SU1293181A1 - Method of producing antiwear additives to carboxylic acid piperazineamide-base wash liquid - Google Patents

Abstract

The invention relates to substituted heterocyclic substances, in particular carboxylic acid piperazinoamides (PAA) of the general formula I K.KSN SNHYUSCH CHg, where (CHjCF NH) C (0) C (CH3) (R, i) - (CH, jCH2) nH; a) R, H, R2 C2Hs; , 12; b) R,;. H; .q; - n 2-10; c) R, -C (0) C (CH3) R2 - () nH; : n-0, 1 or 2; r) R) | -C (0) C (CH,) Rj, - () nH; H , n 2-IO; e) R, H; , , 12; e) R, H; R2 C4Hg; n 2-10; g) R, -C (0) C (CH,) R.2 - (,) H; .j, 1, 2; h) R, CS (0) С (СН,) Р2 (СН2СНг) „Н; n 2-lp; PAA - anti-wear additives for flushing fluids m. The best quality of PAA is achieved by using other precursors processed under different conditions. Synthesis. PAA lead from the corresponding substituted pipedinov and oi-branched acids of the formula P: H- (CH, CH2) „- -CR2 (CH,) C (0) OH, where, at. Acids are taken in the form of 3 fractions: G -,; П - С „Н, and ГГТ - С 27 The process is carried out at 110-130 С in the presence of aromatic hydrocarbons, alcohols or water, followed by distilling off the solvents at 150-200 ° C (10-40 mm Hg). The method provides high quality additives to the washing liquids by reducing the wear rate, for example, 259 mm / h at 12.7 MPa versus 350 mm / h in a known method. 2 tab. g (L N5; o 00 oo

Description

The invention relates to a method for the preparation of anti-wear additives to washing fluid when drilling oil and gas wells based on piperazinoamide of the general formula

Шз СН2Ш2Тда) тСОСЧШ2Шг Н

I-viii

I ii

 R C2H5; ,, , CHIII С - (СН „СН ,,)„ Н;

R

R, C, H ,;

Ch.

z n

,

IV

 -C- (CH ,, CH, j) -H;

R n 2-10;

 R,

 ,; ,

CH,

VIIR CO C- (CH, CH,) H;

2 n

I

R

R C2H5;

CH, VIII C- (CH2CH) H;

R,; n 2-10; .

The purpose of the invention is a method

d) B of the conditions of example 1a, 12.9 g, 25 ml of tol ol and 14.5 g of VIC 1 are loaded into the reaction, heated at 90 ° C for 4 hours, then the temperature is raised to 180 ° C. At 180 ° C / 20 mm, distillation, solvent and light components are produced. Time off

Neither improved anti-wear additives, 45 (8 hours), darkening of the initial quality on the basis of amidopiperazines was observed using available products due to an increase in the duration of heating. Get 21.5 g

branch compounds of branched monocarboxylic acids.

The invention is illustrated by the following examples.

PRI and MER 1. a) In the reactor, which is a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 12.9 g (0.1 M) of H- / 5-aminoethylpiperazine (AEP) are charged, 25 mp of toluene and 14.5 g (0.1 M) fraction (UIC of O-branched monocarboxylic acids (VIC)), the reaction mixture is heated at 110 ° C for 4 hours under a stream of nitrogen, then the solvent is distilled off, and 150-160 ° C / 10-15 mm until the calculated amount of water (4 hours) is distilled off.

24.47 g (95.6%) of product (I) are obtained in the form of a viscous mass.

one

)

brown, IR spectrum (cm 1570 (NH); 1670 (HHSS).

Chemical analysis data are given in table. one .

b) Under conditions of example.1, 12.9 g (0.1 M) -AEP in 30 MP toluene and 22.7 g (0.1 M) of fraction С, -С ,, are loaded into the reactor (VIC 2). The mixture is heated at 120-130 ° C for 2 hours, then the light components are distilled off, simultaneously raising the bath temperature. Distillation is carried out at 170-180 C / 20-30 mm (5 h).

Received 32.4.g (96%) of a dark brown product. IR spectrum

(cm-): 1565 (W); 1670 (NHCO).

The analysis is given in table. one.

 Under similar conditions, by heating a mixture of 12.9 g of Np-AEP, 50 ml of toluene and 32.5 g (0.1 M) of the Cji Cgr fraction (PIC 3), first at, then at 180–200 ° C / 20–40 mm with 41, -2 g (94.5%) of the product (2) are obtained in the form of a dark brown waxy product by subsequent distillation of the light components. IR spectrum (): 1565 (NH), 1670 (CONH).

The analysis is given in table. one.

d) B of the conditions of example 1a, 12.9 g, 25 ml of toluene and 14.5 g of VIC 1 are loaded into the reactor, heated at 90 ° C for 4 hours, then the temperature is raised to 180 ° C. At 180 ° C / 20 mm, distillation, solvent and light components are produced. Time off

 (8 h), there was a darkening of the

(8 h), there was a darkening of the

duct by increasing the duration of heating. Get 21.5 g

(84%) of the product (I) dark brown. IR spectrum (cm 50 (NH); 1670 (Secondary School)).

) 1575

The analysis is given in table. one.

Example 2.a) Under the conditions of Example 1, 2.9 g of 55 (0.1 M) Np-AEP, 50 ml of toluene and 29 g (M) of VIC 1 are loaded into the reactor and heated at 130 ° C for 2 hours, then the temperature increase to 160-170 ° C and produce distillation of water, solvent, and light components.

at 160-170 ° C / 10-15 mm. The distillation time was 6 h. 35 g (92%) of product (3) were obtained as a viscous mass, IR spectrum (cm): ots (NH, NHj), 1675 (CO-N).

The analysis is given in Table 1, b) Under the conditions of Example 2, 12.9 g (0.1 M) of Np-AEP are loaded into 50 ml of toluene and 29 g (0.2 M) of the VIC 1, first at 130 ° C for 4 h, followed by the distillation of light components at 220-230- ° C / 10-20 mm, which leads to the partial formation of tar, charring. Yield 68%.

Example 3. a) Under the conditions of example 2 by heating 12.9 g (0.1 M) of NB-AEP in 50 ml of ethylene glycol k 45.4 g (0.2 M) of the VIC 2, first at 130 ° C for 3 h, then followed by distillation at 180-200 C / 20

40 mm obtained 50.8 g (98%) of the product (4) in the form of a thick viscous mass, IR spectrum (): ots (NH, W) 1670, 1675 (NHCO, NCO)

The analysis is given in table. one.

b) Under the conditions of example 3, of 67.9 g (91%) of the product was obtained from 12.9 g (0.1 M) N- / 3-A3n in 50 ml of xylene and 65 g (0.2 M) VIC 3 4) in the form of a waxy substance. IR spectrum (): OTC, (NH, NH2).

The analysis is given in table. one,

Example4. Charged to the reactor of 8.6 g (0.1 M) piperazine in 25 ml of decyl alcohol and 14.5 g of VIC 1,

heated at 110 ° C for 4 hours, then the temperature is raised and light substances are distilled off at 190–200 ° C / 10–20 mm. 20.6 g (97%) of the product (5) are obtained in the form of a thick mass. IR (cm-): 1565 (NH), 1690 (N-CO).

The analysis is given in table. one.

Example 5. Under the conditions of Example 4, 19.4 g (0.1 M) of piperazine hexahydrate, 25 mp of solvent (mixture of xylenes) and 22.7 g (0.1 M) of the PIC 2 are loaded into the reactor. 130 C Hh, then light substances are distilled off at 200 C / 10 mm.

27.9 g (94.8%) of the product (6-) are obtained.

The analysis is given in table. B.

Example Under the conditions of Example 4 and 5, 34.5 g (92.5%) of a waxy semi-solid product (6) was obtained from 8.6 g of piperazine, 50 mp of toluene and 32.5 g (0.1 M) of PEC 3. IR spectrum (cm-): 1575 (W), 1690 (CON).

five

fO

t5

0

0

five

Yu

five

0

1814

The analysis is given in table. G.

Example 7. Under the conditions described, 8.6 g (0.1 M) piperazine, 40 mp HjO and 29 g (0.2 M) PIC 1 are loaded into the reactor, heated at 110 ° C for 4 hours, then the light components are distilled off at 195-200 C / 10-12 mm.

31.28 g (92%) of a semi-solid 8 product (7) were obtained. IR spectrum (): ots. (NH), 1690 (CON).

The analysis is given in table. one.

Example 8. Under the conditions of example 7, from J9.4 g (0.1 M) piperazine hexahydrate in 50 MP of ethylene glycol and 45.4 (0.2 M) VIC 2, 46.66 g (91.8%) of product 8 was obtained . IR spectrum (): ots. (NH), 1690 (CON).

The analysis is shown in table 1.

Example9. Under the conditions of Example 7, from 6.6 g of piperazine, 50 ml of toluene and 65 g (0.2 M) of PEC 3, 62.3 g (89%) of a waxy product (8) was obtained. IR spectrum (): ots (NH), 1690 (CON).

The analysis is given in table. one.

Determination of anti-wear properties of flushing fluids.

Determination of the anti-wear properties of the washing liquids obtained by mixing compounds 1-VIII and water in a weight ratio of 0.1-0.2: 99.9-99.8 is performed on a friction machine. The determination is that the wear rate of steel is measured. from which the working element of the friction unit is made, when washing the working element of the machine, corresponding to the washing liquid, at different specific loads. Moreover, the lower the wear rate, all other things being equal, the operation of the friction unit, the higher the anti-wear properties of the washing liquid.

Comparative data characterizing the antiwear properties of the compositions of the washing liquid are given in table. 2.4

The required amount of carboxylic acid piperazinoamide supplement is in the range of 0.1-0.2 wt.% With an increase in the indicated amount of carboxylic acid piperazinoamide, the wear rate practically does not change.

Claims (1)

Claim 1 The method of obtaining anti-wear additives to flushing liquids on 54293181 based on piperazinoamide carboxylic acids formulB Shz R - NQN CH CH H toCOCHCHjCVh H R, I-viii Where  R, l, 2;  R, C4Hg; n 2-10; CH-, I R CO-C- (CH2-CH2) n-H, R ,. ,, l, 2, CH, R co-c- (CH, j-CH2) n -H; R, R,; ,  R,, I, 2,  R, C4H ,, n 2-10; VIK-1 (1: 1) light brown color N-p-AEP with Liquid 3.2 VIC 2 (1; 1) dark brown N-E-AEP with Wax-Acid 3.6 VIC 3 (1: 1) different product of dark brown color CH, 15 VIIR CO-C - () - H; Rj 3 R,, l, 2; CH, VIIIR CO-C - (, - H ;; to. R.  R ,,; n 2-10; characterized in that, in order to improve the quality of the target product, the correspondingly substituted or unsubstituted piperazine is reacted with alpha-branched monocarboxylic acids of the formula I 20H - () - C-COOH R, where R, C2H5-,, in the form of 3 fractions: 1 - Cj-Cq (VIK-1); 2 25 s „-C, d (VIC-2); 3 - С, -Сгг (ВИК-3). at 110-130 C in the presence of aromatic hydrocarbons, alcohols or water as solvents, followed by distillation at 150-200 ° C / 1030 .40 mm. Table D 0.20 Full 6.08 0.29 full 6,6 The composition of the washing liquid, mas.ZH Technical water + + 0.1% VIC 1 with N-p-AEP (VIC l: N-p-) Water + 0.1% VIC 1 with piperazine (1: 1) Water + 0.1% PEC 1 with N-p-AEP (2: 1) Water + 0.1% VIC 1 with piperazine Water + 0.1% VIC 2 with N- (3-A3n (1: 1) Water + 0.1% VIC 2 with piperazine (1: 1) Water + 0.1% PEC 3 with N-p-AEP (1: 1) Water + 0.05% PEC 3 with N-fi-AEP (1: 1) Water + 0.2% PEC 3 with N- | i-A3n (1: 1) Water + 0.3% PEC 3 s (1: 1) Water + 0.3% VIC 3 with piperazine (1: 1) Water + 0.1% VIC 3 with piperazine (2: 1) Water + 0.2% VIC 3 (2: 1) Compiled by G. Konnova. Editor I. Segl. Tehred V. Kadar Corrector A. Zimokosov Order 344/26 Circulation 372Subscription VNSHSHI USSR State Committee for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5 Production and printing company, Uzhgorod, ul, Pektna, 4 Wear rate, mm / h under various loads, MPa ten , 6 1 11.3 I 12.0 j 12.7 86,9126.1 144.7 259 X 85,8122,3 140,6 243 78120.2 131.5 239 79,2121.5 136.7 238 83.3 88.6 180 81.9 83.6 177 4), 9 56.2 136 86.5 82.9 172 46.5 54 46,1 52 133 46.0 53.6 132 45.7 52.5 133 44.2 51.9 134 129