SU294349A1 - - Google Patents

Description

METHOD OF OBTAINING MODIFIED COMPLEX

The invention relates to the manufacture of linear elastic plastics and their use for the preparation of elastic structures and coatings.

A method of producing modified polyesters is known by reacting the bischloroformic acid esters of macroglycols with molecular weights of 500-5000 in solution with diamines. The resulting low molecular weight polymers, each having two terminal primary or secondary amino groups per molecule, react with difunctional low molecular weight compounds across the active hydrogen, and mainly linear polymers are formed, which can be molded into elastic fibers or films. The last transformation is called “chain elongation. Polymers prepared in this way, even when heated, hardly dissolve or not dissolve at all in high polar solvents, for example dimethylformamide, so that only acidic aggressive solvents, such as L - / - cresol or formic acid, are used to make spinning solutions. Melt processing of these polymers is difficult due to the thermal decomposition of the polymer at temperatures above 200 ° C.

POLYESTERS

A method of producing modified polyesters with improved elastic properties is proposed by treating them with bishydrazide compounds followed by reaction with difunctional low molecular weight compounds that react on terminal hydrazide groups.

The polymers obtained by the proposed method have a minimum viscosity of 0.5 and are a repeating structural element.

(I)

-NH-NH-.A, -NH-Z

Where Agde f is a divalent acyl residue of a polybasic aliphatic, homocyclic, and heterocyclic carboxylic acid; Z - one of the remnants of the formulas

C- (0) g-X- (0), - C (P);

Iiii

oo

-С-У-С (III)

Oh oh

At its base, the NHN compound has a molecular beam of 400-5000 nt pl. less than 70 ° C, in which the chain can be interrupted by a heteroatom of oxygen, sulfur and separated by the nominal two chains of C-atoms;

V-a) alkyl group with dy chain max. 12 carbon atoms, cycloalkylene, containing 5-8 carbon atoms, phenylep, fennlen-V-phenylene,

moreover, VO-, -S-, -SO;) -, alkylidene

or cycloalkylidene with 5 to 8 carbon atoms, benzfep 1lenova, naphtseley group, with the named groups replaced by lower alknlom, fluorine, chlorine nli carboxyl group;

b) -NH-R-NH-, where R is an alkylene group containing 2 to 12 carbon atoms, (o, o) -syllene nl metlenic acid cyclomethyl group;

c) -O-R-O-, where R is an alkyl group having 2 to 12 carbon atoms or methylene cyclohexylene metlenlen;

d) 1,4-niperazicidinyl; g - About 1 and 1 on average for one residue

-C-Y-C- statistically allocated

II

Ooh

residues-C- (O); X- (O), .- C-; p - rationIIII

OO

the real number is 0.5-5.

As the multi-carbon carboxylic acids, indicated in the general formula A, the following is used: carbonic acid; aliphatic dpcarboxylic acids, such as oxalic, adinic, sebacanova; aromatic dicarboxylic acids, such as isophthalic; heterocyclic dincarboxylic acids, such as furan-2,5-dicarboxylic, thiophene-2,5-dicarboxylic, nnrndn-2,5-dicarboxylic acid, and also azine hydroxy acids, such as derivatives of 2,4-dnoxytriazone, nly o-, m- , yy-diazines, nanrnmer 2,4-dioxy-6-alkyl triazines, 2,4-dioxy-6-monoalkylamino-3-triazines, 2,4-dioxy-6-dinkylaminio-5-triazines, 2,4-dioxane 6-alkoxy-8H., N-NH-A-NH-NH C- (O), - X- (O) 2-C-NH where / g is O, real number; A, X, g are as defined in formulas (I), (I) reacts with the introductory-C-Y-CII II dysfunctional compound. Bishydrazide prepolymers of the formula (IV), manufactured triazines, 3,5-dioxy-1,2,4-trnazine, 2,4-dioxy-6-dialkylamidio-1, 3-diazia, 2,5-dioxy-1,4-diazium, 2, 4-dioxy-5-chloro-6-dialkylamino-1,3-diazines, 1,4-dnoxyphthalase and 2,4-dioxynhinazoline; also heterocyclic hydroxycarboxylic acids, e.g. 2-hydroxy-n-imidine-5-carboxylic, and dioxo compounds, hydroxyl grains of which are located in different rings, e.g. dnox-di-5-tna, such

as N, N-bc-4-oxy-6-dialkylamino-S-tripiazinyl- (2) alkyl diamines and α-iyerazines, as well as similar diazine compounds.

In the formula (P) X, in a particular case, it can be a pure hydrocarbon radical, for example, a growth polyester radical, nanopolymers of ethylene glycol homopolymers, propylene glycol, tetramethylene glycol, hexamethylene glycol, as well as copolymers of the named glycols or polyether ethers obtained by condensing thiodiglycol by means of the same time, they use the same templates and the copolymers used by the self-alkyd glycol, hexomethylene glycol, and the copolymers of the glycol or polythioether obtained by the condensation of the thioglycol glyphs and the copolymers of the glycophenol glycol or the polyether glycol or the polyether glycol or the polyether glycol or the polymethylene glycol or the polystyrene glycol or hexolymethyl glycol. . X may be a polyester radical derived from dicarboxylic acids and aliphatic glycols. Dicarboxylic acids can be aliphatic, such as adipic, glugaric, trimethyladipic, nimelinovy, azelaic, sebacin, isosebacinic acid (mixture of dicarboxylic acids Xu); cycloaliphatic, such as

1,3- or 1,4-cyclohexanedicarboxylic acid; aromatic, such as terephthalic or isophthalic acid, from aliphatic glycols, ethylene glycol is used,

1.2- and 1,3-propylene glycol, 2,2-dimethyl-iroandiol- (1,3), 1,3- or 1,4-butanediol, pentanediol, hexanediol, methylhexanediol or mixtures thereof, and from cycloaliphatic glycols

1.3-or 1,4-cyclohexanediol, 1,3- or 1,4bpsoxymethylcyclohexane. Used for

For the manufacture of polyesters, aliphatic dicarboxylic acids may also contain heteroatoms in the chain, for example, thiodipropionic acid or hydroxypropionic acid. You can use the radicals of e-canrolactic polymers as the nolyester radical.

The method of manufacturing the polymer is that the bishydrazides of the formula

(IV) 55 NH-A-NH-NHIK are liquefied per gram-mole minimum of ½ mol of an acid bishalondanhydride of the formula gAL-C- (O), - X- (O) .- C-gal (V) II, and 00 where a hal is a halogen atom, such as chlorine; X, g, and p are as defined above, and the minimum mole of the polyhydric carboxylic acid bishydrazide, for example, aliphatic, homocyclic, heterocyclic, at minus 20 is plus 100 ° C, preferably at O -40 ° C.

In the case of high molecular weights, the acid bishalide of the acid of formula (V), i.e., at mol. weight. 2500-5000 n choose the meleda 0.5 and 1.5; on the contrary, if the molecular weight of the acid bishalo of the formula (V) is 800-2500, then it is advisable to choose between 1.0 and 3, preferably 1 and 2.5.

The reaction is carried out in solution in the presence of an acid acceptor, preferably in a corrosion-resistant apparatus. Conventional inert organic solvents are used as solvents. When using almost neutral solvents - ethers, nanodimer of dioxane, tetrahydrofuran, 1,2-dimethoxyethane; chloro derivatives of hydrocarbons, for example, methylene chloride, chloroform, tetrachlorethylene; sulfones, for example tetramethylene sulfone, it is recommended to use acidic acceptors — common tertiary bases, for example, triethylamine, pyridine, N-ethyl morpholine; Inorganic acidic accentors, such as carbonates or hydroxy alkali and alkaline earth metals, for example calcium carbonate or sodium hydroxide, are also used. When using preferred weakly basic solvents such as acid amide, for example, hexamethylphosphoric acid triamide, dimethylacetamide, iN-methylpyrrolidone, tetramethyl urea, a mandatory addition of an acidic acceptor is not required, which sometimes even adversely affects the color of the resulting polymers.

Advantageously, 1 mol of bishydrazide or mixture of bishydrazides is dissolved in the solvent, mainly dimethylacetamide or N-methylpyrrolidone, and 0.5-0.75 mol of acid bichloride of formula (V) is added at O-40 ° C with good agitation, large the initial quantities, when cooled in such a way that the temperature does not exceed 100 ° C, preferably 40 ° C. The addition rate should be such as to maintain the specified temperature, the addition time can be from a few seconds to several hours. The solvent is added until complete dissolution of the bishydrazide components. In this way, spinning polymer solutions are obtained which must neither be concentrated nor diluted.

Bischloroformates of polyethers of n / or polythioethers with two mainly terminal hydroxyl groups, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol,

polyethylene propylene, glycol, (1,6-dioxa-9-Tii aundek II) glycol and nol- (1-oxa-4thiahexane) glycol bischloroformate, as well as polyether bis (chloroformates) with two mainly terminal hydroxyl groups, such as polyethylene adipate, polyethylene glyphenes, and a type of pipe (a type of polyether adiphenate), a kind of polymers. , polyethylene sebacate, polyethylene (3-methyladine), poly- (2,2-dimethylpropylene) - (3-ethyladipate), sonoli- {2, 2-dimethylnronylene) - (1-pronylpropylene) adinate, polybutylene - (3,4 - diethyl adipate), polyhexamethylene acetate and polyb-caprolactone bischloroformate.

Bis chloroformates are obtained from diols and phosgene in the absence of bases. It does not matter if there is an excess of phosgene and the diol is slowly instilled neat or dissolved in a suitable inert solvent, for example, in benzene, methylene chloride or dioxane, at minus 20 - plus 80 ° C, preferably at room temperature to 40 ° C , or at these temperatures, the phosgene is introduced into the liquid or dissolved diol before the excess is obtained. In both cases, the excess phosgene and the liberated hydrogen chloride are removed under reduced pressure, best of all by stirring with a dry inert gas such as nitrogen.

As dihydride anhydrides of the acid of formula (V), polyester halides are substituted for with two membranes in the main end of which are carboxyl groups. In this case, for the manufacture of polyesters, the same dicarboxylic acids and glycols, which are used for the synthesis of the above-mentioned polyesters with hydroxyl terminal groups, can be used, only the dicarboxylic acids are introduced in excess. The conversion of the dicarboxylic polyester esters to the desired acid dihydroxyhydrides of the formula V is carried out by conventional methods, i.e., using well-purified thionyl chloride.

Identical or similar dihalogenohydrides of dicarboxylic acids of polyethers and halides of dicarboxylic acids of polyethers are obtained by reacting complex or simple diols with an excess of dicarboxylic acids. As dihydride anhydrides of dicarboxylic acids, which are suitable for reaction with con-. hydroxyl groups of these macrodiols use common aliphatic and aromatic dicharboxylic acid halides, for example, sebacic, adipic, tarephthalic and isophthalic acid dichlorides.

The proposed elastomers with an alternating series of basic structural elements of the formula (I) are prepared by condensation of the above-described bishydrazides of the formula (IV) with the so-called chain extensions, which

the residue -C-Y-C- is introduced in molar from IIN

OO

wearing 0.9-1.1: 1, advantage of 0.95-1.05: 1. This condensation is carried out in the reaction conditions, which are higher for the condensation of acid dihalides of acid of formula (V) with bishydrazides, in particular, these solvents, acidic accentors and concentrations are used. It is advantageous to alternately conduct both condensations in the same reaction vessel. In this case, the extension cord is added in solid or liquid phase, or in solution but possible in a small amount of solvent, with good stirring to the prefabricated bishydrazide of formula (IV) that exists mainly in solution, and, if necessary, the above mentioned temperatures are maintained by cooling. In the manufacture of very highly concentrated and highly viscous solutions, it is advisable to carry out the polyodensation in the mixer.

It is especially advisable to use acid amides as solvents, since in this case, even without acid acceptors, flexible plastics with high molecular weights and with a minimum natural color are obtained. This is of technical importance, since solutions of elastic plastics made in this way can be directly spun, while the use of acid acceptors requires additional filtration before spraying.

Conventional additives for flat and fibrous elastomeric structures, such as nanofillers, matting agents, stabilizers, pigments, dyes, can at some stage be admixed with the manufactured elastomers, preferably the additives are added before condensation, called a price extension.

As chain extenders, acid digestive anhydrides can also be used, as well as isocyanates, bisketones, tetracarboxylic acid danhydrides, as well as substances that have two different functions, for example, monohydride tricarboxylic acids.

Among the acid dihalides, dicarboxylic aliphatic acid dihalohydrides and bischloroformates should be mentioned as chain extenders. Malondyl chloride, adipyl chloride, pimelylipic dibromide, sebacil chloride are used as aliphatic dicarboxylic acid dihalides. With known precautions, dictic carboxylic acid halides, such as 1,3- and 1,4-dichlorides of cyclohexanedicarboxylic acid, in particular mixtures of cis- and g / 7an-isomers and aromatic chlorides of dicarboxylic acids, such as diphenyl ether-4, can also be used. , 4-dichloride of dicarboxylic acid, diphenylthioether-4,4-dichloride of dicarboxylic acid, diphenylsulfo-3, 3- or 4,4-dichloride of dicarboxylic acid, diphecylmethane-4,4-dichloro dicarboic acid, 2,2-b "c (4-chlorocarbonylphenyl) nronan, 2.2 - byc - (4-chlorocarbonylphenyl) buta 1,1-bis- (4-hlorkarbonilfenil) -butane. But especially suitable are terephthaloyl chloride, tsophthaloyl chloride and caftalin2, dicarboxylic acid 6-chloride.

Of the bischloroformates used as chain extenders, bischloroformates of aliphatic diols are used, for example 1,2-dioxyethane, 1,2-dioxypropane, 1,3-dioxypropane, 1,4-dioxybutane, 1,3-dioxy- 2, 2-dimethylpropan-, 1,6-dioxyhexanebischloroformate, and a cycloaliphatic diol, such as 1,4-bisoxnemethylcyclohexanebischloroformate. Similarly, M, L-bischlorocarbonylpiperazine is also used as a chain extender.

Of the isocyanates that are used as chain extenders, aliphatic diisocyanates should be mentioned, especially those formed from amines with four or more carbon atoms in the chain, such as buta-1,4-diisocyanate, hexane-1,6-diisocyanate, dodecane -1,12-dzisocyanat, 2,2,4-trcmethylhexane-1, 6-diisocyanate.

As price extenders, tetracarboxylic acid bisanhydrides — czromellitic acid anhydride, tetracarboxylic acid cyclohexap-1,2,4,5-aigcdride, tetracarboxylic acid butane-1,2,3,4-anhydride, as well as acid halides of tacarboxylic acid acids.

Elastic plastics get the proposed method predominantly in solution. Isolation is carried out by conventional methods, for example by evaporation of the solvent or by adding a precipitant, for example water or a mixture of water with alcohols, and hydrocarbons — hexane, heptap.

The fabrication of films and filaments is carried out by "wet and" dry spinning methods in corrosion-resistant equipment. If acid acceptors are used in polycondensation, in which the salts of halogen-substituted hydrogens in the solvent used are completely or partially insoluble, the elastomer is either first needed with water to remove water-soluble salts, or

the solution must be filtered before molding. It is even possible to carry out polycondensation simultaneously with molding, for example, interfacial polycondensation. Dissolved elastomers for

the moldings are redissolved in suitable solvents. As solvents in the manufacture of solutions for the dry method of spinning, B — dimethylformamide, M, B — dimethylacetamide, tetrasi 1,1,2-trichloroethane and formic acid in a ratio of 60: 40 are achieved, and the spinning rate reaches 900 m / min

It is advisable that elastomeric structures, which are obtained from the reaction solution directly by dry spinning, should be treated with water to remove residual solvents, acid acceptors and their salts and halogenated hydrogen acids until their last insignificant amounts are removed. Water treatment is carried out at 0 ° C and 100 ° C, preferably at 60-90 ° C. It is recommended to start the treatment at room temperature and gradually increase the temperature of the water to the boiling point, and the water should be neutral. Water neutrality must be strictly controlled. On the other hand, exposure to oxygen and other oxidizing agents should be minimal.

It is advisable to make yarns with lower titers using the dry spinning method. Wet spinning is also used for yarns with high denier numbers. The best solvents for both cases are S, M-dimethylformamide and acetamide. The wet-strand yarns of elastomers are additionally treated with warm water.

New elastomers, like all soft nolymer, exhibit greater bonding ability than crystalline solid polymers, such as nylon 66. With appropriate work, this does not lead to any difficulties. If the bobbin is wound under tension, it is recommended that the thread be wound directly for bobbins handle a small amount of steam or cover with talcum powder.

The properties of the resulting elastomers satisfy the requirements of the practice, but can be improved or modified by stretching the films or filaments and subsequent fixing. Stretching occurs at the glass transition temperature of polymers or at a higher temperature, it is more expedient at temperatures from room temperature to 150 ° C. The most favorable effects of strength, initial modulus, stretch, drop, and so on are obtained if stretching is carried out 2-10 times, preferably 4-6 times, at room temperature and the filament or film is the conclusion is fixed under tension at 100-150 ° C for at least 1 hour, preferably several hours.

The proposed elastomers have better light resistance and oxidation resistance, which is expressed in improved yellowing resistance. Significantly increases resistance to flue gases compared to known plastics with other similar properties. In contrast to the well-known elastic plastics, which approach in their light resistance to the proposed elastomers, the latter have improved thermal stability combined with better solubility, which makes it possible to manufacture structures with improved initial properties, B particularly with excellent initial color.

The molecular weight of elastic plastics is advisable to choose as high as possible, the upper limit depends only on solubility.

Flexible plastics should have a viscosity of at least 0.5. Low viscosity products (0.5-1), due to their good flowability, are particularly suitable for the manufacture of elastic coatings from solutions, and in the form of solutions they are sprayed, washed or poured onto the substrate to be coated and, upon evaporation of the solvent, give adherent, highly elastic, colorless and non yellowing coatings. The elastic plastic coating can also be obtained by immersion. For all of these applications, the solubility of elastic plastics is an important criterion, especially the solubility in boiling relatively low-physiologically harmless and non-corrosive solvents, such as common ones, based on ketones, folded and growing esters.

For the manufacture of films and filaments, it is advisable to adopt elastic plastics with a higher (higher than 1) intrinsic viscosity, and elastic plastics with an inherent viscosity of 1.5-4 are mainly used for these purposes. Polymers with such high intrinsic viscosities provide films and filaments with a particularly low drop in patching and favorable softening temperatures. Other things being the same, the elementary threads are the more convenient for practical use, the smaller their patch fall and the higher softening temperature.

If, when used, elastic plastics often come into contact with aggressive media — hot water, acidic or basic fluids — then polymers are preferred that are formed from polyether bischloroformates. Among the and the latter, tri-, tetra-, penta-, and hexamethylyglycol, propylene glycol and neopentyl glycol or copolyesters of glycols with each other or with ethylene glycol are particularly desirable, with a molar ratio of at most 50% polyether. If elastic plastics are used, they are primarily exposed to air at high temperatures, especially during irradiation, polymers, which are formed from polyesters bischloroformates, are preferred. Among the latter, bischloroformates of co-hydroxycarboxylic acid maxi homopolymers or copolymers are desirable.

a kid with 12 carbon atoms and a minimum of 6 carbon atoms in the chain, with the carboxyl group included as poly-e-caprolactone, n complex polyesters from at least one aliphatic dicarboxylic acid with 6-12 carbon atoms, in which both carboxyl soils should be separated minimally 4 saturated carbon atoms, such as Adinov, 2,2,4 trimethyl adipic or sebacic acid, and glycol with 2-12 carbon atoms, in which both hydroxyl groups must be separated by at least two saturated carbon atoms, for example p ethylene glycol, propylene glycol, peopentyl glycol, 1,4-butanediol and 1,12-dodecapdiol.

Elastic plastics, which are made of blocked 2,4-dihydrazino-6-bis lower alkylamine-S-triazines of poly tri- or tetramethylene glycol bis-chloroformate with a mol., Have especially favorable mechanical properties. at. 1000--3000 and terephthalic acid dichloride. The optimum properties of the medium of these polymers are those in which the lower alkyl group of the applied S-triazine contains an unbranched chain of 2-4 carbon atoms, and a polytrimethylene or tetramethylene glycol bischloroformate has a mol. at. 1500-2500 and for the manufacture of which a triazine compound and bischloroformate are used in a molecular ratio from 2: 1 to 4: 3, preferably from 2: 1 to 7: 5, i.e., polymers in which n is 1-3, mostly 1-2,5.

In the examples illustrating the invention, without limiting it, all parts are by weight and are in the same ratio to volumetric parts as kilogram to liter.

Parameters characterizing the properties of elastic plastics.

Inherent viscosity g | (inh)

where c is the concentration of the polymer in g / 100 ml of solvent; TJOTH- is the quotient viscosity of the polymer solution with concentration c and pure solvent.

The intrinsic viscosities were determined at 25 ° C and a concentration of 0.5 g polymer / 100 ml. Of i-cresol.

The tensile strength (g / denier, respectively, kg / mm) refers to the cross section of filaments or films in a perast by the way.

Elongation at break (%) corresponds to an increase in the sample length to break, expressed as a percentage of the original length.

A fall in tension (%) means the percent loss of strain in a sample within a minute after it has been stretched by 50% at an elongation rate of 100% per minute.

Elastic elastic recovery (%) corresponds to the return to the original position, measured one minute after

The sample tension was increased, which lengthened at an elongation rate of 100% per minute by 50% and was maintained at this elongation for 1 minute. The calculation is made

according to the formula - -100,

LI where LO is the initial length;

LI - length after returning to the starting position.

0 Example 1. In a narrow bottle with a volume of 100 parts. A solution of 1.8 parts. 2,4-dihydrazino-6-dipropylamino-5-triazine in 40 vol. including triamide hexamethylphosphoric acid was diluted with 5.3 parts of polytetramethylene glycol bis5 chloroformate and the resulting mixture was unmixed. The reaction mixture is weakly heated and after half an hour at room temperature it is cooled to approx. It is diluted

 0.46 parts of adipic acid dichloride. The resulting mixture is shaken vigorously, and its viscosity is slightly heated for 1 minute. greatly increased. After a 15-minute exposure made so

 by polymerizat precipitated, pouring the reaction solution into water, washed repeatedly with water and dried in a vacuum substance at a pressure of 15 mm RT. Art. and 70 ° C overnight. Bela elastic plastic, having an intrinsic viscosity of 1.38, is easily dissolved in dimethylacetamide and spreads into films from a solution containing 25 g of the polymer in 75 ml of dimethylacetamide. After evaporation of the solvent in a vacuum base cabinet at 70 ° C for 16 hours, colorless transparent films are obtained, showing a drop in tension of 19%, as well as an elastic recovery of 95%.

 The bischloroformate used is prepared as follows. 8 parts of phosgene are condensed in a moisture-free freezer trap. 10 hours are introduced into liquid phosgene with good stirring and cooling to O-4 ° C during 4 hours. Polytetramethylene glycol with an average molecular weight of 960 and an OH number of 117. The reaction solution is stirred for 2 hours at O-5 ° C. after which the main amount of excess phosgene and the resulting hydrogen chloride is removed by many hours blowing dry nitrogen at room temperature.

The polytetramethylene glycol bischloroformate formed during the passage of a weak nitrogen stream is released in vacuum at 40 ° C from residues of phosgene and hydrogen chloride. It is a colorless, viscous liquid containing chlorine.

° 6.58%.

Such elastic plastics are obtained if, instead of 0.46 adipic acid dichloride, equimolar amounts of dicarboxylic dihalohydrohydrides are used the same. In tab. Figure 1 shows the inherent viscosity, elongation at break, and the elastic elastic recovery of the films of these plastics. Table 1

table 2

Example 2. In a narrow bottle with a volume of 100 hours, freed from water and cooled with nitrogen, 10.28 parts of polytetramethylene glycol bis-chloroformate with a chlorine content of 3.45 7o are mixed with a solution of 1.38 parts of 2,4-dihydrazino-6-dimethylamino - S-triazine in 40 vol. including dimethylacetamide. The resulting mixture is shaken vigorously, and with a noticeable heat, it becomes more viscous. After cooling to 5-10 ° C, the mixture is diluted with 0.508 parts of solid terephthalic acid dichloride and immediately shaken vigorously, and the acid chloride goes into solution. The resulting polymerizate is precipitated after approximately 15 minutes by pouring the highly viscous reaction solution into water with vigorous stirring, then washed several times with water and dried in a vacuum oven overnight at 70 ° C. It has a dryness of 1.58 and gives, if the treatment is carried out as in example 1, films with a drop in tension of 18% and an elastic elastic recovery of 94%.

Bis chloroformate is obtained by reacting polytetramethylene glycol with a molecular weight of 1930 with an excess amount of phosgene, as described in Example 1.

Such elastic plastics are obtained if, instead of 1.38 parts. 2,4-dihydrazino-6-dimethylamino-5-triazine, equimolar amounts of S-triazines from Table 1 are used. 2, the same conditions.

Polymer films. A, B, C, D, D, E, F and K after 40 hours of irradiation at the Xenotest exposure meter do not change colors at all, while the films of polymers 3, I and L are slightly yellowed.

Example 3. In a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, to a solution of 2.4 hours. 2,4-dihydrazino-6-diisopropylamino - S-triazine in 60 vol. including dimethylacetamide add at 5 ° C and good stirring a solution of 5.3 hours of polytetramethylene glycol bischloroformate with a chlorine content of 6.58%, manufactured according to example 1, and 10.28 hours of polytetramethylene glycol bischloroformate with a chlorine content of 3.45%, made according to example 2, in 20 about. including dimethylacetamide and washed with an additional small amount of dimethylacetamide. The resulting solution is heated to 12 ° C with an increase in viscosity and after 15 minutes while cooling with ice in the molded product, it is diluted with 1.015 parts of terephthalic acid dichloride. A clear, highly viscous solution is formed, which, without preliminary precipitation, is molded with films with an inner diameter of 1 mm into films, which are dried overnight in a vacuum oven at 70 ° C and a pressure of 15 mm Hg. Art. The films obtained, after being kept in water with a temperature of 50 ° C overnight and after re-drying, have a tension drop of 15% and an elastic elastic recovery of 97%. The newly dissolved film sample has an intrinsic viscosity of 1.73. If, instead of 1.015 parts of terephthalic acid dichloride, an equimolar amount of another chain extender is used, ceteris paribus, elastic plastics from Table 1 are obtained. 3. Table 3 Example 4. 7.2 parts of 2,4-dihydrazino-6-dipropylamino-3-triazine are dissolved in a three-neck flask equipped with mellak, thermometer and addition funnel in 80 vol. including dimethylacetamide. With good stirring, 41.12 parts of molten polytetramethylene glycol bischloroformate are added to this solution with a chlorine content of 3.45%, prepared according to Example 2, and washed with additional 5 vol. including dimethylacetamide. After half an hour, the reaction solution was cooled with an ice bath to 5-10 ° C and diluted with vigorous stirring 2.03 parts of terephthalic dichloride

Example 5. 2,44 hours 2,4-dihydrazino-6-dihexylamino-5-triazine in 30 vol. including dimethylacetamide are reacted as described in Example 3 with 5.50 parts of polypropylene glycol bischlormate with chlorine content of 6.43%. The resulting solution was diluted with 0.42 parts of hexamethylene diisocyanate dissolved in 10 vol. including dimethylacetamide, and there is no instant viscosity increase. After 16 hours at room temperature, the viscosity of the reaction solution increases markedly. The product is isolated, as described above, and is processed, its intrinsic viscosity is 1.195. The product gives, when casting from dimethyl sulfoxide, a film with a tension drop of 20% and elastic recovery 96% 5 10 15 20 25 30 35

Polypropylene glycol bischloroformate is obtained by reacting polypropylene glycol with an average molecular weight of 975 with an excess of phosgene at about -5 ° C and 4 hours of stirring at this temperature with subsequent removal of unconverted phosgene, as described in Example 1.

If, instead of 0.42 parts of hexamethylene diisocyanate, equimolar amounts are used

other chain extenders, ceteris paribus, are similar plastics, whose properties are listed in Table. five.

Example 6. 8.7 o'clock dihydrazide adipic acid condense, as described in

irimere 2, in about 400 including hexamoylphosphoramide with 51.2 parts prepared according to Example 2 with tetramethylene glycol bischloroforcid, which dissolves quickly. Within 10–20 seconds, the icing solution becomes highly viscous and after about 15 minutes, from the fast-rotating knife, the mixer is poured into a large excess of water, with the resulting colorless polymer being deposited in a finely distributed form. The precipitated product is washed several times with water and dried over 70 ° C in vacuum. The elastomer obtained in this way from a solution of dimethylacetamide, as in the examples given, is cast into films that have a drop of nat: 8% and an elastic elastic recovery of 98%. The sample of these films, dissolved in 1-cresol, has an inherent viscosity of 2.45. 25 parts of the described polymer are dissolved in 75 parts of dimethylacetamide and are spun in a conventional unit for a 25 day dry monofilament monofilament. These filaments have a tensile strength of 0.7–0.8 g / denier, an elongation at break of 700– 850%, a fall in tension l: ени 8–10%, and an elastic elastic recovery of 97–98%. By stretching these threads at room temperature, the elastic elastic recovery of filaments from 98 to 99% and tensile strength from 0.8 to 0.9 g / denier is improved 4-fold. If instead of 7.2 parts of the compound S-triazine and 41.12 parts of bischloroform. 4 quantities, ceteris paribus, are similar elastic plastics, whose properties are given in the same table. Table 4

17 Table 5 Miata with a chlorine content of 3.45% at room temperature. After half an hour, the reaction solution is cooled with an ice bath to 5-10 ° C and 5 parts of terephthalic acid dichloride are added with vigorous stirring. After approximately 15 minutes, the polymer formed is precipitated by pouring the reaction solution into water and processing, as described in the examples above. The polymer is insoluble in dimethylacetamide; on the contrary, it gives films with a dimethyl sulphoxide solution that has a drop of 12%, an elastic recovery recovery of 97%, a breaking strength of 3.3 kg / mm and an elongation at break of 800%. If, instead of 8.7 parts of adipic acid dihydrazide, equimolar amounts of dihydrazides are used from Table. 6 ceteris paribus, similar elastic plastics are obtained whose properties are indicated in the same table. Table 6 Example 7. 2.4 parts of 2,4-dihydrazino-6-dipropylamino-5-triazine are condensed, as described in Example 2, in 40 vol. including N-methylpyrrolidone with 4.75 parts of poly-e-caprolactone glycol bischloroformate and chain elongation with the aid of 1.01 parts of terephthalic acid dichloride.

18 The resulting flexible plastic has an inherent viscosity of 1.1 and provides highly elastic coatings from solutions of dimethylformamide, dimethylacetamide, dimethyl sulphoxide or N-methylpyrrolidone. The poly-e-caprolactone glycol bis-chloroformate used is prepared as follows. e-Cairolactam is polymerized with ethylene glycol as the starter of U.S. Patent No. 3186971. The resulting polyester having a molecular weight of 830, with two terminal hydroxyl groups, is converted according to Example 1 to the corresponding bischloroformate with a chlorine content of 7.48%. Example 8. In a double pan mixer with a total volume of 2800 hours, equipped with a cooling jacket, dissolve 16 parts of a 50% paste of titanium dioxide (such as rutile) in dimethyl acetamide in a solution of 57.6 parts of 2,4-dihydrazino- 6-dipropylamino-5-triazine and 0.6 parts of 2-2-diethylaminosulfonylstilbil- {4) -naphtho- () - 1,2,3-triazole. 2.6 parts of 1,3-di-7/7 (g-butyl-2-hydroxy-5- (2-octadecyloxycarbonylethyl) benzene and 2.6 parts of 2- (2oxy-3, 5-di-gr ( g-butylphenyl) -5-chlorobenzotrnazole is thoroughly dispersed in 500 parts by volume of dimethylacetamide .352 parts of polytetramethylene glycol bis-chloroformate with chlorine content of 3.28% and vessel are added to this dispersion in a rotating mixer for 10 min. with the addition, it is washed twice with 125 vol. of dimethylacetamide. During the addition, the reaction mixture is heated to 25 ° C and becomes more viscous. After the addition is completed, the reaction mixture is turned off m cooled for 10 minutes vigorously stirred, then cooled to 15 ° C and, finally, diluted with 16.3 hours of solid terephthalic acid dichloride with a rotating mixer for 3 minutes. With a slight heating at 25 ° C, a very strong increase occurs. the viscosity of the reaction mixture, which, for better homogenization, is intensively stirred by the remaining 15, "uncooled cooling 1.i. The resulting highly viscous elastomer solution can be directly spun by the usual dry or" wet method to filaments with good elastic properties. A sample of the reaction mixture, precipitated after diluting with dimethyl acetalgide and pouring into water, reveals c. - cresol and an intrinsic viscosity of 2.56. The required polytetramethylene glycol bischloroformate with a chlorine content of 3.28% is prepared, as described in Example 1, from a polytetramethyleglycol with a mol. at. 2080. Object of the Invention 1. A method for producing modified polyesters