RU2379280C1 - N,n-diethyl-n-[isoalkoxycarbonylmethyl n-[alkylphenoxypoly(ethyleneoxy)-carbonylethyl]ammonium 2-hydroxypropionates with steel corrosion inhibitor properties - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of novel N,N-diethyl-N-[isoalkoxycarbonylmethyl]-N-[alkylphenoxypoly-(ethyleneoxy)carbonylethyl]ammonium 2-hydroxypropionates of formula

where R¹ is a C₈-C₁₀ alkyl fraction; R² is C₁₂ isoalkyl, C₁₂-C₁₄ isoalkyl fraction, C₁₄ isoalkyl; n is the average oxyethylation degree, equal to 6, with properties for inhibiting steel corrosion in aqueous chloride media. Said compounds are obtained by reacting alkylphenoxy polyethyleneglycol of formula

(R¹, n see above) with methylacrylate in the presence of an acid catalyst and polymerisation inhibitor at temperature 60-80°C, further bonding of diethylamine in isopropanol at 30-40°C, subsequent treatment of the bonding product with isoalkyl monochloroacetates of formula

(R² see above) and a strongly basic anion exchange resin which is a product of copolymerisation of styrene and divinylbenzene with quaternary ammonium groups, such as AB-17-8, in OH^-form, modified 2-hydroxypropionic acid, and which is an anionite salt, at temperature 60-80°C and with the following ratio of reagents in gram equivalents: alkylphenoxy polyethylenegylcol : methylacrylate : diethylamine : isoalkyl monochloroacetate : modified anionite 1.0:(1.0-1.5):(1.0-1.1):(1.0-1.04):(3.8-4.0).

EFFECT: given compounds can be used for protecting equipment in chemical, oil and petrochemical industry, when pickling metals in chemical industry and metallurgy, and when processing oil wells.

3 cl, 1 tbl, 3 ex

Description

The invention relates to organic chemistry, in particular to the synthesis of previously unknown quaternary ammonium compounds such as N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates having the properties of steel corrosion inhibitors in hydrochloric acid aquatic environments that can be used to protect equipment in the chemical, oil and petrochemical industries, as well as in metal etching in the chemical industry and metallurgy, in the processing of oil well in in the oil industry.

Known are quaternary ammonium compounds of the type N, N, N-triethyl-N- [alkoxycarbonylmethyl] ammonium chlorides of the general formula

containing an ester moiety with long chain alkyl radicals [Kozlova N.V., Levina A.S. Surfactant properties of N- [alkyloxycarbonylmethyl] pyridinium chlorides and N- [alkyloxycarbonylmethyl] triethylammonium chlorides // Surfactants. (Synthesis and Properties): Interuniversity. topics compilation. - Kalinin: Ed. KSU, 1980. - S. 35-41].

Known Quaternary ammonium compounds containing polyoxyethylene fragments of the General formula

[Stefanovich E.V., Gershenovich A.I., Chernyavskaya M.A. and others. The use of alkyldi-β-hydroxyethylbenzylammonium chloride as an antibacterial drug // VI All-Union. conf. on surfactants and raw materials for their production: Proc. doc. - Volgodonsk, 1984. - S.303-304].

Also known are N- [alkoxypoly (ethyleneoxy) carbonylmethyl] ammonium chlorides containing ester and polyoxyethyl moieties of the general formula

possessing the properties of additives that regulate the viscoelastic properties of the associated multicomponent oil systems [US Pat. 2221775 RF, publ. 2004.01.20].

The closest in structure to the proposed compounds are N- [isononylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chlorides containing ester, polyoxyethyl and isononylphenoxyl moieties of the general formula

possessing the properties of carbon steel corrosion inhibitors in mineralized hydrogen sulfide-containing aqueous media, also exhibiting fungistatic, bacteriostatic and disinfecting effects [US Pat. 1531416 RU, publ. 1995.04.10]. However, these ammonium compounds exhibit low anticorrosive activity in hydrochloric acid aqueous media.

The technical result of the present invention is the ability to obtain new ammonium compounds - N, N-diethyl -] - N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates having the properties of steel corrosion inhibitors in hydrochloric acidic aqueous media.

The inventive quaternary ammonium compounds N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonyl-ethyl] ammonium 2-hydroxypropionates simultaneously contain ester, polyoxyethyl, alkoxyl and alkylphenoxy radicals, where alkyl and have the general formula

where R ¹ = alkyl fractions C ₈ -C ₁₀ ;

R ² = isoalkyl C ₁₂ , isoalkyl fractions C ₁₂ -C ₁₄ , isoalkyl C ₁₄ ;

n = average degree of hydroxyethylation equal to 6.

These compounds are new and possess the properties of corrosion inhibitors in hydrochloric acid aqueous media.

A known method of producing ammonium compounds containing ester and polyoxyethyl groups, formula

by reacting monochloracetic acid with an alcohol component, which is isononylphenoxypolyethylene glycols, of the formula

and subsequent treatment with amines [US Pat. 1531416 RU, publ. 1995.04.10].

For our claimed N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates, a process for preparing by reacting alkylphenoxypolyethylene glycols is provided, the formula

where R ¹ = alkyl fractions C ₈ -C ₁₀ ;

n = average degree of hydroxyethylation equal to 6,

with methyl acrylate under acid catalysis with the H ⁺ form of a KU-2-8 cation exchange resin and in the presence of a polymerization inhibitor, for example hydroquinone; further addition of diethylamine in a polar organic solvent, for example isopropanol, at a temperature of 30-40 ° C; and subsequent processing of the coupling product with isoalkyl monochloroacetates of the general formula

where R ² = isoalkyl C ₁₂ , isoalkyl fractions C ₁₂ -C ₁₄ , isoalkyl C ₁₄ and modified anion exchange resin AB-17-8, which is a salt of the OH ^- form of anion exchange resin with 2-hydroxypropionic acid at a temperature of 60-80 ° C and ratios of reagents in g-equivalents - alkylphenoxypolyethylene glycol: methyl acrylate: diethylamine: isoalkyl monochloracetate: modified anion exchange resin = 1.0: (1.0-1.5) :( 1.0-1.1) :( 1.0-1.04 ) :( 3.8-4.0).

The basis of the proposed method for producing the claimed N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates are the following chemical transformations (Schemes 1 and 2). Alkylphenoxypolyethylene glycols (1) serve as the basis for the synthesis of new tertiary amines (3) by their initial interaction with methyl acrylate, the formation of the corresponding alkylphenoxypoly (ethyleneoxy) acrylates (2) and the subsequent addition of diethylamine to them

Further, according to the proposed method, the obtained tertiary amines (3) are reacted with isoalkyl monochloroacetates (4) and a modified anion exchange resin AB-17-8 (in the form of a salt of the main form of anion exchange resin with 2-hydroxypropionic acid) (5):

and the desired N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates are obtained (6).

Along with individual compounds, hydroxyethylated alkylphenols produced by the petrochemical industry, including Neonol AF ₉ -6 (TU 2483-077-05766801-98) with an average degree of hydroxyethylation of 6, can also be used as starting alkylphenoxypolyethylene glycols.

As methyl acrylate, you can use both individual methyl acrylic acid ester and an industrial product according to TU 2435-003-52470063-2003.

The acidic heterogeneous catalyst used is the H ⁺ form of the KU-2-8 cation exchange resin, which is a solid, limited-swelling, high molecular weight polysulfonic acid of a styrene-divinylbenzene copolymer of the general formula

and is available in various versions, differing in the amount of divinylbenzene in the copolymer. For example, the KU-2-8- and KU-2-10 cation exchange grades contain 8% and 10% divinylbenzene, respectively [Saldadze KM, Pashkov AB, Titov B.C. High molecular weight ion exchange compounds. Ed. Saldadze K.M. Moscow: Goskhimizdat, 1960].

Diethylamine can be used both as an individual compound and as a commercial diethylamine according to GOST 9875-88.

As a modified anion exchange resin, AB-17-8, a strongly basic anion-exchange resin manufactured by industry according to GOST 20301-74 and representing the copolymerization of styrene and divinylbenzene with functional quaternary ammonium groups in the form of chloride, can be used, of the formula

To obtain a modified form, industrial anion exchange resin is converted into the main OH ^- form by treatment with alkali solutions, and then the resulting anion exchange resin is neutralized with a solution of 2-hydroxypropionic acid, similar to the procedure described in [MacPherson LB Recovery of Lecithin from the Lecithin - Cadmium Chloride Complex // Nature - 1954 - Vol. 173 - No. 4416 - P.1195-1196]. Thus obtained modified anion exchange resin is a salt of 2-hydroxypropionic acid of the formula (5)

and is used as a reagent in the proposed method for producing the target quaternary ammonium compounds.

As 2-hydroxypropionic acid can be used as an individual 2-hydroxypropionic (lactic) acid, as well as an industrially produced product - food lactic acid according to GOST 490-2006.

Isoalkyl monochloracetes were obtained analogously to the method presented in the work [Abramzon A.A., Zaichenko L.P., Fayngold S.I. Surfactants. Synthesis, analysis, properties, application. L .: Chemistry, 1988. P.33] by esterification of monochloracetic acid with individual C12, C14 α-olefins and / or industrial C14, C12-C14 α-olefins, produced according to TU 2411-058-05766801-96.

General Method for the Preparation of Isoalkyl Monochloracets

In a reaction flask equipped with a mechanical stirrer and a reflux condenser, a mixture of 0.3 g-mole of α-olefin, (0.3-0.4) g-mole of monochloracetic acid, H ⁺ form of KU-2-8 cation exchange resin is placed in the amount of 10-15% by weight of monochloracetic acid (as an acid catalyst) and heated at a temperature of 60-80 ° C for 10-12 hours. The reaction is monitored by the amount of unreacted monochloracetic acid, which is determined by potentiometric titration with an alcoholic KOH solution. After the reaction, the resulting reaction mixture was dispersed in vacuo, selecting the target fraction.

Specific Examples of the Invention

Example 1

N, N-Diethyl-N- [isoalkyl (C ₁₂ ) hydroxycarbonylmethyl] -N- [alkyl (C ₈ -C ₁₀ ) -phenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionate with an average degree of hydroxyethylation equal to 6.

A mixture of 145.4 g (0.3 g-equiv) alkyl (C ₈ -C ₁₀ ) phenoxypolyethylene glycol with an average degree of hydroxyethylation equal to 6; 38.7 g (0.45 g-equiv) of methyl acrylate, 3.8 g (10.0% by weight of methyl acrylate) of the H ⁺ form of the KU-2-8 cation exchange resin (as an acid catalyst), and 1.94 g ( 5.0% by weight of methyl acrylate) hydroquinone (as a polymerization inhibitor) is heated with a Dean-Stark trap and refluxed at a temperature of 60-80 ° C until the evolution of methyl alcohol ceases. The reaction time is 10-15 hours. The catalyst is filtered off from the reaction mass. The residual methanol and unreacted methyl acrylate are removed in vacuo, the residue is dissolved in 180 ml of isopropanol, 24.1 g (0.33 g-equiv) of diethylamine are added and the mixture is kept at a temperature of 30-40 ° С for 10 hours. Unreacted diethylamine is removed in vacuo. The product obtained in isopropanol is mixed with 78.8 g (0.3 g-equiv) of isoalkyl (C ₁₂ ) monochloracetate and 110.0 g (1.2 g-equivalent) of modified anion exchange resin AB-17-8 (in the form of a basic salt OH ^- forms of anion exchange resin with 2-hydroxypropionic acid) and with effective stirring are heated at 60-80 ° C for 10-15 hours. The reaction is monitored titrometrically, determining the content of free amines by potentiometric titration with an alcoholic solution of hydrochloric acid. The reaction is stopped when the residual content of free amines is less than 2.0%. The anion exchange resin is filtered off and isopropanol is removed in vacuo. Received 258.9 g of the target product (amine conversion 96.2%) as a yellow viscous liquid.

IR spectrum: ν _{(C = O)} = 1740-1750 cm ^-1 ; ν _(C-O-cycle) = 1115-1140 cm ^-1 ; ν _(C-Oacetate) = 1240-1260 cm ^-1 .

Elemental analysis: found,%: C 71.27; H, 8.65; N, 1.21; calculated,%: C 71.63; H, 8.87; N 1.33.

Example 2

N, N-Diethyl-N- [isoalkyl (C ₁₄ ) hydroxycarbonylmethyl] -N- [alkyl (C ₈ -C ₁₀ ) -phenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionate with an average degree of hydroxyethylation equal to 6.

.Obtained analogously to example 1 from 145.3 g (0.3 g-equiv) of alkyl (C ₈ -C ₁₀ ) -phenoxypolyethylene glycol with an average degree of hydroxyethylation equal to 6; 31.0 g (0.36 g-equiv) of methyl acrylate, 3.1 g (10.0% by weight of methyl acrylate) of the H ⁺ form of the KU-2-8 cation exchange resin (as an acid catalyst), 1.55 g ( 6.0% by weight of methyl acrylate) hydroquinone, 21.9 g (0.3 g-eq) diethylamine, 87.1 g (0.3 g-eq) isoalkyl (C ₁₄ ) monochloracetate and 110.0 g (1, 2 g-eq) of modified AB-17-8 anion exchange resin. Received 298.7 g of the target product (amine conversion 91.8%) as a yellow viscous liquid,

.

IR spectrum: ν _{(C = O)} = 1740-1750 cm ^-1 ; ν _(C-O-cycle) = 1115-1140 cm ^-1 ; ν _(C-Oacetate) = 1240-1260 cm ^-1 .

Elemental analysis: found,%: C 66.37; H 10.07; N 1.55; calculated,%: C 66.60; H 10.16; N 1.47.

Example 3

N, N-Diethyl-N- [isoalkyl (C ₁₂ -C ₁₄ ) hydroxycarbonylmethyl] -N- [alkyl (C ₈ -C ₁₀ ) phenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionate with an average degree of hydroxyethylation equal to 6.

.Obtained analogously to example 1 from 145.4 g (0.3 g-equiv) of alkyl (C ₈ -C ₁₀ ) phenoxypolyethylene glycol with an average degree of hydroxyethylation equal to 6; 31.0 g (0.3 g-equiv) of methyl acrylate; 6.0 g (20.0% by weight of methyl acrylate) of the H ⁺ form of the KU-2-8 cation exchange resin (as an acid catalyst); 1.55 g (5.0% by weight of methyl acrylate) hydroquinone (as a polymerization inhibitor); 21.93 g (0.3 g-equiv) of diethylamine; 86.3 g (0.31 g-equiv) of isoalkyl (C ₁₂ -C ₁₄ ) monochloracetate; 104.5 g (1.14 g-equiv) of modified AB-17-8 anion exchange resin (in the form of a salt of the main OH ^- form of anion exchange resin with 2-hydroxypropionic acid). Received 290.0 g of the target product (90.3% conversion) as a viscous yellow liquid,

.

IR spectrum: ν _{(C = O)} = 1740-1750 cm ^-1 ; ν _(C-O-cycle) = 1115-1140 cm ^-1 ; ν _(C-Oacetate) = 1240-1260 cm ^-1 .

Elemental analysis: found,%: C 66.14; H 10.00; N 1.55; calculated,%: C 66.31; H 10.10; N 1.49.

Tests as steel corrosion inhibitors

Evaluation of the effectiveness of substances as corrosion inhibitors is carried out by the gravimetric method on steel samples St.3 in freely agitated 1 N, 0.1 N and 0.01 N hydrochloric acid solutions that are stirred. The sizes of the plates from Art. 3, their preparation and processing were carried out according to OST 39-099-79. Inhibitors were administered at a dosage of 50 mg / L in the form of 5% aqueous solutions. The protective effect of corrosion inhibitors (Z) was calculated by the formula

Z = ((P ₁ -P ₂ ) / P ₁ ) 100%

Where

P ₁ - weight loss of the steel sample after testing in hydrochloric acid medium without inhibitor, g;

P ₂ - weight loss of a steel sample after testing in hydrochloric acid medium with the addition of an inhibitor, g

The corrosion inhibition coefficient (γ) was calculated by the formula

γ = P ₁ / P ₂

The test results of substances as corrosion inhibitors are shown in the table.

As reference standards are taken: structural analogue - N, N-dimethyl-N-alkyl-N- [isononylphenoxydec (ethyleneoxy) carbonylmethyl] -ammonium chloride fraction C ₁₀ -C ₁₆ (Preparation F-761) of the formula

where R = alkyl C ₁₀ -C ₁₆ [US Pat. 1531416 RF, publ. 1995.04.10], as well as a widely used corrosion inhibitor “Catamine-A” [Ugryumov OV, Ivshin Ya.V., Fakhretdinov P.S. and others // Protection of metals. 2001.V. 37. Number 4. S.380-385].

The effectiveness of corrosion inhibitors in 1 N aqueous hydrochloric acid at a dosage of 50 mg / l No. p.p. Inhibitor Braking coefficient, γ Protective effect Z,% one Example 1 3,55 71.8 2 Example 2 3.62 72,4 3 Example 3 3.56 71.9 four Structural analogue "Preparation F-761" 1,64 39.0 5 Industrial Corrosion Inhibitor "Catamine-A" 2.49 59.8

As can be seen from the data in the table, the proposed N, N-diethyl-N- [isoalkoxycarbonylmethyl] -N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates with an average degree of hydroxyethylation equal to 6 excel in inhibitory activity in hydrochloric acid aqueous media structural analogue “Preparation F-761”, as well as the corrosion inhibitor “Catamine-A” used in the oil industry.

The proposed corrosion inhibitors can be used in acid etching of metals in metallurgy, chemical industry and heat power engineering, as well as in acid treatment of oil and gas wells to restore or increase the filtration characteristics of the bottom zone of oil or gas reservoirs in the oil and gas industry.

The proposed method for producing the claimed compounds is simple, not requiring special conditions and special equipment and can be carried out in almost any chemical production.

Claims (3)

1. N, N-Diethyl-N- [isoalkoxycarbonylmethyl] -
N- [alkylphenoxypoly (ethyleneoxy) carbonylethyl] ammonium 2-hydroxypropionates of the formula

where R ¹ = alkyl fractions C ₈ -C ₁₀ ;
R ² = isoalkyl C ₁₂ , isoalkyl fractions C ₁₂ -C ₁₄ , isoalkyl C ₁₄ ;
n = average degree of hydroxyethylation equal to 6,
possessing the properties of steel corrosion inhibitors in hydrochloric acid aqueous media obtained by the interaction of alkylphenoxypolyethylene glycols of the formula

,
where R ¹ = alkyl fractions C ₈ -C ₁₀ ;
n = average degree of hydroxyethylation equal to 6,
with methyl acrylate in the presence of an acid catalyst and a polymerization inhibitor at a temperature of 60-80 ° C, further addition of diethylamine in isopropanol at a temperature of 30-40 ° C, followed by treatment of the product of addition with isoalkyl monochloracetates of the general formula

,
where R ² = isoalkyl C ₁₂ , isoalkyl fractions C ₁₂ -C ₁₄ , isoalkyl C ₁₄ ,
and a strongly basic anion-exchange resin, which is a product of the copolymerization of styrene and divinylbenzene with quaternary ammonium groups, such as AB-17-8, in OH ^- form, modified with 2-hydroxypropionic acid, and representing an anionite salt, at a temperature of 60-80 ° С and at the following reagent ratios in g-equivalents: alkylphenoxypolyethylene glycol: methyl acrylate: diethylamine: isoalkyl monochloracetate: modified anion exchange resin = 1.0: (1.0-1.5) :( 1.0-1.1) :( 1.0-1, 04) :( 3.8-4.0). 2. The compound obtained according to claim 1, characterized in that when receiving as the acid catalyst using the H ⁺ form of the cation exchange resin KU-2-8, taken in an amount of 10-20 wt.% By weight of methyl acrylate. 3. The compound obtained according to claim 1, characterized in that upon receipt as a polymerization inhibitor use hydroquinone taken in an amount of 5.0-6.0 wt.% By weight of methyl acrylate.