JPH10310885A - Use of amino group-containing thiol as corrosion inhibitor for metal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high corrosion inhibiting effect even under acidic conditions and to effectively inhibit the corrosion of carbon steel by gaseous CO2 and/or gaseous H2 S by using specified mono- or polythiols as a corrosion inhibitor for a metal. SOLUTION: Thiols represented by the formula are used as a corrosion inhibitor. In the formula, R<1> -R<4> are independently H, 1-10C alkyl or an atom. group, R<1> and R<2> may bond to each other to form a hydrocarbon ring, R<3> and R<4> may bond to each other to form a hydrocarbon ring, R<5> is 8-30C straight or branched alkyl or alkenyl, R<6> is 1-30C straight or branched alkyl, 2-30C straight or branched alkenyl or -(CR<1> R<2> -CR<3> R<4> -S)n -H and (m) and (n) are 1-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal corrosion inhibitor, a composition for preventing metal corrosion, and a method for preventing metal corrosion. More specifically, the present invention relates to a metal corrosion inhibitor, a composition for preventing metal corrosion, and a method for preventing metal corrosion in the petroleum industry such as oil production, transportation, storage, and oil refining. The present invention relates to a corrosion inhibitor, a composition for corrosion prevention, and a corrosion prevention method for suppressing carbon steel corrosion by carbon dioxide gas and / or hydrogen sulfide gas in the petroleum industry such as transportation, storage and petroleum refining.

[0002]

2. Description of the Related Art At present, means for protecting metals from corrosion include:
It is mainly done by using corrosion inhibitors based on nitrogen-containing organic compounds or on phosphate esters, such as amines, quaternary ammonium derivatives, amidoamines and imidazolines.

[0003] It is known that the addition of sulfur element improves the corrosion inhibition efficiency of nitrogen-containing organic compounds (DE-A-3437936). Also, mixtures of sulfur-containing organic compounds and nitrogen-containing organic compounds have been exemplified as effective corrosion inhibitors (US-A-5,368,77).
No. 4, US Pat. No. 4,295,979; and US Pat. No. 4,446,056). In addition, compounds containing both sulfur and nitrogen in the molecule have also been reported as corrosion inhibitors: US-A-4,633.
No. 3,019 discloses compounds of the following formula as corrosion inhibitors:

[0004]

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R ₁ represents an alkyl, cycloalkyl or hydroxyalkyl group having 1 to 18 carbon atoms; R ₃ represents an alkyl group having 1 to 4 carbon atoms; and R ₅ represents a carbon element. The number represents an alkyl group of 1 to 18. Further, Movsum-Zad
z, MM); Mamedov FN; Saltanova, NR; Zafarova
Nvbuy (Dzhafarova NV) is a member of Korroz.Zashch.Neftega.
zov. Prom-sti.) (1980), (10), 8-10
Report the following compounds as corrosion inhibitors:

[0006]

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[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal corrosion inhibitor, a protective composition and a protective method which exhibit a higher corrosion inhibiting efficiency than known compounds.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on metal corrosion inhibitors having high corrosion inhibition efficiency, and have found that a group of novel compounds having higher corrosion inhibition efficiency than known compounds. In particular, it exhibits a high corrosion inhibition efficiency even under acidic conditions of pH 6 or less where metal corrosion is promoted, and is used in the petroleum industry such as oil production, transportation, storage and petroleum refining, and furthermore, carbon dioxide and / or hydrogen sulfide. A metal corrosion inhibitor that effectively suppresses the corrosion of carbon steel by gas has been discovered. Based on the above findings, the present invention has been completed.

That is, the above objects are as follows:
(D) is achieved.

(A) Mono- or poly-thiols selected from the group consisting of (i) and (ii) below: (i) Thiols of the following formula (Ia):

[0011]

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Wherein R ¹ , R ² , R ³ and R ⁴ are
Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, wherein the substituent R ¹
And R ^3, or R ² and R ⁴ may form a hydrocarbon ring with the carbon atoms of both bonded to each other; R ⁵
Represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms; and R ⁶ represents a linear or branched alkyl group having 1 to 30 carbon atoms;
Or carbon atoms straight or branched chain alkenyl group of 2 to 30, ^{or, - (CR 1 R 2 -CR} 3 R 4 -
Represents S) _n -H group; m and n each may be the same or different, represent and the same or different integer of 1 to 10, the ^{-CR 1 R 2 -CR 3 R 4} -S- chain the total number of m and n (m + n) is not more than 20; and (ii) thiols of formula (Ib):

[0013]

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Wherein R ¹ , R ² , R ³ and R ⁴ are
Are the same as defined above; R ^'5 are carbon atoms 7-29
Of a straight chain or branched chain alkyl or alkenyl group; and A, the following groups bonded to -CO- side is R ^'5 (II); or

[0015]

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The following group in which the carbon atom side is bonded to R ^'5 (II
I) represents:

[0017]

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However, x and y are each independently 0
Or represents an integer of 1 to 10 and the sum of x and y is 1 to
10 (1 ≦ x + y ≦ 10); q, r, o and p
Is the average number of —CR ¹ R ² —CR ³ R ⁴ —S— chains and may be 0, and each —CR ¹ R ² —CR ³ R ⁴ —
The S-chains may be the same or different, r may be different when x is greater than 1, p may be different when y is greater than 1,
Q + {r + o + @ p when A is a group (II)
Or q + Ａr when A is group (III) is greater than 0 and not more than 30; or at least one compound of formula (IV):

[0019]

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Where R ¹ , R ² , R ³ and R ⁴ are
An adduct to at least one compound having at least one amino group or imino group selected from the group consisting of the following (a) to (c) as defined above: (a) an adduct of the following formula (V): Aliphatic amines:

[0021]

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Wherein R ⁵ is the same as defined above;
R " ⁶ is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, or 2 to 2 carbon atoms.
Represents 30 linear or branched alkenyl groups; (b) amidoamines of the following formula (VI):

[0023]

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Wherein R ⁷ has the same meaning as R ′ ⁵ ; x and y are as defined above; and (c) imidazolines of the formula (VII):

[0025]

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Wherein R ⁸ has the same meaning as R ′ ⁵ ; and z represents an integer of 0 or 1 to 10; as a metal corrosion inhibitor.

(A) The use according to (a) above, wherein the metal corrosion inhibitor is used under acidic conditions of pH 6 or less, preferably pH 4 or less, more preferably pH 2 or less.

(C) The use according to (a) or (a) above, which is intended for use in the petroleum industry such as oil production, transportation, storage and petroleum refining.

(D) Carbon dioxide in the petroleum industry and / or
Alternatively, the use according to the above (c), for the purpose of suppressing corrosion of carbon steel due to hydrogen sulfide gas.

(E) In the formula (Ia), the total number (m + n) of m and n is 10 or less,
Use according to any of the above.

(F) In the formula (Ib), A is a group (I
Q + {r + o +} p or A when A) is a group (I)
The use according to any one of the above (A) to (E), wherein q + Δr in the case of II) is 0.5 to 10.

(G) R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ¹ and R ³ , or The use according to any one of the above (A) to (F), wherein R ² and R ⁴ may be mutually bonded to form an alkylene chain.

(G) In the formula (Ia), R ⁵ is a coconut oil fatty acid chain (copra chain) and an oleic acid chain (oleic chai chain).
n) etc.
amine), and R ⁶ is-(CR ¹ R ² -CR ³
R ⁴ —S) _n —H groups and the resulting dithiol is in the form of a mixture; or R ⁵ and R ⁶ represent the residues of a secondary complex fatty amine and (A), (a), (c), (d), (e) or (g), wherein the thiol is in the form of a mixture.
Use as described in.

[0034] In (Ke) formula (Ib), R ^'5 represents a residue of an amide of a composite fatty acid, resulting mono - or poly - thiol in the form of a mixture, wherein (a) to (g)
Use according to any of the above.

(Co) A mixture of compound (VI) and compound (VII) wherein the above adduct is composed of the product of the dehydration condensation reaction between a fatty acid and a polyamine during the production of amidoamine and the partial ring closure of the polyamine to imidazoline. The use according to any one of the above (a) to (d), which is an adduct of at least one compound of the formula (IV).

(S) Compounds of formula (IV) are ethylene sulfide, propylene sulfide, 1,2-dimethylthiirane, 2,2-dimethylthiirane, n-octylthiirane, cyclohexene sulfide, styrene sulfide and 1,2-diphenylthiirane The use according to any one of the above (A) to (D), which is selected from the group consisting of:

(S) The amine of the formula (V) is decylamine,
Undecylamine, laurylamine, myristylamine, cetylamine, stearylamine, primary amines derived from fatty acids obtained from coconut oil, primary amines derived from oleic acid, primary amines derived from fatty acids obtained from soybean oil Amines, didecylamine, diundecylamine, dilaurylamine, dimyristylamine, dicetylamine,
The above (A) to (D), which are selected from distearylamine, secondary amines derived from fatty acids obtained from coconut oil, secondary amines derived from oleic acid, and secondary amines derived from fatty acids obtained from soybean oil. (D) Use according to any of the above.

(S) Use according to any one of (a) to (d), wherein the amidoamine of the formula (VI) is selected from the following: monoamide of lauric acid with ethylenediamine; amide of lauric acid with diethylenetriamine; Amides of lauric acid with triethylenetetramine; amides of lauric acid with tetraethylenepentamine; and analogs of the above amides with stearic acid, oleic acid, fatty acids from coconut oil and fatty acids from soybean oil.

(C) The use according to any one of the above (a) to (d), wherein the imidazoline of the formula (VII) is selected from the following: 2-undecylimidazoline; 1- (2-aminoethyl) -2 -Undecylimidazoline; 1- [N-
(2-aminoethyl) -2-aminoethyl] -2-undecylimidazoline; 2-heptadecylimidazoline;
1- [2-aminoethyl) -2-heptadecylimidazoline; 1- [N- (2-aminoethyl) -2-aminoethyl] -2-heptadecylimidazoline; and imidazoline produced by the following dehydration and ring closure: Amides of lauric acid with tetraethylenepentamine; amides of stearic acid with tetraethylenepentamine; monoamides of oleic acid with ethylenediamine; amides of oleic acid with diethylenetriamine; amides of oleic acid with triethylenetetramine; olein Amide of acid with tetraethylenepentamine; Amide of coconut-derived fatty acid with triethylenetetramine; Amide of coconut-derived fatty acid with tetraethylenepentamine; Monoamide of soybean-derived fatty acid with ethylenediamine; Soybean oil Diethylene of fatty acid derived from Amides of tetraethylenepentamine soybean oil-derived fatty acids; amides of triethylenetetramine soybean oil-derived fatty acids; amides of Riamin.

In the (so) adduct, the compound of the formula (IV) is previously added in an amount of 1 to 20 mol per 1 mol of (a); and 0.5 to 30 mol per 1 mol of (b) or (c). The use according to any one of the above (A) to (D), which is added at a ratio of

(T) The use according to any one of (A) to (D) above, wherein the adduct is an adduct of 2 mol of ethylene sulfide to 1 mol of laurylamine.

(H) The use according to any one of (a) to (d) above, wherein the adduct is an adduct of about 2 to 3 mol of ethylene sulfide to 1 mol of 2-aminoethyldodecanamide. .

(T) When used in a corrosive solution composed of an oil phase, at least one of the mono- or poly-ones described in any of the above (A) to (H) in at least one organic solvent. -When used in a corrosive liquid composed of or comprising a solution of thiol and / or at least one adduct and comprising said aqueous phase or composed of an aqueous phase and an oil phase, A composition for protecting metals against corrosion, in particular carbon steel against corrosion by carbon dioxide and / or hydrogen sulfide gas in the petroleum industry, comprising a surfactant.

(T) used in a corrosive liquid composed of an oil phase, which is composed of or contains the following and the total of (A) and (B) is 100 parts by weight, A composition as described: (A) 20 to 50 parts by weight of at least one mono- or poly-thiol and / or at least one adduct according to any of the above (A) to (H); and (B) 50-80 weight of methanol, ethanol, n-
Propanol, isopropanol, n-butanol, t
-Alcohols such as butanol, heptanol, 2-ethylhexanol and cyclohexanol, glycol mono- or di-ethers such as di- or tri-ethylene glycol and polypropylene glycol, white spirits, heavy oil, petroleum fractions such as kerosene and naphtha. At least one organic solvent preferably selected from the following:

(G) composed of or containing the following, and the total of (A), (B) and (C) is 100 parts by weight, composed of an aqueous phase or composed of an aqueous phase and an oil phase (A) 20 to 40 parts by weight of at least one mono- or poly- according to any one of (A) to (H) used in a corrosive solution. (B) 40 to 20 parts by weight of at least one organic solvent preferably selected from glycol ethers, more preferably butyl glycol; and (C) 20 to 40 parts by weight of a fatty chain. At least one surfactant preferably selected from oxyethylenated derivatives of amino acids and fatty amines having the formula:

(N) treating the metal with a composition according to any of (a) to (g) above at a temperature from room temperature to 180 ° C., preferably at 120 ° C., A method of protecting carbon steel against corrosion by carbon dioxide and / or hydrogen sulfide gas, especially in the petroleum industry.

(D) The composition has a ratio of 1 to the total volume of the liquid.
The method according to (a), wherein the solution is continuously injected into the etching solution using a dosing pump at a loading of 0 to 20 ppm.

(V) the composition is 100 to 1000 ppm
Used to form a protective film for 2 hours at a rate of
The method according to (a), wherein the film may be maintained in a much smaller amount on the order of 5 ppm.

(F) A "squeeze treatment" such that the injection volume of the composition is in the range of 2-20% relative to the liquid injected into the wells as plugs.
Performing the method described in the above (n).

[0050]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.

According to one aspect of the present invention, a mono- or poly-thiol selected from the group consisting of (i) and (ii): (i) thiols of the following formula (Ia):

[0052]

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Where R ¹ , R ² , R ³ and R ⁴ are
Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, wherein the substituent R ¹
And R ^3, or R ² and R ⁴ may form a hydrocarbon ring with the carbon atoms of both bonded to each other; R ⁵
Represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms; and R ⁶ represents a linear or branched alkyl group having 1 to 30 carbon atoms;
Or carbon atoms straight or branched chain alkenyl group of 2 to 30, ^{or, - (CR 1 R 2 -CR} 3 R 4 -
Represents S) _n -H group; m and n each may be the same or different, represent and the same or different integer of 1 to 10, the ^{-CR 1 R 2 -CR 3 R 4} -S- chain the total number of m and n (m + n) is not more than 20; and (ii) thiols of formula (Ib):

[0054]

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Where R ¹ , R ² , R ³ and R ⁴ are
Are the same as defined above; R ^'5 are carbon atoms 7-29
Of a straight chain or branched chain alkyl or alkenyl group; and A, the following groups bonded to -CO- side is R ^'5 (II); or

[0056]

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The following group (II) having a carbon atom bonded to R ′ ⁵
I) represents:

[0058]

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However, x and y are each independently 0
Or represents an integer of 1 to 10 and the sum of x and y is 1 to
10 (1 ≦ x + y ≦ 10); q, r, o and p
Is the average number of —CR ¹ R ² —CR ³ R ⁴ —S— chains and may be 0, and each —CR ¹ R ² —CR ³ R ⁴ —
The S-chains may be the same or different, r may be different when x is greater than 1, p may be different when y is greater than 1,
Q + {r + o + @ p when A is a group (II)
Or q + Ａr when A is group (III) is greater than 0 and not more than 30; or at least one compound of formula (IV):

[0060]

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Where R ¹ , R ² , R ³ and R ⁴ are
An adduct to at least one compound having at least one amino group or imino group selected from the group consisting of the following (a) to (c) as defined above: (a) an adduct of the following formula (V): Aliphatic amines:

[0062]

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Wherein R ⁵ is the same as defined above;
R " ⁶ is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, or 2 to 2 carbon atoms.
Represents 30 linear or branched alkenyl groups; (b) amidoamines of the following formula (VI):

[0064]

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Wherein R ⁷ has the same meaning as R ′ ⁵ ; x and y are as defined above; and (c) imidazolines of the formula (VII):

[0066]

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However, it is provided that R ⁸ has the same meaning as R ′ ⁵ ; and z represents an integer of 0 or 1 to 10 as a metal corrosion inhibitor.

In the above formula (Ia), R ¹ , R ² , R
³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, preferably an alkyl group having 1 to 8 carbon atoms or a phenyl group, The substituents R ¹ and R ³ or R ² and R ⁴ may be mutually bonded to form a hydrocarbon ring, preferably an alkylene group, by both carbon atoms. Also,
R ⁵ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, preferably a primary complex fat such as a coco oil fatty acid chain (copra chain) and an oleic acid chain (oleic chain). Amine (primary complex fatty amine)
And R ⁶ is a linear or branched alkyl group having 1 to 30 carbon atoms, or a linear or branched alkenyl group having 2 to 30 carbon atoms, or - ^{(CR 1 R 2 -CR 3 R} 4 -S) n -H group, preferably - represents ^{(CR 1 R 2 -CR 3 R} 4 -S) n -H group, this time, the resulting dithiol It is preferably in the form of a mixture. Or according to another preferred embodiment, R
⁵ and R ⁶ are simultaneously a secondary complex fatty amine (secondary c
omplex fatty amine) (for example, coconut fatty acid chain (copra
chain)), wherein the resulting monothiol is in the form of a mixture.

In the above formula (Ib), R ¹ , R
² , R ³ and R ⁴ are the same as defined in the above formula (Ia). Also, R ^'5 represents a linear or branched alkyl or alkenyl group having a carbon number of 7 to 29, preferably represents the residue of an amide of a composite fatty acid, this time, the resulting mono - Or the poly-thiol is in the form of a mixture.

The adduct according to the invention is a mixture of the compounds (VI) and (VII) constituted by the products of the dehydration condensation reaction of fatty acids with polyamines during the preparation of amidoamines and the partial ring closure of polyamines to imidazolines. To at least one compound of formula (IV).

The compounds of the formula (IV) are preferably ethylene sulfide, propylene sulfide, 1,2-dimethylthiirane, 2,2-dimethylthiirane, n-octylthiirane, cyclohexene sulfide, styrene sulfide and 1,2-diphenyl Selected from the group consisting of Thiiran.

The amines of the formula (V) are, for example, decylamine, undecylamine, laurylamine, myristylamine, cetylamine, stearylamine, primary amines derived from fatty acids obtained from coconut oil, primary amines derived from oleic acid. Primary amines derived from fatty acids obtained from soybean oil, primary amines derived from soybean oil, didecylamine, diundecylamine, dilaurylamine, dimyristylamine, dicetylamine, distearylamine, and secondary amine derived from fatty acids obtained from coconut oil , Secondary amines derived from oleic acid and secondary amines derived from fatty acids obtained from soybean oil.

The amidoamines of the formula (VI) are preferably selected from: monoamides of lauric acid with ethylenediamine; amides of lauric acid with diethylenetriamine; amides of lauric acid with triethylenetetramine; Amides with pentamine; and analogs of the amides with stearic acid, oleic acid, fatty acids from coconut oil and fatty acids from soybean oil.

The imidazoline of the formula (VII) is preferably selected from: 2-undecylimidazoline;
1- (2-aminoethyl) -2-undecylimidazoline; 1- [N- (2-aminoethyl) -2-aminoethyl] -2-undecylimidazoline; 2-heptadecylimidazoline; 1- (2- Aminoethyl) -2-heptadecylimidazoline; 1- [N- (2-aminoethyl)
-2-aminoethyl] -2-heptadecylimidazoline; and imidazoline prepared by the following dehydration and ring closure: amide of lauric acid with tetraethylenepentamine; amide of stearic acid with tetraethylenepentamine; oleic acid Monoamide with ethylenediamine; amide of oleic acid with diethylenetriamine; amide of oleic acid with triethylenetetramine; amide of oleic acid with tetraethylenepentamine; amide of fatty acid derived from coconut oil with triethylenetetramine; Amide of fatty acid with tetraethylenepentamine; monoamide of fatty acid derived from soybean oil with ethylenediamine; amide of fatty acid derived from soybean oil with diethylenetriamine; amide of fatty acid derived from soybean oil with triethylenetetramine; derived from soybean oil Amides of tetraethylenepentamine fatty acids.

In the adduct according to the invention, the compound of formula (IV)
Is previously 1 to 20 mol per 1 mol of (a);
And 0.5 to 30 to 1 mol of (b) or (c)
It is preferable to add in a molar ratio.

The addition reaction for obtaining the product of the present invention comprises:
It is usually carried out in an organic solvent which is inert under the conditions of the reaction; however, no solvent may be used here. Specific examples of the organic solvent that can be used in the present invention include aromatic compounds such as benzene, toluene and xylene; ether compounds such as diethyl ether, ethyl isobutyl ether, tetrahydrofuran and dioxane; methanol, ethanol, n-propanol, isopropanol; alcohol compounds such as n-butanol, t-butanol, heptanol, 2-ethylhexanol and cyclohexanol; nitrile compounds such as acetonitrile and benzonitrile; amide compounds such as N, N-dimethylformamide and N-methylpyrrolidone; And dimethyl sulfoxide.

The reaction temperature is not particularly limited.
The temperature is 10 to 200 ° C, preferably 50 to 120 ° C.

Adducts which are particularly preferably used in the present invention include the following: an adduct of 2 mol of ethylene sulfide to 1 mol of laurylamine; and about 2 mol to 1 mol of 2-aminoethyldodecanamide. ~ 3 moles of ethylene sulfide adduct.

According to another aspect of the invention, at least one mono- or poly-thiol and / or at least one organic solvent according to the invention in at least one organic solvent when used in a corrosive liquid composed of an oil phase. When used in a corrosive solution composed of or containing a solution of at least one adduct and comprising the above solution, or composed of an aqueous phase and an oil phase, at least one surfactant is further used. A composition is provided for protecting metals against corrosion, in particular carbon steel against corrosion by carbon dioxide and / or hydrogen sulfide gas in the petroleum industry.

When the composition of the present invention is used in a corrosive liquid composed of an oil phase, it is composed of or contains the following, and the total of (A) and (B) is 100 parts by weight. It is preferred that: (A) 20 to 50 parts by weight of at least one mono- or poly-thiol and / or at least one adduct according to the invention; and (B) 50 to 80 parts by weight of methanol, ethanol, n-
Propanol, isopropanol, n-butanol, t
-Alcohols such as butanol, heptanol, 2-ethylhexanol and cyclohexanol, glycol mono- or di-ethers such as di- or tri-ethylene glycol and polypropylene glycol, white spirits, heavy oil, petroleum fractions such as kerosene and naphtha. At least one organic solvent preferably selected from the following:

When the composition of the present invention is used in a corrosive liquid composed of an aqueous phase or composed of an aqueous phase and an oil phase, it comprises (A): Preferably the sum of (B) and (C) is 100 parts by weight: (A) 20 to 40 parts by weight of at least one mono- or poly-thiol and / or at least one adduct according to the invention; B) 40 to 20 parts by weight of at least one organic solvent, preferably selected from glycol ethers, more preferably butyl glycol; and (C) 20 to 40 parts by weight of amino acids and fatty amines having fatty chains (tallow) Or at least one surfactant preferably selected from oxyethylenated (2 to 20 units) derivatives of coconut oil (copra).

According to yet another concept of the invention, the treatment of metals with corrosion at temperatures from room temperature to 180 ° C., preferably at 120 ° C., with metals of the invention, in particular in the petroleum industry, A method is provided for protecting carbon steel against corrosion by gas and / or hydrogen sulfide gas.

[0083]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Reference Examples and Examples, but the following Reference Examples and Examples do not limit the concept of the present invention. In Reference Examples A to T below, methods for preparing the compounds or products A to T of the present invention are described, respectively. The following abbreviations are used.

ES: Ethylene sulfide DMF: N, N-dimethylformamide AEDAM: 2-Aminoethyldodecanamide AEOAM: 2-Aminoethyloctadecanamide 1 mol of amine (a) (Reference Examples A to H and S to T) or amidoamine (b) (Reference Examples IL) or a mixture of amidoamine (b) and imidazoline (c) (Reference Examples MR) The average number of moles of ES added was determined by ¹ H-NMR analysis. Calculated on a basis.

Reference Examples AH describe the preparation of compounds of the following formula, which are obtained by adding m + n moles of ES to 1 mole of the primary amine (a) of the formula R ⁵ NH ₂ :

[0086]

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Reference Example A : R ⁵ = n—C ₁₂ H ₂₅ and the average number of m + n = 2 In a three-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 30.0 g of laurylamine ( 16
2 mmol) and 49.5 g of dioxane.
The temperature was raised to 7 ° C. and refluxed. 19.5 g (324 mmol) of ES was added dropwise to the reaction mixture obtained above while maintaining this temperature over 4 hours. After completion of the dropwise addition, the mixed compound was continuously reacted at the same temperature for 4 hours. After completion of the reaction, the obtained reaction solution was distilled, and the solvent was distilled off to obtain 48.2 g of a colorless and transparent liquid (yield: 97%).

Reference Example B : R ⁵ = n—C ₁₂ H ₂₅ and the average number of m + n = 5 Almost the same as Reference Example A in a three-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel. ES adduct of laurylamine obtained by the method of (Average number of ES additions:
2.3) 30.0 g (92 mmol), 25.0 g of acetonitrile and 5.0 g of dioxane were added, and the temperature was raised to 78 ° C. 16.6 g (276 mmol) of ES was added dropwise over 40 minutes to the reaction mixture obtained above, maintaining this temperature. After completion of the dropwise addition, the mixed compound was continuously reacted at the same temperature for 3.5 hours. After the completion of the reaction, the obtained reaction solution was returned to room temperature, and 4.8 g of a white solid insoluble in the solvent was removed by filtration. The filtrate was distilled and the solvent was distilled off, yielding 40.5 g of a pale yellow, waxy product (87% yield).

[0089] Reference Example ^{C: R 5 = n-C} 18 H 37 and m + n
Average number = 2.3 As a reaction raw material, 30.8 g of stearylamine (111
Mmol) and 25.4 g (423 mmol) of ES, and 44.7 g of dioxane as solvent.
By performing the reaction in the same manner as in Reference Example A, 44.0 g of a white wax-like product was obtained (78% yield).

Reference Example D : R ⁵ = n—C ₁₈ H ₃₇ and m + n
The average number of m + n is 4.85 by operating as in Reference Example C with more ESs.
I got

Reference Example E : R ⁵ = coconut oil fatty acid chain (coprah
chain) and the average number of m + n = 2 As a reaction raw material, aliphatic primary amine derived from coconut oil (total amine 4.98 meq / g by non-aqueous titration) 25.
0 g (124 mmol) and ES 28.4 g (47
2 mmol) and 53.4 g of dioxane as a solvent.
The reaction was carried out in the same manner as in Reference Example A, except that was used, to obtain 38.9 g of a slightly cloudy liquid (yield 73
%).

Reference Example F : R ⁵ = coconut oil fatty acid chain (coprah
chain) and the average number of m + n = 4.6. The above product was obtained by operating as in Reference Example E using more ES.

Reference Example G : R ⁵ = oleic acid chain (oleic cha)
in) and the average number of m + n = 1.9 As a reaction raw material, an aliphatic primary amine derived from oleic acid (total amine 3.69 meq / g by non-aqueous titration) 2
5.0 g (92 mmol) and ES 13.8 g (2
The reaction was carried out in the same manner as in Reference Example A, except that 38.8 g of dioxane was used as a solvent, thereby obtaining 36.3 g of a red-brown liquid (94% yield).

Reference Example H : R ⁵ = oleic acid chain (oleic cha)
in) and the average number of m + n = 4.8. The above product was obtained by operating as in Reference Example G with more ES.

The following Reference Examples IL illustrate the preparation of adducts obtained by adding p moles of ES to 1 mole of the amidoamine (b) of the formula:

[0096]

Embedded image

Reference Example I : R ⁷ = nC ₁₁ H ₂₃ ; average number of p = 2.7 5 equipped with a stirrer, thermometer and Dimroth type cooler
AEDAM 60.0 g in a 00 ml four-necked flask
And 180 g of dioxane, and the temperature was raised to 101 ° C. while maintaining a nitrogen atmosphere. While maintaining this temperature, 44.6 g of ES (A) placed in a dropping funnel was added into this solution.
(EDAM / ES = 1 / 3.0 molar ratio) was added dropwise over 7 hours. After the completion of the dropwise addition, the reaction was continued at the same temperature for 1.5 hours. After completion of the reaction, the reaction solution was cooled to room temperature and filtered to remove a small amount of insolubles (0.3 g). The filtrate was distilled under reduced pressure to remove the solvent by volatilization to obtain 98.8 g of a pale yellow wax-like product (yield: 95%).

Reference Example J : R ⁷ = nC ₁₁ H ₂₃ ; average number of p = 5.6 2 equipped with a stirrer, thermometer and Dimroth type cooler
In a 00 ml four-necked flask, 38.0 g of the product obtained in Reference Example I, 57 g of DMF, and 57 g of dioxane were added, and the temperature was raised to 101 ° C. while maintaining a nitrogen atmosphere. While maintaining this temperature, 16.9 g of ES put in a dropping funnel was dropped into this solution over 2.5 hours.
After completion of the dropwise addition, the reaction was performed at the same temperature for 0.5 hour. After completion of the reaction, the reaction solution was cooled to room temperature and filtered to remove a very small amount of insolubles. The filtrate was distilled under reduced pressure to remove the solvent by evaporation, thereby obtaining 54.6 g of a pale yellow wax-like product (yield: 99%).

Reference Example K : R ⁷ = nC ₁₇ H ₃₅ ; average number of p = 2.7 5 equipped with a stirrer, thermometer and Dimroth type cooler
AEOAM 80.0 g in a 00 ml four-necked flask
And 240 g of dioxane, and the temperature was raised to 103 ° C. while maintaining a nitrogen atmosphere. While maintaining this temperature, 36.8 g of ES (A
(EOAM / ES = 1 / 2.5 molar ratio) was added dropwise over 4 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 7 hours. After completion of the reaction, the reaction solution was subjected to vacuum distillation to evaporate the solvent by volatilization, and then concentrated to about a half amount. An insoluble substance was precipitated, and this was removed by filtration (21.5 g). The filtrate was distilled under reduced pressure to evaporate off the solvent, and 94.0 g of a pale yellow wax-like product was obtained.
Was obtained (80% yield).

Reference Example L : R ⁷ = nC ₁₇ H ₃₅ ; average number of p = 5.5 2 equipped with a stirrer, thermometer and Dimroth type cooler
In a 00 ml four-necked flask, 40.0 g of the product obtained in Reference Example K, 60 g of DMF and 60 g of dioxane were added, and the temperature was raised to 105 ° C. while maintaining the nitrogen atmosphere. While maintaining this temperature, 14.7 g of ES placed in a dropping funnel was dropped into this solution over 2 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 0.5 hour. After the reaction,
The reaction solution was subjected to vacuum distillation to evaporate the solvent to obtain 54.6 g of a pale yellow wax-like product (yield: 99%).

The following Reference Examples MR illustrate the preparation of adducts of ES to the product (d) obtained by condensation and dehydration of fatty acids and polyamines, as shown in Table 1 below:

[0102]

[Table 1]

Reference Example M 5 equipped with a stirrer, thermometer and Dimroth type cooler
Product (d1) 68.3 in a 00 ml four-necked flask
g (active amine hydrogen equivalent: 339.1 milliequivalents) and 273.3 g of dioxane.
The temperature was raised to 02 ° C. While maintaining this temperature, 21.3 g (equivalent) of ES placed in a dropping funnel was added into this solution.
Was added dropwise over 5 hours. After the completion of dropping, at the same
Allowed to react for hours. After completion of the reaction, the reaction solution was cooled to room temperature and filtered to remove insolubles (12.1 g). The filtrate is vacuum distilled to evaporate off the solvent and give a pale yellow, waxy product 7
7.5 g were obtained (86% yield).

The product (d1) 1 was obtained from ¹ H NMR analysis.
The average number of moles of ES added per mole was 0.7, indicating that the resulting product had an imidazoline content of 74% by weight.

Reference Example N 5 equipped with a stirrer, a thermometer and a Dimroth type cooler
In a 00 ml four-necked flask, 70.6 of the product (d2) was added.
g (active amine hydrogen equivalent: 756.1 milliequivalents) and 280 g of dioxane.
The temperature was raised to ° C. While maintaining this temperature, 45.4 g of ES placed in a dropping funnel was dropped into this solution over 6 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour.
After the completion of the reaction, the reaction solution was returned to room temperature, and filtered to remove insolubles (3
2.3 g) were removed. The filtrate was vacuum distilled to evaporate off the solvent to give 83.2 g of a yellow, waxy product (yield 72).
%).

From the ¹ H NMR analysis, it was found that the product (d2) 1
The average number of moles of ES added per mole was 1.8, indicating that the resulting product had an imidazoline content of 61% by weight.

Reference Example O 5 equipped with a stirrer, thermometer and Dimroth type cooler
The product (d3) 65.0 was placed in a 00 ml four-necked flask.
g (active amine hydrogen equivalent: 929.0 meq.) and dioxane (267.5 g) were added.
The temperature was raised to 02 ° C. While maintaining this temperature, 55.9 g of ES put in a dropping funnel was dropped into this solution over 6 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 0.5 hour. After the completion of the reaction, the reaction solution was returned to room temperature and filtered to remove insolubles (28.6 g). The filtrate was distilled under vacuum to remove the solvent by volatilization to obtain 92.1 g of a yellow turbid liquid product (yield: 76%).

The product (d3) 1 was obtained from ¹ H NMR analysis.
The average number of moles of ES added per mole was 2.5, indicating that the resulting product had an imidazoline content of 26% by weight.

Reference Example P 5 equipped with a stirrer, a thermometer and a Dimroth type cooler
In a 00 ml four-necked flask, 75.7 the product (d4) was added.
5 g (active amine hydrogen equivalent: 929.0 meq) and dioxane (303.9 g) were added, and the temperature was raised to 102 ° C while maintaining a nitrogen atmosphere. While maintaining this temperature, 48.6 g of ES placed in a dropping funnel was dropped into this solution over 5 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 0.5 hour. After completion of the reaction, the reaction solution was returned to room temperature and filtered to remove insolubles (36.4 g). The filtrate was vacuum distilled to remove the solvent by evaporation, and 87.7 g of a yellow turbid liquid product was obtained.
Was obtained (yield 71%).

From ¹ H NMR analysis, it was found that the product (d4) 1
The average number of moles of ES added per mole was 1.3, indicating that the resulting product had an imidazoline content of 64% by weight.

Reference Example Q 5 equipped with a stirrer, a thermometer and a Dimroth type cooler
In a 00 ml four-necked flask, 71.6 of the product (d5) was added.
g (active amine hydrogen equivalent: 537.1 milliequivalents) and 286.4 g of dioxane.
The temperature was raised to 04 ° C. While maintaining this temperature, 48.4 g of ES placed in a dropping funnel was dropped into this solution over 7 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. After the completion of the reaction, the reaction solution was returned to room temperature and filtered to remove insolubles (39 g). The filtrate was subjected to vacuum distillation to evaporate the solvent to obtain 79.8 g of a yellow turbid liquid product (yield: 67%).

From ¹ H NMR analysis, it was found that the product (d5) 1
The average number of moles of ES added per mole was 1.2, indicating that the resulting product had an imidazoline content of 68% by weight.

REFERENCE EXAMPLE R 5 equipped with a stirrer, thermometer and Dimroth type cooler
The product (d6) 73.1 was placed in a 00 ml four-necked flask.
g (active amine hydrogen equivalent: 862.5 milliequivalents) and 291.4 g of dioxane.
The temperature was raised to 03 ° C. While maintaining this temperature, 52.0 g of ES put in the dropping funnel was dropped into this solution over 5 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, the reaction solution was returned to room temperature and filtered to remove insolubles (40.5 g). The filtrate was subjected to vacuum distillation to evaporate the solvent, thereby obtaining 84.1 g of a yellow turbid liquid product (yield: 67%).

From ¹ H NMR analysis, it was found that the product (d6) 1
The average number of moles of ES added per mole was 1.8, indicating that the resulting product had an imidazoline content of 74% by weight.

In the following Reference Examples S and T, mmol of ES was added to 1 mol of the secondary amine (a) of the formula R ⁵ R ^"6 H wherein R ⁵ = R ^{" 6} = coconut fatty acid chain. Illustrates the preparation of a compound of the formula:

[0116]

Embedded image

Reference Example S : Average number of m = 1.7 As a reaction raw material, an ES adduct of an aliphatic secondary amine derived from coconut oil obtained by a method similar to that of Reference Example A (average E
The reaction was carried out in the same manner as in Reference Example A, except that 30.0 (65 mmol) of ES and 0.78 g (130 mmol) of ES were used, and 18.9 g of dioxane and 18.9 g of DMF were used as solvents. By doing
31.8 g of a cloudy liquid was obtained (84% yield).

Reference Example T : The above product was obtained by operating in the same manner as in Reference Example S using an ES having an average number of m less than 1.

Example 1 The effects of Compounds A to T on inhibiting corrosion of carbon steel were as follows:
Tafel plots `` Structural Effect of Quaternary Ammonium Group on Inhibition on Steel (Structural
effect of quaternary ammonium group on inhibition
on steel), D. Bernard, M. Haim and TE Pou,
Proceeding of the 6th European Symposium on Cor
rosion Inhibitors) (6SEIC), Ann Univ. Ferrara, NS, Sezbui, Sapuru N8 (Ann. Un
iv. Ferrara, NS, Sez. V, Suppl. N.8), p. 149
7, 1985) by measuring the instantaneous corrosion rate of a test piece made from carbon steel.

The test consisted of 600 ml of heat-resistant glass (Pyrex) having the following three electrodes fixed to the cell by gas inlet, gas outlet and rubbing:
A working electrode made of carbon steel with a contact area of 1 cm ² with the corrosive liquid; a saturated Mel reference electrode; and a platinum counter electrode with a very large contact area with the solution.

The cell was filled with 500 ml of the corrosive liquid. The etchant was a 50 g / liter solution of NaCl and 0.1 g / l.
Consists of 25 g / l acetic acid. Next, a counter electrode and a reference electrode were inserted. The solution was degassed by bubbling with nitrogen for 1 hour and the solution was saturated by bubbling with either CO ₂ or H ₂ S for an additional hour, depending on the type of corrosion being investigated. The test was performed at room temperature.

Compounds AT were used dissolved or dispersed in isopropyl alcohol until added to the etchant.

In conducting each test, a solution or dispersion of the test compound was added to the corrosive solution to a constant concentration. Next, the measurement electrode is immersed in the above-mentioned corrosion liquid. Measure the corrosion potential. When the corrosion potential has stabilized, the experiment is started according to the following parameters: starting potential = −1000 mV with respect to the potential of the reference electrode Final potential = 100 mV with respect to the corrosion potential Sweep of potential = 1 mV / sec The corrosion current (i _corr ) is applied to the anode and It is measured by the intersection of the Tafel plot (see references above) of the cathode.

Protection rate (% P) indicating the corrosion inhibition rate of the compound
Is as follows:% P = (i ⁰ _corr− i _corr / i ⁰ _corr ) × 100 where i ⁰ _corr represents the corrosion current without inhibitor; and i _corr is a constant amount of It represents the corrosion current in the presence of the inhibitor.

The protection rates (% P) obtained with the various compounds at concentrations of 1 to 200 ppm are shown in Table 2. These results indicate that Compounds A, E and I are effective.

[0126]

[Table 2]

Example 2 The procedure of Example 1 was repeated, except that H ₂ S was used instead of CO ₂ .

The protections (% P) obtained with the various compounds at concentrations of 1 to 200 ppm are shown in Table 3. These results indicate that Compounds A, H and I are effective.

[0129]

[Table 3]

Example 3 The effects of Compounds A and I on inhibiting corrosion of steel sheets under acidic conditions were evaluated as follows.

First, Compounds A and I, and laurylamine (Structural Formula C ₁₂ H ₂₅ NH ₂ ; manufactured by Wako Pure Chemical Industries, Ltd.) and Nimeen L202 [Structural Formula C ₁₂ H ₂₅ N
(C ₂ H ₄ OH) ₂ ; manufactured by NOF CORPORATION]
g was added to a beaker containing 100 g of a 5N HCl aqueous solution in advance, and then the beaker was placed in an ultrasonic washer (manufactured by Shibata Kagaku Kikai Co., Ltd., SU-3TH type). Sonicate for 1 min
A sample solution was prepared by uniformly dispersing in an aqueous solution. The pH of this sample solution was 1 or less.

A steel plate (JIS G 3141 (SPCC-
SB); Cold-rolled steel sheet (1.0 × 30 × 50 mm) is immersed in acetone, subjected to the same ultrasonic treatment as described above, washed with acetone, thoroughly wiped the steel sheet surface with a Kim towel, and weighed the steel sheet. Weigh it, and let this be the weight before the steel sheet (g). Next, the steel plate was immersed in the sample solution and left at room temperature for 5 hours. After a predetermined time, the steel sheet is taken out of the sample liquid, immersed in ion-exchanged water, subjected to the same ultrasonic treatment as described above, washed with ion-exchanged water and acetone in this order, and weighed at this time. This is referred to as (g) after the weight of the steel sheet. Before the steel sheet weight (g) to after the steel sheet weight (g)
Minus the weight (g) [(before steel sheet weight (g))-
(After the weight of the steel sheet (g)) = reduced weight (g)], and the corrosion prevention rate (%) was calculated from the reduced weight by the following equation. The weight loss (g) when no sample was charged was 0.1 g.
4,652 g.

[0133]

(Equation 1)

The results of each sample are shown in Table 4 below.

[0135]

[Table 4]

Table 4 shows that compounds A and I according to the invention
Are laurylamine and Nymin L as comparison controls
The corrosion inhibition rates of 202 were 93.7% and 84.3%, respectively.
%, It shows an excellent corrosion inhibition rate of nearly 99% even under a very strong acidic condition of pH 1 or less.

Example 4 Preparation of Composition for Protecting Carbon Steel A composition having the following composition was prepared.

[0138]

[Table 5]

The composition, which is oil-soluble and water-dispersible, has a proportion of from 10 to 20 ppm, based on the total liquid volume,
A dosing pump can be used to continuously inject into the etchant.

The above composition is kept at 100 to 1 for 2 hours.
It can be used to form a protective film at a rate of 000 ppm. The film is further reduced in considerably smaller quantities (5p
pm order).

"Squeeze" processing ("squeeze" treatmen)
In t), the amount of composition injected is in the range of 2-20% relative to the liquid injected into the wells as plugs.

[0142]

As described above, the present invention provides a compound of the formula (Ia)
Or a mono- or poly-thiol selected from thiols of the formula (Ib) and at least one selected from the group consisting of aliphatic amines, amidoamines of the formula (VI) and imidazolines of the formula (VII) Wherein an adduct obtained by adding at least one compound of the formula (IV) to the at least one compound having an amino group or an imino group and the formula (V) is used as a metal corrosion inhibitor.

Mono- or poly-thiols selected from thiols of the formula (Ia) and thiols of the formula (Ib) according to the invention, or aliphatic amines, amidoamines of the formula (VI) and amides of the formula (VII) An adduct obtained by adding at least one compound of formula (IV) to at least one compound having formula (IV) to at least one compound having at least one amino group or imino group selected from the group consisting of imidazolines exhibits high corrosion inhibition efficiency Accordingly, a metal corrosion inhibitor and a protective composition having high corrosion inhibition efficiency can be obtained.

Further, mono- or poly-thiols selected from the thiols of the formula (Ia) and the thiols of the formula (Ib) according to the present invention, or the aliphatic amines of the formula (V)
At least one compound having at least one amino group or imino group selected from the group consisting of amidoamines of I) and imidazolines of formula (VII) has the formula (IV)
The adduct obtained by adding the formula (V) to at least one compound of the formula (1) exhibits an excellent corrosion inhibition rate even under acidic conditions of pH 6 or less, which generally promote metal corrosion. Therefore,
The corrosion inhibitor and the protective composition according to the present invention have a pH of 6
Exhibits high corrosion inhibition efficiency under the following acidic conditions.

Furthermore, mono- or poly-thiols selected from the thiols of the formula (Ia) and the thiols of the formula (Ib) according to the present invention, or the aliphatic amines of the formula (V)
At least one compound having at least one amino group or imino group selected from the group consisting of amidoamines of I) and imidazolines of formula (VII) has the formula (IV)
An adduct obtained by adding at least one compound of the formula (V) effectively inhibits metal corrosion by carbon dioxide gas and / or hydrogen sulfide gas. Therefore, by using the corrosion inhibitor and the protective composition according to the present invention, it is possible to exhibit a high corrosion inhibition efficiency, and to produce a metal against corrosion, particularly carbon dioxide and gas in the petroleum industry such as oil production, transportation, storage and petroleum refining. And / or a composition for protecting carbon steel from corrosion by hydrogen sulfide gas.

Furthermore, by treating the metal with the composition of the present invention, it is possible to efficiently protect the metal against corrosion, particularly the carbon steel against the corrosion due to carbon dioxide and / or hydrogen sulfide gas in the petroleum industry. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Tomita 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Daniel Bernard France 92400 Courbevoie-Ru-Pierre Brossollette 11 (72) Inventor Tong Eak Poe France 95800 Courdimanche Chemin de Luoisler 1

Claims (24)

[Claims] 1. A mono- or poly-thiol selected from the group consisting of the following (i) and (ii): (i) Thiols of the following formula (Ia): However, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, wherein the substituents R ¹ and R ³ ,
Or R ² and R ⁴ may combine with each other to form a hydrocarbon ring with both carbon atoms; R ⁵ is a linear or branched alkyl or alkenyl having 8 to 30 carbon atoms. And R ⁶ has from 1 to 3 carbon atoms.
0 straight-chain or branched-chain alkyl group, or straight-chain or branched-chain alkenyl group having 2 to 30 carbon atoms, or-(CR ¹ R ² -CR ³ R ⁴ -S) _n- Represents an H group; m and n each represent an integer of 1 to 10 and may be the same or different, and are the same or different;
The total number of m and n (m + n) in the CR ¹ R ² —CR ³ R ⁴ —S-chain is 20 or less; and (ii) thiols of the following formula (Ib): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as defined above; R ′ ⁵ represents a linear or branched alkyl or alkenyl group having 7 to 29 carbon atoms; and a is represented by the following group (II) which binds to -CO- side is R ^'5; or embedded image Represents the following group (III) in which the carbon atom side is bonded to R ^'5: embedded image However, x and y are each independently 0 or 1-1.
Represents an integer of 0 and the sum of x and y is 1 to 10 (1 ≦ x
+ Y ≦ 10); q, r, o and p are -CR ¹ R
² -CR ³ the average number of R ⁴ -S- chain, may be 0, each ^{-CR 1 R 2 -CR 3 R 4} -S- chain is a is also or different have the same When x is greater than 1, r may be different; when y is greater than 1, p may be different; and when A is a group (I
Q + {r + o +} p or A when A) is a group (I)
Q + Σr when II) is greater than 0 and not more than 30; or at least one compound of the following formula (IV): However, R ¹ , R ² , R ³ and R ⁴ are at least one amino group or at least one amino group having at least one amino group selected from the group consisting of the following (a) to (c) as defined above. Adducts to compounds: (a) Aliphatic amines of formula (V): Provided that R ⁵ is the same as defined above; R ″ ⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, or a straight-chain or branched alkyl group having 2 to 30 carbon atoms. (B) amidoamines of the following formula (VI): Wherein R ⁷ has the same meaning as R ′ ⁵ ; x and y
Is as defined above; and (c) imidazolines of formula (VII): Wherein R ⁸ has the same meaning as R ′ ⁵ ; and z
Represents 0 or an integer from 1 to 10; use of the metal as a corrosion inhibitor. 2. Use according to claim 1, wherein the metal corrosion inhibitor is used under acidic conditions of pH 6 or less. 3. Use according to claim 1 or 2 for use in the petroleum industry. 4. The use according to claim 3, wherein the carbon steel and / or hydrogen sulfide gas is used in the petroleum industry to suppress corrosion of carbon steel. 5. The use according to claim 1, wherein in formula (Ia) the total number of m and n (m + n) is 10 or less. 6. In formula (Ib), q + {r + o +} p when A is a group (II) or A is a group (III)
And q + Σr is 0.5 to 10 when
The use according to any one of claims 1 to 5. 7. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ¹ and R ³ or R
² and R ⁴ may form an alkylene chain bonded to each other, use of any of claims 1-6. 8. In the formula (Ia), R ⁵ represents a residue of a primary complex fatty amine, and R ⁶ represents — (CR ¹ R ² —CR
³ R ⁴ —S) _n —H groups and the resulting dithiol is in the form of a mixture; or R ⁵ and R ⁶ represent the residues of secondary complex fatty amines and the resulting monothiol is in the form of a mixture. The use according to claim 1, 2, 3, 4, 5, or 7, wherein 9. A compound according to claim 1, wherein in formula (Ib), R ′ ⁵ represents the residue of an amide of a complex fatty acid and the resulting mono- or poly-thiol is in the form of a mixture. Use of. 10. A mixture of compound (VI) and compound (VII) wherein the adduct comprises a product of a dehydration condensation reaction between a fatty acid and a polyamine upon production of an amidoamine and partial ring closure of the polyamine to imidazoline. Is an adduct of at least one compound of formula (IV)
4. Use according to any of 4. 11. The compound of formula (IV) is derived from ethylene sulfide, propylene sulfide, 1,2-dimethylthiirane, 2,2-dimethylthiirane, n-octylthiirane, cyclohexene sulfide, styrene sulfide and 1,2-diphenylthiirane. The use according to any one of claims 1 to 4, which is selected from the group consisting of: 12. The amine of formula (V) is decylamine, undecylamine, laurylamine, myristylamine,
Cetylamine, stearylamine, primary amines derived from fatty acids obtained from coconut oil, primary amines derived from oleic acid, primary amines derived from fatty acids obtained from soybean oil, didecylamine, diundecylamine, diamine Laurylamine, dimyristylamine, dicetylamine, distearylamine, secondary amines derived from fatty acids obtained from coconut oil, secondary amines derived from oleic acid, and secondary amines derived from fatty acids obtained from soybean oil The use according to any one of claims 1 to 4, wherein the use is selected from the group consisting of: 13. The use according to claim 1, wherein the amidoamine of the formula (VI) is chosen from: monoamides of lauric acid with ethylenediamine; amides of lauric acid with diethylenetriamine; Amides with ethylenetetramine; amides of lauric acid with tetraethylenepentamine; and stearic acid,
Analogs of the amide with oleic acid, fatty acids from coconut oil and fatty acids from soybean oil. 14. The use according to claim 1, wherein the imidazoline of the formula (VII) is selected from:
-Undecylimidazoline; 1- (2-aminoethyl)
1- [N- (2-aminoethyl) -2-aminoethyl] -2-undecylimidazoline; 2-heptadecylimidazoline; 1- (2-
Aminoethyl) -2-heptadecylimidazoline; 1-
[N- (2-aminoethyl) -2-aminoethyl] -2
-Heptadecyl imidazoline; and imidazolines prepared by the following dehydration and ring closure: amides of lauric acid with tetraethylenepentamine; amides of stearic acid with tetraethylenepentamine; monoamides of oleic acid with ethylenediamine; Amide with diethylenetriamine; Amide of oleic acid with triethylenetetramine; Amide of oleic acid with tetraethylenepentamine; Amide of coconut oil-derived fatty acid with triethylenetetramine; Monoamide of soybean oil-derived fatty acid with ethylenediamine; amide of soybean oil-derived fatty acid with diethylenetriamine; amide of soybean oil-derived fatty acid with triethylenetetramine; soybean oil-derived fatty acid tetraethylene Amides of Ntamin. 15. In the adduct, the compound of the formula (IV) is previously added in an amount of from 1 to 20 mol per mol of (a); and from 0.5 to 30 mol per mol of (b) or (c). Use according to any of the preceding claims, added in proportions. 16. The use according to claim 1, wherein the adduct is an adduct of 2 mol of ethylene sulfide to 1 mol of laurylamine. 17. Use according to any of the preceding claims, wherein the adduct is an adduct of about 2-3 mol of ethylene sulfide to 1 mol of 2-aminoethyldodecanamide. 18. The method according to claim 1, wherein when used in a corrosive liquid composed of an oil phase, at least one organic solvent is used.
A solution of at least one mono- or poly-thiol and / or at least one adduct according to any of claims 17 to 17 in a corrosive liquid composed of an aqueous phase or composed of an aqueous phase and an oil phase. A composition for protecting metals against corrosion, which when used further comprises at least one surfactant. 19. The composition according to claim 18, which is used in a corrosive liquid composed of an oil phase, comprising: (A) and (B), wherein the sum of (A) and (B) is 100 parts by weight: 20) 50 parts by weight of at least one mono- or poly-thiol and / or at least one adduct according to any of claims 1 to 17; and (B) 50 to 80 parts by weight of at least one organic solvent. . 20. Use in a corrosive liquid composed of an aqueous phase or composed of an aqueous phase and an oil phase, comprising: (A), (B) and (C), the sum of which is 100 parts by weight. A composition according to claim 18, wherein: (A) 20 to 40 parts by weight of at least one mono- or poly-thiol and / or at least one adduct according to any of claims 1 to 17; (B) 40 to 20 parts by weight of at least one organic solvent; and (C) 20 to 40 parts by weight of at least one surfactant. 21. A method of protecting a metal against corrosion, comprising treating the metal with a composition according to any of claims 18 to 20 at a temperature from room temperature to 180 ° C. 22. The composition according to claim 1, wherein said composition comprises 10
22. The method according to claim 21 wherein the metering pump is continuously injected into the etchant at a loading of ~ 20 ppm. 23. A composition comprising 100 to 1000 p for 2 hours.
22. The method of claim 21, wherein the method is used to form a protective film at a rate of pm, wherein the film may be maintained in fairly small amounts. 24. The method according to claim 21, wherein the “squeezing” process is performed such that the injection amount of the composition is in the range of 2 to 20% with respect to the liquid injected into the well as the plug. .