alkyl radical. 3. Polyamides according to claim 1, characterized in that Y of the formula is the radical of a secondary cyclic Diamine's general formulas HN S NH or Η R. represents in which η is zero or an integer from 1 to 8, R is a lower alkyl or aryl radical, m is an integer between 0 and 3 »Rr is H or an alkyl radical and R _{2 is} H or CH ^. 4. Polyamides according to claim 1, characterized in that that Y of the formula the radical of a diamine containing cycloaliphatic rings of the general formulas or 2098 19/1066 / Λ R. I- represents, in which ρ and ρ ¹ , which can be the same or different, zero or an integer from 1 to 6, RH or an alkyl radical, η zero or an integer from 1 to 10 and Z -CH ₂ -, - ( CHg) ₂ -, -C (CH,) ₂ -, -0-, -SO ₀ - or -Si (CH ^) ₀ -. 5. Polyamides according to claim 1, characterized in that that Y of the formula the radical of an aromatic carbocyclic rings containing diamine of the general formulas R _n -Ar ^NH NH. or ^CH 2> p -z- CH P ¹ NH. 2098-9 / 1066 represents, in which Ar is an aromatic carbocyclic radical, p, - p ¹ and Z the above in claim L \. Have the meaning mentioned, RH or an alkyl radical and η zero or an integer between 1 and the number of H atoms bonded directly to the aromatic system. 6. Polyamides according to claim 1, characterized in that Y of the formula is the radical of an aromatic heterocyclic Rings containing diamines of the general formula H ₂ N-Ar-E-Ar-NH ₂ in which E one or more aromatic heterocyclic rings having 5 or 6 carbon atoms and 1 or more Heteroatoms, such as 0, S, N or Se, R H, an alkyl or aryl radical and η zero or an integer from 1 up to the number directly attached to the aromatic heterocycle 2098 19/1066 2Ί36931 bonded Η atoms, and Ar and Z mean the above Have the meaning mentioned, represents. Ty method of making the linear poly- Amides according to Claims 1 to 6, characterized in that a primary aliphatic diamine or a secondary cyclic diamine or a diamine with cycloaliphatic, carbocyclic aromatic or aromatic heterocyclic rings at low temperature with the ρ dihalide of a dicarboxylic acid of the general formula AIg-OC-G ■ C-CO-AIg it It N N V / in which X is 0 or S and AIg is Cl or Br, polycondensed. 8. Ancestors according to claim 7 »characterized in that that the dihalide of the dicarboxylic acid is the di- * Chloride of 1,2,5-thiadiazole-3i4-dicarboxylic acid used. 9. The method according to claim 7 »characterized in that that the dichloride of 1,2,5-0xadiazole-3,4-dicarboxylic acid is used as the dihalide of the dicarboxylic acid. 10. Polyamide obtained by polycondensation of trans-2,5-dimethylpiperazine and the dichloride of 1,2,5-thiadiazole-3, if-dicarboxylic acid has been received. 209819/1066 11. Polyamide obtained by polycondensation of piperazine and the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid has been received. 12. Polyamide obtained by polycondensation of 4i4'-trimethylene dipiperidine and the dichloride of 1,2,5-thiadiazole-3> 4-dicarboxylic acid has been obtained. 13. Polyamide obtained by polycondensation of 1,3-propylenediamine and the dichloride of 1,2,5-thiadiazole. 3,4-dicarboxylic acid has been obtained. 14 · polyamide obtained by polycondensation of trans-2,5-dimethylpiperazine and the dichloride of 1,2,5-0xadiazole-3 »4-dicarboxylic acid has been received. 15 · polyamide obtained by polycondensation of 2-methylpiperazine and the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid has been received. 16. Polyamide obtained by polycondensation of 1,6-hexamethylenediamine and the dichloride of 1,2,5-oxadiazole-3i5-dicarboxylic acid has been received. 17. Polyamide obtained by polycondensation of 1,6-hexamethylenediamine and the dichloride of 1,2,5-thiadiazole-3> 4-dicarboxylic acid has been obtained. 18. Polyamide, which by polycondensation of m-phenylenediamine and the dichloride of l, 2,5-thiadiazole-3tA · - 2 0 9 8 19/1066 dicarboxylic acid has been obtained. 19. Polyamide obtained by polycondensation of if, V-diaminodiphenyl ether and the dichloride of 1,2,5-thiazole-3,4-dicarboxylic acid has been received. 20. Polyamide obtained by polycondensation of ktk ^x - methylene-bis (cyclohexylamine) and the dichloride of 1,2,5-thiadiazole-3, ^ - dicarboxylic acid. W 21. Polyamide, obtained by polycondensation of tri - methylhexamethylenediamine and the dichloride of 1,2,5-thiadiazole-3i4-dicarboxylic acid has been received. 22. Polyamide obtained by polycondensation of 2,5-diamine-1,3 > 4-thiadiazole dihydrochloride and the dichloride of 1,2,5-thiadiazole-3, ^ - dicarboxylic acid has been obtained is· 23. Films, fibers, plates and finished goods which have been produced from the polyamides according to claim 1 are. For: Montecatird Edison S.p.A. To the right 9 η 1 tf / 1 c e 6