SU1526283A1 - Copper corrosion inhibitor and method of its production - Google Patents

Description

The invention relates to the protection of copper from corrosion in neutral and alkaline solutions and can be used in the production process and during storage of copper wire and other copper products.

The purpose of the invention is to increase efficiency in an aqueous medium at pH = 7-11.

Example 1. An oxidation inhibitor of honey is obtained in a batch laboratory apparatus, which is a thermostatic glass vessel with a capacity of 1 liter, equipped with a stirrer, thermometer, Dean-Stark nozzle, a refrigerator with a gas supply tube for supplying inert gas (nitrogen) to the upper part of the reaction vessel, with a vacuum line .

The condensation of aliphatic acids or their methyl esters with amines is carried out in accordance with the following process conditions.

To a mixture of amines containing 84 g (70 wt.%) Of ethylenediamine (EDA) and 52 g (30 wt.%) * Piperazine (PP), 34 g of water are added and mixed for 5 minutes. K'170 g (2 mol) of a 25% aqueous solution of the obtained mixture of EDA with PP with an average mol.m. 68 add 212 g (1 mol based on the average mol.m.) of synthetic fatty acids (FFA) of fraction C _1o- C _{) 5} . P1526283 A1 is turned on to supply nitrogen to the upper part of the reaction vessel and the reaction mixture is stirred for 30 minutes at 6 ° -9 ° C. The temperature is raised to 90 ° C due to the exothermic reaction of acid neutralization with amines with formation of amine soaps. Then, heating is turned on and the temperature is gradually raised over 4 hours from 90 to 23 ° C. 23 ° C for 2 hours, continuously removing water and excess amines from the reaction zone into the Nina – Stark nozzle. Turn off the nitrogen supply, connect the vacuum and at a temperature of 22O-23O ° C, a residual pressure of 50 mm RT »Art. (6.65 kPa) heat the reaction mass for another 1.5 hours, distilling off excess amines and reaction water. ”Then the product is distilled in vacuum, collecting substances boiling in the temperature range 15O-25O ° C at 1-5 mm as the main fraction. Hg "(0.133-0.665 kPa), the yield of the target product 216

In appearance, the oxidation inhibitor is a viscous liquid of light brown color with a faint amine odor, soluble in water, aqueous solutions of mineral acids. ethyl and isopropyl alcohols, benzene, partially in heptane ”A.ch. = = 160, 1 mg NS 1 / g, K.Ch. = 5, I mgKOH / g. ' Structure:

"

RCONHCHjCHzNH *

NH

()

N-COR where R = - 0 ^ H _zs is an aliphatic radical containing saturated bonds.

The composition is given in Table I. (the structure and composition of the antioxidant were determined ^ 0 using the methods of IR and UV spectroscopy, functional and elemental analysis).

Example 2. To a mixture of amines containing 102.2 g (85 wt.%) EDA n 55 25.8 g (May 15, 2) PP, add 32 g of water and mix for 5 minutes To 160 g (2 mol) of a 25% aqueous raster of the resulting mixture of EDA with PP with an average mol.m. 64 g add 225 g (1 mol cf. mol.m.) FFA fr. C ₍₀ -C ₍₆ .

Condensation of acids phr С C _(o- C _<6 with amines is carried out according to the procedure described in example 1. The reaction mass is heated at 220-230 ° C, vacuum 50 mm Hg (6.65 kPa) 3 h "Product do not distill. Yield 247 g.

In appearance it is a waxy product of a light yellow color with a faint amine odor; it is soluble in alcohol, benzene, in aqueous solutions of mineral acids, disperses in water, partially soluble in heptane. T _u = 45-50 ° C. A.ch. = 176.7 mg HCl / g. K.ch. = 6.3 mg KOH / g

Structure:

N NH Y

R rconhch ₂ ch ₂ nhx

Nx

COR where X = H, COR; R = C _q H _n -C ₁₅ H „, an aliphatic radical containing mainly (up to 852) saturated bonds and up to 15% unsaturated, hydroxy, keto and iso groups.

Example 3. To 160 g (? Mol cp.m. 64) of a 25% aqueous solution obtained by the method described in example 2, 295 g (1 mol) of FFA fr. C ( ₇ ~ C 2 _O "heated to 60 ° C (melt temperature), and the reaction mixture is stirred at 80-90 ° C for 15 minutes. Condensation of acid FR, C _<7 -C 2 _O with a mixture of amines is carried out according to the method described in example 1. During distillation, a fraction boiling in the temperature range 200-280 ° C (1-5 mm Hg 0.133-0.65 kPa) is selected. Yield 195 g.

In appearance it is a waxy product of a slightly yellow color with a faint amine odor; it is soluble in alcohol, benzene, in aqueous solutions of mineral acids, disperses in water, partially soluble in heptane. ' T pd ”50-55 S. A.ch. = 150 mg HCl / g. K.ch. = 5.4 mg KOH / g

Structure: ____ Guin

R

RCONHCH ₇ CH ₂ NH ₂ )

NX () ~ N

I COR where X = H; COR; R - C ₄₆ H _J? - C _4q H ₃₉ , an aliphatic radical containing up to 80% saturated bonds and up to 20% unsaturated bonds of hydroxy, keto and iso groups.

Example D. In this example, fatty acids are used, obtained as a by-product of alkali.

smelting of castor oil during the production of sebacic acid. In their composition, fatty acids contain the following aliphatic acids (25 according to chromatographic analysis), May 7: unidentified to C _1o 2.6; capric 0.4; undecyl 1,2; lauric 1.9; myristic 3.8; palmitic 10.8; seba- jq cinder 0.4; stearic 11.6; oleic 25.8; linoleic 2.7; peanut 5.6; linolenic 4.8; arachidonic 10.1; oxystearic 11.2; ricinoleic 2.8, unidentified above C _2o 4.3.

To a mixture of amines containing 84 g (70 wt.%) EDA and 52 g (May 30, 7 ") PP, 34 ml of water are added and mixed for 5 minutes. To 170 g (2 mol) of a 25% aqueous solution of the resulting mixture of EDA with PP with an average mol.m, 68.5 add 280.5, g (1 mol by parts per hour, = = 200 mg KOH / g) of fatty acids a by-product of the production of sebacic acid. Turn on the nitrogen supply to the upper part of the reaction vessel and mix the reaction mixture for 30 minutes at 60-90 ° 0, turn on the heating and gradually raise the temperature from 90 to 180 ° C, maintain the reaction mass at 180 ° C for 2 hours, continuously removing water from the reaction zone and excess amines in the Dean - Stark nozzle. Turn off the nitrogen supply, connect at 180 ° C the vacuum and raise the temperature to 210 ° C. At a vacuum of 100 mm Hg (13.3 kPa), at a temperature of 210 ° C, the reaction mixture is kept for 1.5 hours, driving off excess amines and according to::. Yield 293.4 g,

In appearance, a puffed oxidation inhibitor - that a viscous brown liquid with a weak amine odor, soluble in alcohol, benzene, heptane, is dispersible in ’ode, soluble in complete solutions of mineral acids, A.h. = = 150.6 mg HCl / g. K.ch. = 9.4 mg KOH / g

Structure:

R

RC0NHCH ₂ CH ₂ NH ₂ j

NH

I COR where R = C ₂ H, _s -с _? О Нч, the aliphatic radical contains up to 60% saturated bonds and up to 40% unsaturated hydroxy, keto groups.

EXAMPLE 5. To a mixture of amines containing 102.2 g (85 wt.%) EDA and

25.8 g ^ 15 wt.%) PP, 32 mm of water are added and mixed for 5 minutes. To 160 g (2 mol) of a 25% aqueous solution of the resulting mixture of EDA with ΙΠΙ with an average mol.m. 64 g add 254 g (1 mol cf. mol.m.) of methyl esters of FFA fr. С _(О -С _4Й . The nitrogen supply to the upper part of the reactor is _turned on, stirring, heating, and the temperature is raised to 120 С. The reaction mass is held at 120 ° С for 2 hours, then the temperature is raised from 120 to 180 ° С and kept for 4 hours at ) 80 ° C, driving methanol, water and excess amines into the Dean - Stark nozzle. Turn off the nitrogen supply, connect at 180 ° C the vacuum and raise the temperature to 230 ° C, gradually gaining a residual pressure of 50 mm Hg (6.65 kPa). At 230 ° C and 50 mm Hg, Art. (6.65 kPa) the excess amines, residues of water and the resulting methanol are distilled off for 1.5 hours. Without distillation, the yield of the oxidation inhibitor was 262 g.

In appearance it is a waxy product of a light yellow color with a faint amine odor ', soluble in alcohol, benzene, in aqueous solutions of mineral acids in water dispersion

I>

r rfiin nif: rastornorm-partially, T _pl = 43-48 ° С. A. h, = 189.3 mg HCl / g. K.ch. = 7.1 mg KOH / g

Structure:

W ^z '

I R

RC0NHCH ₂ CH ₂ NH _g

NH

COR where X is H, COOR; R =% H ₁₉ -C _{| 7} H „is an aliphatic radical containing saturated bonds of normal structure.

Example 6. To 100.6 g (1 mol cf. mol.m) of a mixture of amines containing 72.1 g (70 wt.%) Diethylene triamine (PETA) and 38.7 g (30 wt.%) Β-aminoethylpiperazine (β-ΑΠΙΐ), add 256 g (2 mole cf. mol.m, 128) FFA fr. With ₅ ~ C ₆ include the supply of nitrogen to the upper part of the reaction vessel and mix the reaction mass for 30 minutes at 80-110 ° C.

the temperature rises to 110 ° C due to exothermic reactions of the neutralization of acids by amines with the formation of amine soaps. Then they turn on the heating and gradually increase the temperature from 80110 ° С to 210 ° С for 4 hours, maintain the reaction mass at 210 ° С for 2 hours, continuously removing from the reaction zone to the Dean-Stark plating .. Turn off the nitrogen supply, connect the vacuum and temperature 2 ° C, residual pressure 100 mm Hg (13.3 kPa) warm the reaction mass for another 1.5 hours, driving off water and impurities of low molecular weight amines. Yield 297.4 g.

In appearance, it is a viscous liquid of light brown color, soluble in water, bignol, alcohol, heptane, chloroform, aqueous solutions of mineral acids. A.ch. = 148.5 kg HCl / g. K.ch, = 9.7 mg KOH / g.

Structure: N ^ VrCHzCHjNHCOR AND

RCONH (CH ₂ ) ₂ NH (CH ₂ ) _Z NHCOR

COR

I

!

CH ₂ CH ₂ YANSOK gd .; R =, an aliphatic radical of normal structure containing saturated bonds.

II EXAMPLE 7 (K 107 g (1 mol cfm) of a mixture of amines containing 87.6 g (85 wt.%) DETA and 19.4 g (| 5 wt.%) Β ~ APP, add 280 g (2 mol, cf. mol.m. 140 g) FFA fr. C-f-C ^, including the supply of nitrogen to the upper part of the reaction vessel, was stirred for 10 minutes at 70-100 ° C. Next, turn on the heater for 4 hours, raise the temperature from 70-100 ° C to 230 ° C, hold for 2 hours, driving water into the Dean-Stark nozzle. Then they lower the temperature to 200 ° C, turn off the vacuum and raise the temperature to 230 ° C. At a vacuum of 50 mm / Hg (6.65 kPa), at a temperature of 23 ° C, water is distilled off for 1 h. The product is distilled by selecting a fraction boiling at 150–270 ° C) of 1–5 mm Hg. 243 g

In appearance, it is a light brown viscous liquid soluble in benzene, heptane, sulfuric ether, acetone, in aqueous solutions of mineral salts, disperses, forming a stable emulsion. A.ch. = 150.2 mg HCl / g. K.ch. = 5.8 mg KOH / g

Structure:

₂ CH ₂ BN C0R

R

RC0NH (CH _z ) ₂ NH (CHj ₂ NHCOR sleep

I

I

CH ₂ CH ₂ b1HC0K where R = C ₆ H _,? -С _е Н _1Г , an aliphatic radical of a normal structure containing saturated bonds.

An example. K161 g (1.5 mol cf. mol.m. 107.3 g) of a mixture of amines containing 132 g (85 wt.%) DOTA and 29 g

K) (15 wt.%) Β-ΛΠΠ, 212 g (1 mol by average molecular weight) are added. FFA, fr, C, _о С The process is carried out according to the technological conditions described in example 7. Yield 200 g.

In appearance, the oxidation inhibitor is a light brown viscous liquid with a weak amine odor, soluble in alcohol, benzene, sulfuric ether, acetone, water, and aqueous solutions of mineral acids. A.ch. = 230.1 mg HCl / g. K.ch. = 6.6 mg KOH / g

Structure:

rconh (ch ₂ ) ₂ nh (ch ₂ ) _z nhx;

ch ₂ ch ₂ hhcor where X = H, COR; R = C ^ H _n -C ₁₂ H _{ZS is an} aliphatic radical of normal structure. Containing saturated bonds. . thirty

PRI me R 9. To I6l r (l, 5 mol, average mol. 107.3 g) of a mixture of amines containing 132 g (85 wt.%) DETA and 29 g (15 wt.%) (5-APP, add 225 g (1 mol cf. mol.m.) SLC 35.

fr. C < ₀ -C _(6. The process is conducted according to the technological conditions described in example 7. The product is not distilled. Yield 294 g.

In appearance, it is a light-brown · 40 brown semi-crystalline mass with T _PA = 35–40 ° C, soluble in alcohol, benzene, partially in heptane, disintegrated in water, and soluble in aqueous solutions of mineral acids. A.h ” ^I 45 = 195.3 mg HC1 / g. K.ch. = 7.8 mg KOH / g.

Structure:

G — I

ΝγΝ0Η ^ Η ₂ ΝΗΧ R

RCONHiCHj ^ NHfCH ^ NHX)

I ch ₂ ch ₂ nhcor where X = I, COR; R - -С „Н„ is an aliphatic radical containing up to 85% of saturated bonds of normal structure and up to I5% of unsaturated bonds of hydroxy, keto and iso groups. Example 10. To 191.2 g (1.5 mol, cf. mol.m, 110.8) of a mixture of a 15% aqueous solution of amines containing 108.2 g (70 wt.%) DETA and 58 g (30 wt. .%) r-APP, add 2.95 g (1 mol on average mol.m) FFA fr. C _|? -So _go . The process is conducted according to the technological conditions described in example 7. The product is not distilled. Yield 373 g.

In appearance it is a light yellow waxy mass with T _pA = 55-60 ° C, soluble in alcohol, benzene, partially in heptane, dispersible in water, soluble in aqueous solutions of mineral acids. A.ch. = 146.8 mg HCl / g. K.ch. = 5.5 mg KOH / g

Structure:

n ^ nch ₂ ch _z nhx

R ruonh (ch ₂ ) ₂ nh (ch _z ) _g dnx)

Nx

I.

bN ₂ CH _? KHSSA where X = H, COR; R = CH ₃ , -C _,? H „is an aliphatic radical containing up to 80% saturated bonds of normal structure and up to 20% unsaturated bonds of hydroxy, keto and iso groups.

Example 11. To a mixture of amines. containing 131.5 g (85 wt.%) DETA and 29 g (15 wt.%) ^ -APP, 24.5 ml of water are added and mixed for 15 minutes. To 185 g (1.5 mol, cf. mol. M. 107) of a 15% aqueous solution of the resulting mixture of DETA with β-APP, 270 g (1 mol with cf. mol. M 270) of fatty acids formed during alkaline melting of castor oil during the production of sebacic acid (see composition in example 4). Next, the process of obtaining a copper oxidation inhibitor is carried out similarly to the method described in example 4. Yield 349 g.

I I

In appearance, it is a viscous brown liquid with a slight amine odor, soluble in alcohol, benzene, heptane, dispersible in water, soluble in aqueous solutions of mineral acids. A.ch. = "187.4 mg HCl / g. K.ch. "9.5 mg KOH / g.

Structure:

N ^ CHpI ₂ NHX

R

RCONH (CH 2) 2 NH (CH ₂ ) ₂ NHX ^

Nx

I ch ₂ ch ₂ nhcor where X ~ H, COR; R = C ₂ H 5 - C ₂ θ, - the aliphatic radical contains up to 60Z saturated bonds and up to 40% unsaturated hydroxy, keto groups.

Example 12. A copper oxidation inhibitor is prepared according to the method described in Example 5 by reacting 254 g (1 mol cf. mol.m.) of methyl esters of FFA fr. С _{| о} -С <8 with 107 g (I mol cfm) of an amine mixture containing 87.6 g (85% 1 LETA and 19.4 g (I5Z) 0-APP. Yield 275.5.

The waxy product is light yellow in color with a faint amine odor; it is soluble in alcohol, benzene, in aqueous solutions of mineral acids, and disperses in water. T _P c 38-47 * S, A.ch. 180.7 mg HCl / g. K.ch. = 5.0 mg KOH / g.

Structure:

MooSnr! £ SH and

RCONH ((CH ^) ^ NHj ^ X

Ch ₂ CH ₂ NHCOR where X = H, COR; R ⁼ -C _o H _iy .

Example 13. An inhibitor of copper oxidation is obtained by the method described in example 1, by the interaction of 318 g (1.5 mol srmol.m.)

GLASS FR. С к, -С <5 s 150 g (I mol, cf. mol.m.) of a mixture of amines containing 124 g (85 wt.%) Triethylenetetramia (THETA) and 26 g (157,) di-0-aminoethyl piperazine ( di-r-APP), The product yield without distillation was 428 g.

In appearance it is a viscous liquid of light yellow color, it is soluble in benzene, alcohol, water. ”A.ch. = 228.1 mg HCl / g. K.ch. = 6.7 mgKOH / g.

Structure:

1Tsd5SN ₂ CH ₂ U

R

RC0Nh [(CH ₂ ) ₂ NH], X n-ch ₂ ch ₂ nhx n-ch ₂ ch ₂ nhcor

-C _n H _2S where the aliphatic radical is of normal structure.

Y ^ HHCH ₂ CH ₂ NH ₂ ^ KHCHjCHjUHCOR, νΏτI

R

Example 14. An inhibitor of copper oxidation is obtained by the method described in example 1, by the interaction of 296 g (I mol cf. mol.m.) FFA fr. Cfj-Cjo with 150 g of an amine mixture containing 124 g (85% by weight of THETA and 26 g (15% by weight) of di-0-APP. The yield without distillation was 404 g.

In appearance, it is a viscous semi-crystalline mass of light yellow color, soluble in benzene, alcohol, dispersible in water. A. h, 151.3 mg HCl / g. K.ch, = 9.8 mg KOH / g.

Structure:

N ^ N (CH ₂ CH ₂ NH) ₂ X i

R x = n, COR J R

RC0 h [(CH) ₂ NH] _} X;

n-ch ₂ ch ₂ nhx

() n-ch ₂ ch ₂ nhcor

52.6 28 1 where X = AND, COR; R is C, ₆ 11 „-C, _λ H is an aliphatic radical containing up to 807 saturated bonds and up to 202 unsaturated bonds of hydroxy, keto, iso groups.

Example 15. A copper oxidation inhibitor is obtained according to the method described in example 4 by reacting 270 g (1 mol cf. mol.m) of sebacic acid waste fatty acids (LCI) with 154 g of an amine mixture containing 102 g, ( 70 wt. 7.) TETA and 52 g (30 wtL) di - ^ - ΛΠΠ. Yield 372 g.

A viscous product of brown color, ed soluble in alcohol, benzene, water ”A.ch. 175.5 mg HCl / g. K.h „= 10 mg KOH / g.

Structure:

I ------- 1 x,. twenty

N <yN (CH ₂ NH (CH _g ) ₂ TS ₂

R κοονκ [(οη,), νη] ₅ χ

N-CHaCHaNHX ²⁵ (J

N-CH ₂ CH ₂ NHCOR where X = H, COR; R ⁼ CyN _{) <5} —C _go H ₄ ,.

Example 16 "A copper oxidation inhibitor is obtained according to the method described in example 5 by reacting 254 g (1 mol cf. mol.m") of methyl FZO esters of the C ^ _O -C _{5Y fraction} with 154 g of an amine mixture containing 102 g of ³⁵ ( 70 wt.%) TETA and 52 g (30 wt.%) Diβ-ΛΠΪΙ. Yield 308.8 g.

The product is a light yellow viscous liquid, soluble in alcohol, benzene, water. A, h "= 218.4 mg HCl / g. K.ch. = 6.2 mg KOH / g

Structure:

N ^ N (CH a) ₂ NH (CH ₂ ) a ™ g

R

RCON1I [(cn ₂ ) _g gh] ₃ n;

N - CH, CH, ΝΗ,

ABOUT

N-CH ₂ CH ₂ : NHCOR where R C ₉ H _1d -0.7 N „.

Example 17. A copper oxidation inhibitor is prepared according to the method described in Example 1 by the interaction of 212 g (1 mol cf. mol.m.) FFA of fraction C, o “C, 5 s 173 g (1.2 mol cf. mol. 144) a mixture of amines containing the following substances:

g May. % NETA 36.0 25 β-ΑΠΗ 23.0 eighteen THETA 36.5 25 di-6-ΛΠΠ 20.5 12 TEPA * ’ 67.0 38

'GEPA - tetraethylene pentamine.

The mixture was analyzed by gas liquid chromatography. ”It corresponds to the composition of commercially available PENA m. A (TU 6-02-594-80). Without distillation in vacuum, the yield of a copper oxidation inhibitor was 310 g. In appearance, it is a semi-crystalline viscous mass soluble in alcohol, benzene, dispersible in water, soluble in aqueous solutions of mineral acids.,

A. h “- · 227.4 mg HC1 / g” = 5.0 mg KOH / g

Structure:

ΪΤγΝ (СН аСНрш) _p · X К

RC0NH (CH ₂ CH ₂ NH) _{nt (} X)

Nx

N- (CH ₂ CH ₂ NH) _n X

where η = 1-4, X = H , COR; R = C, H „- S, _g H ₂₅ . At measures 18 " Inhibigor Oxide copper get according to the method luge in the example 1, interoperability Wii 225 g (1 mol on average.mol.m ») СЖК fractions 0 s Π <6 ^s 148 g (1.2 mol,

Wed.mol.m. 123) a mixture of amines containing the following substances:

g wt.% NETA 46,4 45 r-APP 12.9 10 TEPA 18.9 10 THETA 36.5 25 Tsi-r-app 8.6 5

The mixture was analyzed by gas chromatography. It corresponds to the composition of the manufactured industrial PEPA m. B (TU 6-02-594-80).

Without distillation in vacuo, the yield of the copper oxidation inhibitor was

300 g. Light yellow waxy product, soluble in alcohol, benzene, heptane, aqueous solutions.

I 5 mineral acids are dispersible in water. A.ch. "186.6 mg HCl / g. C.ch. = = 5.2 mg KOH / g T _ll = 42-52 s.

Structure;

N ^ N (CH ₂ CHp {H) n X n

RCONHiCHjCHjNH) ^, X;

NX Y- (sn ₂ sn _{2 η} · χ where η is 1-3; X = H, COR; R - CH C ₁₅ H „.

Example 19, a Copper oxidation inhibitor is obtained by the method described in example 4, by the interaction of 270 g (1 mol cf. mol, m.) Of fatty acids, waste products of the production of sebacic acid with 148 g (1.2 mol cf. mol.m. 123) a mixture of amines, the composition of which is described in example 18. Without distillation in vacuo, the yield of the copper oxidation inhibitor was 357 g.

A viscous semi-crystalline mass of brown, soluble in alcohol, benzene, heptane, aqueous solutions of mineral acids, disperses in water. A.ch. = 145.8 mg HCl / g. K.ch. = 5.8 mg KOH / g

Structure:

nZ? N (CH ₂ CHjNH) „X

R rconh (sn ₂ sn _g ΝΗ) _{η +} _, x;

NX ^ (sn _g sn ₂ kn) _n- x

PRI me R 20. A copper oxidation inhibitor is obtained according to the method described in example 5, by the interaction of 2-54 g (1 mol cf. mol.m.) of methyl esters of FFA fr. С, _о -С ₁₈ with 148 g (1.2 mol, cf. mol.m. 123) of the amine mixture, the composition of which is described in Example 18. The distillation-free distillation brine in vacuum yields an oxidation inhibitor 310 g

In appearance it is a waxy product of a light yellow color. T _P6 = 54-64 C. It is soluble in alcohol, benzene, aqueous solutions of mineral acids, dispersible in water.

RC0NH (CH ₇ CH ₂ NH) _hji X;

NX ^ - (ch ₂ ch ₂ nh) „x where η = 1-3; X = AND, COR; R - С Н „С <7 Н _Э5 .

Example 21 ₀ To 103 g (1 mol) of diethylenetriamine DETA add 450 g (2 mol on average mol.m.) FFA fr.

Technological example of semi-Cris, ₀ -C ₄₆ . The process is conducted according to the chemical regimes described 6. The yield is 403.6 g.

In appearance '* this is a tallic mass of light yellow color, not in water. soluble and non-dispersible, soluble in benoleol, alcohol at 50 ° C. A.h. = 75.3 mg HC1 / g. K.ch. = 9.3 mg KS> N / g.

Structure:

N ^ NCHjCHaNHCOR

R ^ CH, CH, NHCGR nhCL ^ cn ₂ si ₂ bs, where R = C ^ H, _C- C, ₅ Hg _> , is an aliphatic radical of normal structure containing saturated bonds.

Example 22. To 103 g (1 mol) of DETA add 225 g (1 mol cf. mol.m.) FFA FR. Cjq-cig. The process is conducted according to the technological conditions described in example 4. Yield 244.3 g,

In appearance it is a viscous liquid of a light yellow color, it disperses in water, it is soluble in benzene, alcohol, heptane, and aqueous solutions of mineral acids. A.ch. ^and ~, = 173.5 mg HCl / g. K.ch. = 4.7 mg KOH / g.

Structure:

RCONHCH! CH _g UNSN _g CH ₂ ΝΗ _g

RCONH (CH _g ) _Z NH (CH _? ) _? NHCOR,

'15 26283 <s where Η = С _Ч И ₍ , -С _{| 5} П _Л |, is an aliphatic radical of normal structure containing saturated bonds.

Example 23. To 120 g (2 mol) of $ ethylenediamine (EDA), 225 g (I mol cf. mol.m.) of FFA Fr, C, ₀ C _{1 () are} added. The process is conducted according to the technological modes described in example 5.

Structure: ₁₀

G ~ 1 N ^ N-H

R

RCONHCH _z CH ₂ NHCOR where R = ^C 3 ^lf V ·) “ ^С “ 5 ^Н 'is a normal structure aliphatic radical containing saturated bonds.

Example 24. To 300 g (5 mol) jo EDA add I40 g ¢ 1 mol cf., mol.m.) FLC Fr, C _t -C ,. The process is conducted according to the technological conditions described in example 1. Yield 372.8 g.

In appearance, it is a pasty 25-light yellow product, soluble in water at 50 ° C, benzene, alcohol, heptane, chloroform, and aqueous solutions of mineral acids. A. h, = = 156.3 mg HCl / g. K.ch. = 2.7 mg zo

KOH / g

Structure:

N MN

Y r

RC0NHCH ₂ CH _t NII ₂ where R is C ₆ H, ₃ -C ₀ H ₁₇ , an aliphatic dd radical of normal structure containing saturated bonds,

I PRI me R 25. To 146 g (1 mol) of triethylenetetramine (THETA) add 225 g (1 mol cf. mol.m.) FLC 45 fr. C _{| 0} -C _{) 6} . The process is conducted according to the technological conditions described in example 1. Yield 309.2 g.

In appearance, it is a viscous liquid of light brown color, readily soluble in water, benzene, alcohol, heptane, aqueous solutions, mineral acids. A.ch. = 252.7 mg HC1 / g, K.Ch. = 5.1 mg KOH / g

Structure:

^ UKSN ₂ CH ₂ INSN ₂ sn ₂ pl ₂

R

RCCWH (SP y} _g PN (CH _? ) _Z NH (SP. No. 1 ,, · where R = 158 ,,. Aliphatic radical of normal structure containing saturated bonds.

II Example 26, K 141 g (I, 5 mol) of piperazine are added 140 g (1 mol on average, mol.m.) FFA fr, C ₇ -C _? . The process is conducted according to the technological conditions described in example I. Yield 223.8 g.

In appearance it is a crystalline mass of light yellow color, it disperses in water, it is soluble in benzene, heptane, sulfuric ether, in aqueous solutions of mineral acids when heated. . A.ch. = 158.7 mg HCl / g. K.ch. = 8.4 mg KOH / g.

Structure:

NH ()

N-COR where R = C _e H _n -C ' _in -C ₄₇ , a normal-structure aliphatic radical containing saturated bonds,

Example 27. To 205.5 g (1.5 mol) of [3-aminoethylpiperazine (β-ΛΓΙΐί) are added 225 g (1 mol cfm) of FFA fr. C _(O- C _16. The process is conducted according to the technological conditions described in example I. Yield 340.5 g.

In appearance, it is a pasty product of a light yellow color, it is soluble in benzene, heptane, sulfuric ether, in aqueous solutions of mineral acids, disperses in water, forming a stable emulsion. A.ch. i = 214.5 mg HC1 / g. K.ch. = 2.8 mg KOH / g. .

Structure: ΝΗ O-CH ₂ CH ₂ NHC0R where R = C ^ H _{1 <?} -С ₍₅ Н _Э1. Aliphatic radical of normal structure, containing saturated bonds.

Tests of the oxidation inhibitor were carried out on copper plates measuring 53 * 140 mm. By re-testing, the surface of the plates was protected with a fine sandpaper from oxides, and rubbed with alcohol. The plates were placed in vessels in which water was filled with hardness

3.5-10 mEq / l and an aqueous solution of in-, oxidation inhibitor with a concentration

I 9

0.06-0.5 mg / l. The plates were kept for 4 h in these solutions at 50 ° C. To maintain a constant temperature, the vessels were placed in heated chambers.

Similarly, experiments were carried out on samples of copper wire 10 cm long, 2 mm cross-section at room temperature, and exposure for 12 hours. Then, the surface of the plates and wire. rubbed with alcohol and visually assessed the quality of the surface, comparing with the control sample. The imagery processed in this way was left in air with a relative humidity of 60–95% and a temperature of 20–30 ° C (storage conditions in warehouses). The effect was visualized by the presence of oxide. dark films on the surface of copper products in comparison with a control sample. The test results of the degree of protection of copper plates; ok and wire from oxidation are given in table. one.

As follows from the data given in Table 1, the optimum concentration of an additional surface-active oxidation inhibitor is in the range of 0.080.25 g / l (for homologues, the country alkyl radical С _t- С „concentrate alium rises to 0.35 g / l).

The copper plates and the wire treated with the inhibitor solution were pulled out in air at 20 ° C. The efficiency of the oxidation inhibitor was visually assessed by the appearance of the plates after 1.35 seconds. The test results of the samples showed that the proposed composition allows you to save a clean shiny surface of copper for more than 5 months, which reduces the irretrievable loss of copper wire and copper products.

Table 1 (examples 22-27) and table 2 show comparative examples corresponding to the prototype and composition containing individual components of the composition and their combinations, confirming the positive effect of the invention.

The optimal concentration for the proposed inhibitor is 0.080.25 g / l, for benzotriazole - 0.5 1 g / l, urea - 5-10 r / l. Thus, the proposed method makes it possible to obtain, in one step, a complex composition of a highly effective inhibitor of copper oxidation based on available raw materials (synthetic fatty acids, fraction differences, polyethylene polyamines).

Claims (4)

R m of the invention 1. A copper corrosion inhibitor containing alkylimidazolines and alkylamido amines, characterized in that, in order to increase the efficiency in an aqueous medium at pH = 711, it additionally contains Nacylpiperazines and / or N- (acylaminoalkyl) piperazines in the following mixture wearing, wt "%: Alkppimidazolines and Alkyl Amidoamines 70-90 N-acylpiperazines and / or N- (acylaminoalkyl) piperazines 10-30 2. A method of obtaining a copper corrosion inhibitor, including alkylimycazolines and alknamideamines, by acylation of a mixture of aliphatic amines kshg;^g fatty acids days with their lower alkyl esters when heated and reduced pressure, characterized in that, in order to increase efficiency in an aqueous medium at pH 7-11, a mixture of fatty acids of fractions C is reacted_s~ C_2o or their sword silt ethers and a mixture of polyethylene polyamides with piperazines in a ratio of from 70-30 wt.₀% to 85-15 wt.%, respectively, and the condensation process is carried out in a stream of nitrogen supplied above the surface of the reaction mixture at a temperature of 21O ~ 23O ° C, a pressure of 50-100 mm Hg, st, (b, 65 13.3 kGe) to obtain a reaction product with an amine number of 150-230 mg HCl / g and an acid number of 5-10 mg KOH / g 3. The method according to claim 2, characterized in that the synthetic fatty acids of the C ₅ ~ C ₆ , C ₇ -C <j fractions are taken as fatty acids, C to “CB> C jo - C ₍₆ , C ₍₇ -C _zo . 4. The method according to claim 2, with the fact that the fatty acids of the C ₅ ~ C fractions are taken as fatty acids. _2O , waste from the production of sebacic acid resulting from the alkaline melting of castor oil.