NL7908160A - PROCESS FOR PREPARING ALFA, OMEGA-BISALKYL ESTER DERIVATIVES OF ALFA, ALFA-AZOBIS-ISOBUTIC ACID. - Google Patents

Description

* -1- 21019 / Vk / iv «" * * ·

Applicants: Anatoly Andreevich Syrov, Leningrad; Sergei Stepanovich Ivan-chev, Leningrad; Oleg Nikolaevich Primachenko, Leningrad;

Valentina Alexandrovna Demidova, Leningrad; Boris Vladimirovich Polozóv, Leningrad; Vladimir Ilich Fionov, Leningrad; 5 Evgeny Nikolaevich Barantsevich, Leningrad, USSR.

Short designation: Process for the preparation of,-is-bisalkyl ester derivatives of cc, d. Az-azobis-isobutyric acid.

The invention relates to a process for the preparation of derivatives of a1, k-azobis-isobutyric acid <JL, U-bisalkyl esters of formula 1, indicated on the formula sheet, wherein R has the meaning of formulas 2, 3 or 4 where n is 2-3 or of formulas 5 or 6, where n is 2-4 or of formula 7 or 8. The above derivatives are suitable as initiator for radical type polymerizations of ethylenically unsaturated compounds as well as for starting material for the preparation of highly active polymers.

A number of radical polymerization initiators are known. These can be represented by aliphatic azo compounds of formula 9, indicated on the formula sheet, which have been prepared by chlorinating 20 azines, ketones with molecular chlorine in the presence of acetic acid, as described by S. Goldschmidt, B. Achsteiner, J. Liebigs Ann. Chem.

1958, 61, 8, pp. 173-185 and by W. Bracke, J.A. Empen, and C.S. Marvel, Macromolecules, 1968, 1161, pp. 465-468.

Furthermore, as radical polymerization initiators, symmetrical aliphatic compounds of formula X (CH2) nCR1R2N = NCR ^ (CH2) are used, wherein X is Cl or Br, R1 and R2 are each an alkyl group with 1 or 2 carbon atoms and n is 0-5, as described in German Patent 2,546,377.

These compounds, when used as a radical polymer initiator of ethylenically unsaturated monomers, have a high thermal stability, which hinders the reaction, and often even prevents its use, especially when using reactive telechelate oligomers.

Furthermore, the above-mentioned compounds contain primary chloralkyl-35 groups with a low reactivity in the reaction involving polycondensation or polyquatemization, as described by E.N. Barantze-vich, N.K. Berseneva, A.E. Kalaus, T.S. Saburova in "Kauchuk i Rezina", 1976, no. 9, pp. 7-9, in "General Practicum in Organic Chemistry", MIR Publishing House, M., 1965, p. 318 and by B.N. Pronin, E.N. Barantze-40 vich, S.S. Ivanchev in "Vysokomolekularnyje Soedinenija", 1977, 19 (3), 790 8 1 60% -2- 21019 / Vk / iv biz. 455-548.

A free radical polymerization initiator is known from U.S. Pat. No. 4,088,642, namely 2- (tert-butylazo) -2-acetoxy-4-methyl-4- (tert-butyl-peroxy) pentane of formula 10, indicated on the formula-5 sheet. Due to its asymmetry during decomposition, this compound gives radicals of different chemical structure, making it impossible to use them as an initiator for the preparation of telechelate oligomers with identical functional groups.

Furthermore, a process is known for preparing d., CL '-bis-10 alkyl ester derivatives of ct, ct'-azo-bis-isobutyric acid of formula 11, indicated on the formula sheet, wherein R is C 1 -C 12 Cl, - ( These compounds are prepared by treating o (-, o'-azo-bis-isobutyric acid dinitrile and ethylene chlorohydrin or ethylene glycol or polyethylene glycol with hydrogen chloride in an organic dissolution medium, followed by.

Treating the resulting reaction mixture with water and separating the desired product by distilling off the solvent from the desired product, extracting or recrystallizing the desired product, as indicated in German Offenlegungsschrift 2,124,000.

These compounds contain, as reactive functional groups, 20 OC 2 CH 3 Cl or -OCH 4 Cf 2 OH, the use of which is limited to a small number of chemical reactions, in particular radical polymerizations, poly-quaternisations and polycondensations.

The nieufae compounds according to the invention, viz. The <x, (D-bis-alkyl ester derivatives of o, od'-azo-bis-isobutyric acid, have hitherto not been described in the literature. The process according to the invention is characterized herein » that C'-azo-bis-isobutyric acid dinS trile and a derivative of a monovalent alcohol with a saturated alkyl group of formula R OH, wherein R has the above meaning, are reacted with gaseous hydrogen chloride in an organic solvent medium in the presence of 0.5 to 5% by weight of a water-soluble ether, at a temperature of -5 ° C to 6 ° C, after which the reaction mixture is treated with water at a temperature of 0 to -5 ° C and the desired product is separated.

The present process is therefore aimed at the preparation of the new compounds, i.e. the derivatives of <RTI ID = 0.0>, cc'-azo-bisisobutyric acid-</RTI> io-bisalkyl esters, which make it possible to use this compound as starting material in reactions such as copoly condensations or copoly quaternisations or as an initiator in radical polymerizations of ethylenically unsaturated compounds, to obtain new high molecular weight substances with improved properties by using a simple 790 8 1 60 * -3-21019 / Vk / iv process whereby high molecular compounds are obtained with a high impact resistance, resistance to high and low temperatures, a gas impermeability and an increased dielectric property.

It is desirable to use benzene, pentane, diethyl ether or methylene chloride as the organic solvent.

In order to increase the yield of the desired product, it is recommended that the process of interacting the starting material be conducted in the presence of tetrahydrofuran, dioxane, trioxane, diethylene or triethylene glycol dimethylate.

The process for preparing derivatives of C 1-10 azo-bis-isobutyric acid 0.16-bis-alkyl esters is accomplished by using <*, <* '- azo-bis-isobutyric acid dinitrile and a monovalent alcohol with a saturated alkyl radical of the formula ROH, wherein R has the above meaning, is reacted with gaseous hydrochloric acid in an organic <15 solvent in the presence of 0.5 to 5% by weight water-soluble ether, followed by further treatment of the obtained reaction mixture with water.

To obtain a higher yield of the desired product, the organic solvent used is benzene, pentane, diethyl ether, and methylene-2-chloride, while the water-soluble ether uses tetrahydrofuran, dioxane, trioxane, diethylene glycol or triethylene glycol dimethylate.

The above-mentioned amount of the water-soluble ether is optimal at 0.5-5% by weight. The addition of the catalyst in an amount less than 0.5 wt% is inefficient, while above 5 wt% undesirable influences arise due to the associated catalyst separation and further use problems. As a result of the above-mentioned reaction, the nitrile group of .alpha.-azo-bis-isobutyric acid dinitrile is converted to an ester group. Generally, the synthesis of the derivatives of ^,,,,, az-azo-bis-isobutyric acid, &, - bis-alkyl esters is accomplished according to scheme 12, indicated on the formula sheet, where R is as defined above.

The action of the gaseous hydrochloric acid on the starting materials is effected at a temperature between -5 ° C and + 6 ° C. The subsequent treatment of the resulting reaction mixture with water is carried out at a temperature between 0 ° C and -5 ° C.

In order to increase the yield of the desired product, the starting materials are used in the following amounts by weight with respect to organic solvent or gaseous hydrogen chloride or water, namely 40 resp. 1: 3 to 20.

7908160 1 ^ - -4- 21019 / Vk / iv

After the completion of the operation, the resulting reaction mass is treated with water at a temperature between 0 and -5 ° C. Without this water treatment of the reaction mass, it is impossible to ensure that the desired products are formed and can be separated.

Recovery of the derivatives of oc, azobis isobutyric acid in the form of bis bis alkyl esters can be accomplished by any known technique. Thus, recovery of the products obtained from the cooled reaction mass can be accomplished by separating the aqueous phase with the water-soluble ether and hydrochloric acid from the solvent with the desired product, residual amounts of the unreacted compounds and hydrochloric acid. Then the solvent is washed with a 5% solution of sodium bicarbonate and water to obtain the negative reaction to chlorine ions. The solution is then dried with anhydrous sodium sulfate and distilled off under reduced pressure to obtain the desired end product. To ensure additional purification of the desired product to separate the impurities, it is possible to recrystallize from a mixture of petroleum ether, diethyl ether or through the mixture. 20 to run a chromatographic column using aluminum oxide as an absorbent.

The product thus obtained was a pale yellow liquid or white crystalline prism-like solid components with a specific odor.

The temperature at which the half-life with respect to the decomposition of the azo and peroxy group in the compound according to the invention for 10 hours is equal to 70 ° C and 130 ° C, respectively.

The structure of the products obtained is confirmed by various physico-chemical analyzes.

. The IR spectrum has been obtained in a thin layer of CCl 4 using an UR-10 instrument ("Karl Zeiss", GDR) with the range -1 being between 800 and 1800 cm.

The UV spectra are recorded in ethylbenzene using CF-8 equipment manufactured by "LOMOi" enterprise, Leningrad, USSR, taken at 365 nm.

35 The PMR spectra were recorded using an i'Perkin

Elmer "(USA) instrument at 80 MHz relative to the internal reference standard hexamethyldisiloxane. Molecular weight is determined cryoscopically in dioxane or benzene by measuring the thermal condensation effects (MTEC method).

40 The thin layer chromatography performed with the obtained 790 8 1 60 f -5-21019 / Vk / iv compounds is accomplished using nSilusol ”plates with a silica layer applied to an aluminum substrate prepared by" Kavalier ", Czechoslovakia, Als eluent is used a mixture of toluene, hexane, methanol and acetic acid used in a volumetric ratio of 12: 5: 2: 1, respectively.

The peroxy compounds are developed by spraying plates after immersing the solution of the compounds to be tested and eluting with a 2% aqueous solution of HJ, followed by heating the plates at a temperature of 70 ° C for 10 minutes .

The derivatives of o ', oc'-azo-bis-isobutyric acid c (., Q-bis-alkyl ester thus prepared) are suitable as initiator in radical polymerizations of ethylenically unsaturated compounds as well as for starting material in the preparation of new hitherto unknown reactive polymers with improved properties such as improved impact strength, resistance to low and high temperatures, high dielectric properties and oligomers with reactive functional groups.

Furthermore, the method according to the invention for preparing the. van-ob-azobis-isobutyric acid, D, G) -bis-alkyl ester derivatives a single step and simple process because inexpensive and readily available products can be used as starting materials. The invention is further illustrated by the following non-limiting examples.

Example I

In a reaction vessel with a gas supply tube, 5 g (0.0305 mol) <*, * '- azobis isobutyric acid dinitrile, 20 g (0.149 mol) / 3-hydroxyethyl tert-butyl peroxide, 0.5 ml (1.8 wt. % of the total mass of the reagents) over calcium hydride distilled tetrahydrofuran and dried chlorine-hydrogen is passed through the resulting suspension at a temperature of 0 ° C and in an amount of 1 1 per hour for 5 hours until complete solution has oC, oL'-azo-bis-isobutyric acid dinitrile. The resulting reaction mixture is then stored in a refrigerator at a temperature of + 6 ° C for 20 hours. It is then treated with 100 ml of ice-cold water for 2 hours at a temperature of 0 ° C with strong stirring. After the obtained reaction mass is divided into two layers, the oily phase containing the desired product, the residual amounts of starting material and hydrochloric acid are separated from water and washed with 150-200 ml of a 5% solution of sodium bicarbonate and water until no chlorine ions are present. and then dried over anhydrous sodium sulfate. The solution containing the desired product is passed through a column of aluminum oxide with 790 8 1 60 -6- 21019 / UK / IV to remove impurities. The solvent is distilled off from the desired product under reduced pressure at a temperature of 0.01 mm of mercury.

There is thus obtained 8 g (61% of the theoretical amount) of pale yellow g of product which, after analysis, appears to correspond to oL, ύ-bis (tert-butylperoxyethyl) ester of oC'-azo-bis-isobutyric acid.

The data for the physico-cheraic analyzes are as follows: elemental analysis for C20 ^ 33 ° 8 ^ 2 * 10 C (%) H (%) N {%) found 56.1 9.0 6.6 calculated 55.30 8.76 6.45 3 3

Gas number: found 52 cm / g; calculated 52 cm / g.

In the IR spectrum (CCl, thin layer), an absorption band with a frequency = = 1,740 cm ^ was observed, which corresponds to a C = 0 bond.

In the UV spectrum (ethylbenzene), a maximum in the absorption band is observed at a wavelength m mxx = 365 nm and a coefficient £20 = 26 corresponding to the N = N bond.

In the PMR spectrum, lines with a phemic shift b - 1.16 ppm, 1.38 ppm, 4.0 ppm, 4.22 ppm are observed with respect to hexamethyldisiloxane corresponding to the respective groups O-CiCH ^) ^ Nc-ch3l o-ch2-ch2-o.

A thin layer chromatogram of the desired product obtained is obtained on a "Silusol" plate prepared by l'Kavalier ", a company in Czechoslovakia. As eluent, a mixture consisting of toluene, hexane, methanol, acetic acid in a volumetric ratio of 12: 5: 2: 1 respectively A developer (2% aqueous 20 ° pl ° ssinS of HJj after heating the plate to a temperature of 70 ° C

a blue spot with a dissolution factor Rf = 0.60 for 5 minutes.

20

Refractive index nn = 1.4410 on υ 7

Density d ^ u = 1.014 g / cirr

Example II

2g In a reaction vessel equipped with a bubble tube and a stirrer, 5 g (0.0305 mol) of α, ^-azo-bis-isobutyric acid dinitrile, 8.17 g (0.0610 mol) of β-hydroxyethyl tert-butyl peroxide, 0.1 g 15 ml (0.5 wt.%) Of tetrahydrofuranf distilled over calcium hydride and 20 ml of benzene distilled over sodium. Dry gaseous hydrochloric acid was passed through the resulting slurry 40 in an amount of 1 L per hour for 4 hours at a temperature of + 7 ° 2/019 / Vk / iv of + 6 ° C to a complete solution of d, ai '. -azo-bis-isobcter acid dinitrile was obtained. Then, the resulting reaction mixture was stored in a refrigerator for 18 hours at a temperature of + 6 ° C. The reaction mixture was then mixed with 100 ml of ice-cold water for 2 hours under strong stirring at a temperature of 5-5 ° C. A further separation of the product was effected in the manner as indicated in Example 1. Thus 7 795 g (60.1% of the theoretical amount) of o, u-bis (tert-butylperoxyethyl) ester of <*>, Azobis isobutyric acid obtained with the same physicochemical properties as indicated in Example 1. The compound obtained is suitable as an initiator for the polymerization of butadiene and is obtained in the manner described below.

_3

In a 150 ml glass ampoule, 2.6 g (6.0 x 10 mol) of bis (tert-butylperoxyethyl ester of dazo-bis-isobutyric acid, 40 ml of acetone and 30 ml of butadiene were added and the mixture was stirred for Maintained for 20 hours at a temperature of 70 ° C. After the completion of the polymerization, the unreacted monomer was vented as gas and the oligobutadiene formed was washed four times with an aqueous acetone mixture (1: 1 parts by volume) to give the remaining amount of initiator and to completely remove the decomposition products Oligobutadiene was dried at a temperature between 70 and 80 ° C under a residual pressure of 2 to 5 mm of mercury to obtain 5.8 g of oligobutadiene The yield is equal to 30% of the theoretical amount The molecular weight was 2600.

Example III

The procedure as described in Example II was carried out with the exception that 25 ml of diethyl ether were used as solvent and 1.5 ml (5% by weight) of dioxane were used as catalyst.

The reaction temperature was -5 ° C. Thus, 10.45 g (79% of the theoretical value) of al, Ca-bis (tert-butylperoxyethyl Jester of C, <* 4-azo-bis-isobutyric acid with the same physical chemical properties as indicated in example was obtained in Example I.

Example IV

The procedure as described in Example II was repeated with the exception that 20 ml of methylene chloride were used as solvent and 1.2 ml (3% by weight) of dioxane as catalyst. The reaction temperature was 0 ° C. Thus, 8.60 g (65.1% of theory) of oC, 4J-bis (tert-butylperoxyethyl) ester of d, oc1-azo-bis-isobutyric acid was obtained with the same physicochemical properties as indicated in Example 40 I.

790 8 1 60 * -8- 21019 / Vk / iv

Example V

The procedure as described in Example II was repeated, with the difference that * 0.2 ml (0.6% by weight) of dimethyl ether of ethylene glycol was used as the catalyst. Thus, 10.1 g (76% of the theoretic amount) of el, Go-bis (tert-butylperoxyethyl) ester of i10'-azo-bis-isobutyric acid were obtained with the same physicochemical properties as indicated is in Example I.

Example VI

The procedure as in Example II was repeated except that 15 g (0.112 mole) of β-hydroxyethyl tert-butyl peroxide were used. Thus, 8.03 g (60.7% of the theoretical amount) of?,--Bis (tert-butylperoxyethyl) ester of d, d1-azo-bis-isobutyric acid was obtained with the same physicochemical properties as indicated in example I.

Example VII

The procedure indicated in Example II was repeated, except that 20 ml of diethyl ether were used as solvent and 0.3 ml (1% by weight) of trioxane as catalyst. The reaction temperature was 0 ° C. Thus, 9.4 g (71% of the theoretical amount) of io-bis (tert; 20-butylperoxyethyl) ester of <X, ot'-azo-bis-isobutyric acid having the same physicochemical properties as indicated in example I.

The compound obtained is suitable as a starting material for the preparation of reactive polymers which can be obtained by the method mentioned below.

In an ampoule, 1.05 g (2.4 x 10 mol) οί, 6J-bis (tert-butylperoxyethyl) ester of oi, oc'azo-isobutyric acid, 10 g of methyl methacrylate and 0.01 g tetramethylene pentamine done. The oxygen dissolved in the monomer was removed under reduced pressure.

The ampoule was kept at a temperature of 25 ° C using a thermostat. After 24 hours, the conversion rate from methyl methacrylate to polymer was 90%. The presence of the azo group in the backbone was evidenced by the ability of the resulting product to initiate the radical polymerization of styrene with the formation of block copolymers of the ABA type. To this end, the product thus obtained was dissolved in 20 g of styrene and heated to a temperature of 60 ° C for 24 hours. The polymer formed was dissolved in benzene and reprecipitated in ethanol. The presence of the block copolymer was demonstrated by the fact that a 40% solution of the final product in chloroform was not stratified over a period of 13 days while a mixture of a 14% solution of polystyrene and polymethyl methacrylate 790 8 1 60 µg 21019 / Vk / iv are incorporated in chloroform in a ratio of 1: 1 and prepared under the same conditions and are layered within 15 minutes.

Example VIII

The procedure indicated in Example II was repeated with the exception that 20 ml of methylene chloride was used as solvent and 0.15 ml (0.5% by weight) of diethylene glycol dimethylate as catalyst. The reaction temperature is -5 ° C. Thus, 9,55 g (68.3% of theory) of t, U-bis (tert-butylperoxyethyl) ester of o (. Cd * -azobis-isobutyric acid) was obtained with the same physicochemical properties as indicated in example I.

Example IX

The process was carried out in the same manner as in Example 2, except that 1.1 g (3% by weight) of triethylene glycol dimethylate were used as the catalyst. Thus, 8.9 g (67% of theory) of ot, fo-bis (tert-butylperoxyethyl) ester of ¢ (., .L * -azo-bis-isobutyric acid with the same physicochemical properties as indicated in example I.

The resulting compound is suitable as an initiator of a radial polymerization of styrene accomplished by carrying out the method indicated below.

-A

To this end, 100 ml of styrene with 5.10 mol of egg, ÉD-bis (tert-butylperoxyethyl) ester of «, οί'azo-isobutyric acid was heated to a temperature of 70 ° C and kept at this temperature until the desired product was formed. . The polymerization rate was controlled to increase the density of the reaction mass, thereby demonstrating polystyrene formation.

-A

At a conversion of 5%, the polymerization rate was 1.1 x 10

-A

mol / liter and at the 10% conversion, the polymerization was 1.0 x 10 mol / l.

For comparison, the polymerization rate was determined in the absence of the initiator at conversion values of 5 and 10%, and was found to be A, 5 x 10 mol / l.

Example X.

The procedure was carried out as described in Example II except that hydroxyalkyl tert-butyl peroxide was using JT-hydroxy-propyl tert-butyl tert-butyl peroxide. Thus, 12.6 g (90% by weight of the theoretical amount) of oi. (O bis (tert-butylperoxypropyl) ester of QL, OC-azo-bis-isobutyric acid. This compound is a yellow liquid. The physicochemical properties of the compound are as follows.

A0 _ 790 8 1 60 4 -10- 21019 / Vk / iv

• Basic analysis data for 0sbF «W

0 «) H (*) H (%) found 57 * 10 9» 01 6.08 · 5 calculated 57.14 9 »09 6.06

In the IR spectrum (CCl, thin layer), an absorption band was observed with a frequency of P = 1.470 cm -1, corresponding to a bond C = 0. In the UV spectrum (ethylbenzene), a maximum of 10 of the absorption band at a wavelength λ max = 465 nm corresponding to a bond N = N and a coefficient 26.

The cryoscopic molecular weight (benzene) found was 467 and its calculated value is 462.

Example XI

The procedure as described in Example II was repeated, except that 6-hydroxybutyltert-butylperoxide is used as hydroxyalkyl tert-butyl peroxide.

14.2 g (95% of the theoretical amount) of 6,6-bis- (tert-butylperoxybutyl ester of 0.10U-azo-bis-isobutyric acid were obtained.

The product consists of a pale yellow liquid. The compound has the following physicochemical properties.

The data related to the elemental analysis for ^ 24H46 ° 8 ^ 2 are: C (%) H (%) N (%) 25 found 58.81 9.30 5.80 calculated 58.78 9.39 5.71

In the IR spectrum (CC1, thin layer), an absorption band was observed at a frequency of 1740 cm, which corresponds to a 30 C = O bond.

In the UV spectrum (ethylbenzene), the absorption band was observed which had a maximum at a wavelength λ max = 365 nm, corresponding to the bond N = N and coefficient £ = 26.

The cryoscopic determination of the molecular weight (in dioxane) was 495 while the calculated value was 490.

The compound obtained is suitable as an initiator of the radical polymerization in the polymerization of butadiene obtained by carrying out the process as described in Example II, except that instead of oi-bis (tert-butylperoxybutyl) ester of <*, < * * -azo-bis-iso-40 butyric acid as initiator for the polymerization use was made of 79O8160 -11-21019 / Vk / iv 2.94 g (6.0 x 10 mol) egg, (J-bis (tert. butylperoxybutyl) ester of cL, 0'-azo-bis-isobutyric acid, thus obtaining 5.9 g of oligobutadiene, yield equal to 30% of theory.

Example XII

This procedure was carried out in the same manner as in Example II, except that the hydroxyalkyl tert-butyl peroxide used was k-hydroxyisopropyl tert-butyl peroxide, which was used in an amount of 15 g (0.101 mol). Thus, 12.1 g (87% of the theoretical amount) of * U-bis (tert-butylperoxy-et- (methyl) / ethyl) ester of ((α'-azo-bis-isobutyric acid) were obtained. compound was obtained in the form of a pale yellow liquid The product obtained had the following properties.

The data from the elemental analysis for C22 ^ 42 * ^ 8 ^ 2 are: C (%) H (%) N (%) 15 found 57.20 9.09 6.05 calculated 57.14 9.09 6, 06

The IR and UV spectra contain characteristic absorption bands corresponding to the functional groups identical to those indicated in Example 1. The cryoscope molecular weight in dioxane was found to be 469 while the calculated value is 462.

Example XIII

This procedure was carried out in the same manner as in Example II, except that hydroxyalkyl terbutyl peroxide was used with hydroxy-.alpha. X bis (methyl ethyl terbutyl peroxide). Thus, 13.3 g (89% of the theoretical amount) of od, 4) -bis (tert-butylperoxy-c (, Od '-bis (methyl) ethyl) ester of d, 0L' -azo-bis-isobutyric acid. This compound consisted of a pale yellow liquid The product had the following physicochemical properties.

30 The data from the elemental analysis for C24H46 ° 8N2 are! 0 (») H («) »(*) found 58.80 9.33 5.69 calculated 58.78 9.39 5.71

The intrinsic absorption bands characteristic of the functional groups of the obtained compound are identical to the bands found for the compound described in Example I.

The crystallized molecular weight in benzene was 493 while the calculated value is 490.

The compound thus obtained is suitable as an initiator for a radical polymerization of butadiene obtained in Example 2, except 7908160 -12-21019 / Vk / iv 4 which, instead of od, 1 *) - bis (tert-butyl-peroxyethyl Jester) of <RTI ID = 0.0> q-</RTI> azo-bis-iso] oteric acid as an initiator for the polymerization of butadiene was used. q was used from 2.94 g (6.0 x 10 mol) of d. CO-bis (tert. butylperoxy) oi, oc> -bis (methyl) ethyl) ester of <* -, <* · »-azo-bis-isobutyric acid. Thus, 5.8 g of oligobutadiene was obtained. The yield is equal to 30% of the theoretical amount.

Example XIV

A bubble tube was placed in a reaction vessel, to which was added 5 g (0.0305 mol) octai-azo-bis-isobutyric acid dinitrile, 11.37 g (0.061 mol), mono-n- (chloromethyl) phenylate of ethylene glycol, 0 .5 g (2.96% by weight of the total reagents) of anhydrous tetrahydrofuran and 150 g of anhydrous benzene. Dry hydrogen chloride was fed through the bubble tube at a rate of 1 L per hour for 5 hours, after which the reaction mixture was stored in a refrigerator for 18 hours at a temperature of + 6 ° C and then stirred vigorously at a temperature of -2 ° C with 100 ml of ice cold water for 2 hours. After the reaction mixture was layered, the oily phase was separated from the aqueous phase. The oily phase contained the desired products, residual amounts of starting materials and hydrochloric acid. It was washed with a 5% -. " 2o aqueous solution of sodium bicarbonate (150-200 ml) and water (100 ml) until no more chlorine ion could be detected and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure of 20-30 mm of mercury and 0.01 mm of mercury and the residue was recrystallized from a mixture of diethyl ether and petroleum ether. The product had the following physicochemical properties.

The data related to the elemental analysis for C26H32N2C12 ° 6 are! C (%) H (%) N (%) Cl (%) 30 found 57.80 6.01 5.03 13.20 calculated 57.88 5.94 5.19 13.17 q

The amount of gas (cm / g) was found to be 41.5 while the calculated value is 41.5.

The crystallized molecular weight in dioxane was 539 while the calculated value was 539.

The ester number (mg KOH / g) was 205 while the calculated value was • 208.

An absorption band was observed in the IR spectrum (CC1, thin layer).

* "* 1 names with a frequency i = 1745 cm", which corresponds to a binding 40 C = 0, a frequency V = 1680 cm ", which corresponds to a 7908150 -13-21019 / Vk / iv aromatic ring, ^ = 820 cm-1, corresponding to the bond C-Cl, ^ = 1040 cm (ROAr), Ί = 1568 cm ”, corresponding to the bond -N = N-.

In the UV spectrum (ethylbenzene) an absorption band has been observed with a maximum at a wavelength X = 365 nm, corresponding to the bond -N = N- and coefficient £ = 26. According to these data, the product corresponds to formula cL, U-bis- ((o) -p- (chloromethyl) phenylOxyethylene ester of o (.cabazo-bis-isobutyric acid).

The desired product obtained is suitable as an initiator for a radical polymerization of styrene and as a starting material in the preparation of reactive polymers.

Listed below is the use of CL, J-bis - (<i) -p- (chloromethyl) phenyl) oxyethylene ester of eL, o'-azo-bis-isobutyric acid in the polymerization of styrene, which polymerization on the following way is accomplished.

Under anaerobic conditions, 100 ml of styrene was heated with 5.10 mole of d. G) -bis (£-(p-chloromethyl) phenyl) oxyethylene ester of t ((azo-bis-isobutyric acid) to temperature of 85 ° C and held at this temperature for several hours The polymerization rate was controlled by increasing the density of the reaction mass, which was indicative of polystyrene formation.

The polymerization rate under these conditions at a conversion of 5% was 9.7 x 10 mol / l, at a conversion of 10% the rate was 9.2 x 10 mol / l. The polymerization rate of styrene in the absence of the initiator at a conversion of the values of 5 and 10% was equal to 0.92 x 10 mol / l.

Preparation of reactive polydivinyl with an azo group in the polymer chain was accomplished as follows.

To a solution of 100 ml of o ', O-bis (lithium) oligodivinyl with a molecular weight of 1000 in 450 ml of toluene at a temperature of 25 ° C was added a solution of a stoichiometric amount of oC, 4) bis- (6J -p (chloromethyl) phenyl) oxyethylene ester of CC, L L '-azo-bis-isobutyric acid in toluene (150 ml) and the mixture was stirred for 2 hours. The formation of reactive polydivinyl was determined by increasing the intrinsic viscosity of polydivinyl at a temperature of 35 ° C in toluene from 1.73 to 3.22 dl / g and by the formation of lithium chloride precipitate.

Example XV

The synthesis was carried out as described in Example XIV, except that as derivative of the monovalent saturated alkyl alcohol use was made of n-chloromethylphenol and as solvent n-pentane 790 8 1 60 i -14-21019 / Vk / iv while when water-soluble ether dioxane was used.

The compound thus prepared had the following physicochemical properties:

The data for the elearning analysis for the compound 5 C22H24C12N2 ° 4 are: C (%) H (%) N (%) Cl (%) found 58.23 5.40 6.11 15.91 calculated 58.84 5 , 32 6.21 15.74 3

Gas number (cm / g) is 49.2 while the calculated value is 49.6.

The cryoscope molecular weight determined in benzene was 449 while the calculated value was 451.

The ester number (mg KOH / g) was 247 while the calculated value was 249.

In the IR spectrum (CCl ^, thin layer), an absorption band was observed at the frequency ^ = 1765 cm "1, corresponding to the bond C = 0, f = 1680 cm" 1, corresponding to the aromatic ring, ^ = 820 cm-1, corresponding to the bond C-Cl, Ί = 1568 cm-1, corresponding to the bond -N = N-.

In the UV spectrum (ethylbenzene), an absorption band maximum at a wavelength λ = 365 nm was observed, correspondingly

nicLX

with the bond -N = N- and with coefficient £ s 26.

The product obtained on the basis of these data was Ü-bis- (n- (chloromethyl) -phenyl) ester of -azo-bis-isobutyric acid. The desired product was obtained in an amount of 65% of the theoretical quantity..

Example XVI

The synthesis was carried out in the same manner as in Example XIV, except that as derivative of an alkyl monovalent saturated alcohol, iD-1- (chloromethyl) phenyl] ethanol was used and diethyl ether was used as solvent while as in water soluble ether using diethylene glycol diethylate. The compound thus prepared had the following properties:

The data from the elemental analysis for compound C26H32N2 ° 4Cl2 are: 35 C (%) H (%) N (%) Cl (%) found 61.25 6.70 5.40 14.30 calculated 61.54 6.31 5.52 14.00 3

The gas number (cm / g) was 43.8, while the calculated value was 44.0.

40 The cryoscope determined molecular weight (dixoan) was found to be 502 7908150 -15-21019 / Vk / iv while the calculated value was 507.

The ester number (rag KOH / g) was found to be 225 while the calculated value was 221.

In the IR spectrum (CC1, thin layer), an absorption band was observed at a frequency of 1740 cm, corresponding to the C = O bond, 1 = 1680 cm, corresponding to the aromatic ring, V = 820 cm- ^ corresponding to the bond C-Cl, ^ = 1568 cnT1, corresponding to the bond -N = N—

In the UV spectrum (ethylbenzene) an absorption band was observed which was maximum at a wavelength λ = 365 run, corresponding to max the bond -N = N- and coefficient £ s 26. These data allow to Assume that the product corresponded to the formula [i], 6J-bis- ([p-chloromethyl) phenyl] ethyl] ester of .alpha.-azo-bis-isobutyric acid.

The resulting compound was suitable as an initiator for a radial polymerization of divinyl, which was accomplished in the following manner.

Divinyl and ot, Co-bis- (n-chloromethyl) phenyl (ethyl) ester of o, oc'-azo-bis-isobutyric acid were dissolved in carefully dried dioxane. The solution was deoxygenated and then brought to a temperature of 65 ° C using a thermostat.

Further data regarding the reaction conditions and the final product are shown in Table A.

Table A

25 experiment monomer initiator time yield molecular concentration concentration luren) (wt%) weight _ (mol / 1) _ (mol / 1) _ 1 5 3 70 30 2,500 2 10 3 70 30 3,900 30_

The product was recovered by removing the residual amounts of monomer and initiator by degassing and precipitation. The presence of chlorine in the oligomer was determined by a qualitative determination of chlorine by the Folghardt method.

The resulting oligomers of divinyl with p- (chloromethyl) -phenyl groups were used for the preparation of reactive polymers. To this end, the oligodivinyl in an amount of 100 mg was dissolved in 450 ml of toluene. The solution was mixed with an equimolar amount of N, N'-40 (dimethyl) hexamethylene diaraine, at a temperature of 20 ° C. One hour 790 8 1 60 -16-21019 / Vk / iv later, the viscosity of the solution was found to be increased from 1.7 to 4.5 dl / g. For comparison, CEL 1 -3 CICHpCHpO (0) C-C terminal oligodivinyl was used under the same conditions where after

<L c> I

CH3 no reaction took place with N, N '- (dimethyl) -hexamethylenediamine because the viscosity of the resulting solution varied from 1.6 to 2.0 dl / g.

Example XVII

The synthesis was carried out as indicated in Example XIV, except that JJ- (p- (chloromethyl) phenyl) propanol was used as the hydroxyl-containing compound and methylene chloride was used as the solvent.

The product obtained had the following physical-chemical properties.

Data from the elemental analysis for the compound of formula C28H36N2 ° 4C1 has been * n: C (%) H (%) N (7.) Cl (%) found 62.0 6.80 4.95 13 , 50 20 calculated 62.80 6.73 5.23 13.27 2

The gas number (cm / g) was found to be 45.8 while the calculated value is 46.0.

The molecular weight of the cryoscope determined in dioxane was found to be 530 while the calculated value was 532.

The ester number (mg KOH / g) was found to be 208 while the calculated value was 210.-

In the IR spectrum (CCl ^, thin layer), an absorption band was observed at a frequency l) = 1740 cm - **, corresponding to the C = 0 bond,] | = 1680 cm - "*, corresponding to the aromatic ring, Ü = 820 -1 η _i 30 cm, corresponding to the bond C-Cl, V = 1568 cm, corresponding to the bond -N = N—.

In the UV spectrum (ethylbenzene), an absorption band was maximal at a wavelength% = 365 nm, corresponding to the bond -N = N- and a coefficient of t = 26.

According to these data, the product had formula OL, O-bis (U- - tp-chloromethyl) phenyl] propyl ester of &quot; -azo-bis-isobutyric acid.

The yield of the desired product was 89% of the theoretical amount.

Example XVIII

The synthesis was accomplished as indicated in Example XIV

790 8 1 60 -17- 21019 / Vk / iv except that the hydroxyl-containing compound used was Ο - (φ— (chloromethyl) benzoate) ethanol.

The obtained compound had the following physicochemical properties: 5 The elemental analysis data for compound C28H32C12N2 ° 8 are found: C (%) H (%) N (%) Cl (%) found 56, 50 5.50 4.60 12.10 calculated 56.47 5.38 4.71 11.93 o 10 Gas number (cm / g) was found to be 37.8 while the calculated value was 37.6.

The cryoscope determined molecular weight (dixoan) was found to be 590 while the calculated value was 595.

The ester number (mg KOH / g) was found to be 372 while the calculated value was 376.

In the IR spectrum (CC1., Thin layer), an absorption band where

* * A

taken at the frequency V = 1740 cm ", corresponding to the bond C = 0, \) s 1680 cm" 1, corresponding to the aromatic ring, \) = 820 cm-1, corresponding to the bond C-Cl, V = 1568 cm -1, corresponding to the bond -N = N-.

In the UV spectrum (ethylbenzene) an absorption band was observed which was maximum at the wavelength \ 365 nm, corresponding max with the bond -N = N- and coefficient = = 26. According to these data, the product obtained corresponded to formula ü bis - (& - p- (chloromethyl) benzoate) ethyl esters of ol, o-azo-bis-isobutyric acid.

- CONCLUSIONS - 790 8 1 60

Claims (3)

A process for the preparation of derivatives of or, c1'-azo-bis-isobutyric acid o, bis-alkyl ester of formula 1, indicated on the formula-5 sheet, wherein R has the meaning of formulas 2, 3 or 4 where n = 2-3 or of the formulas 5 or 6 where n = 2-4 or of the formula 7 or 8, characterized in that o,, c <- azo-bis-isobutyric acid dinitrile and a derivative of a monovalent alcohol with a saturated alkyl group of formula ROH, where R is as defined above, are reacted with gaseous hydrogen chloride in an organic solvent medium in the presence of 0.5 to 5% by weight of a water-soluble ether at a temperature from -5 ° C to + 6 ° C, after which the reaction mixture is treated with water at a temperature of 0 to -5 ° C and the desired product is separated. 2. Process according to claim 1, characterized in that the organic solvent used is benzene, pentane, diethyl ether, or methylene chloride. 3. Process according to claim 1, characterized in that as water-soluble ether use is made of tetrahydrofuran, dioxane, triox-20-on, diethylene glycol or triethylene glycol dimethylate. 7908160 -19- 21019 / Vk / iv -FORMULA SHEET- CH, CH, 1. I * I 3 R - 0 - (O) G - C -IT sH - 0 - 0 (0) - 0 - RII ch3 ch3 S010¾ - 0 - * 010 ^ 0 - 0 - 0¾¾ - * 010¾ - 0- «®,) n - * 010¾. 0 - C (0) - 0-0¾¾. L. (ch3) 3 - C - 0 - 0 - (0¾ ^ - "* CH, - C - 0 - 0 - CH - CH - CH ~ - 3 (2 CH, 3 * CH, RR * I 3 5. II (CH,), -CQOC-CH, - C1-CN = HC-C1 * 2 (1 CH3 EE CH3 0¾ μ. II 3 (CH,), -CH = NC- CH0 - C- 0-0-C - (CH,), 33 f ώ I 'C = 0 CH, 6 5 CH, 3 „CH, CH7 1. i 5 i 2 RCH2CH20 (0) C - G- N = HC - C (0) 0CH2CH2R CII3 CH3 7908160 rt '-20 - 21019 / Vk / iv - SHEET (continued) - 53¾ 2HC1 / 2H ^ 0 HC - 0 - N = 3ü - C - CJST + 2R0H - II CHX CH, 5 50H, CH, I 3 | ^ R0 (0) C G-IT = NG - C (0) 0R II cI3 0H3 7908160