JPS6393769A - Corrosion prevention for metal surface using perfluoroalkyl group-containing triazoles - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION J This invention relates to the use of perfluoroalkyl group-containing triazoles as oil-soluble corrosion inhibitors for metal surfaces and to novel triazoles containing perfluoroalkyl groups. [Prior art 1 French patent 2028493 discloses reaction products of benzotriazoles and perfluoroalkylcarboxylic acids as oil-soluble corrosion inhibitors. [Means for solving the problem] More specifically, one embodiment of this invention is as follows:
This invention relates to a method for preventing corrosion of a metal surface by treating the metal surface with a compound represented by the following formula in an amount effective for corrosion prevention 1). or in both formulas, R is a) unsubstituted or substituted with a hydroxyl group, a lower alkoxy group or a halogen, and also represents oxygen, sulfur,
an alkylene group having up to ia 18 carbon atoms, including a carboxamide group, a sulfonamide group, an aminosulfonyl group, an aminocarbonyl group, a carbonyloxy group, a sulfinyl group or a sulfonyl group, or b) an ffl-substituted group; or substituted with a hydroxyl group, a lower alkoxy group, or a halogen, and with oxygen, sulfur, a carboxamide group, a sulfonamide group, an aminocarbonyl group, an aminesulfonyl group, a carbonyloxy group, a sulfinyl group, or a sulfonyl group in between; A sulfonylaminoalkylene group or a carbonylaminoalkylene group or a sulfonylaminoaralkylene group or a carbonylaminoaralkylene group having up to a16 carbon atoms without sandwiching, and R4 is a perfluoroalkyl group having from 2 to 16 carbon atoms or from 4 to 16 carbon atoms. is a perfluoroalkoxyalkyl group having up to carbon atoms, and R, -R, is
each independently hydrogen, hydroxyl or halogen, or an alkyl, lower alkanoyloxy, lower alkoxy or lower alkanoylamino group of up to 10 carbon atoms, each of which is unsubstituted or ct -cto 7-aryl group, C, -07
a cycloalkyl group, a C3-C, azacycloalkyl group, a lower alkoxy group, a hydroxyl group, a halogen, a cyano group, or a polylower alkyleneoxy group, or a group substituted with two adjacent R, -R4 groups. The above compounds combine to form one or more carbon-bonded rings or hetero-bonded rings each consisting of 5 to 8 atoms, or a mixture thereof. Preferred R,, R2, R3 and R4 are hydrogen or lower alkyl or lower alkoxy groups which are unsubstituted or substituted as described above, with unsubstituted being more preferred. Preferably, at least one of R, to R4 is hydrogen, and most preferably, R, to R4 are hydrogen. R is an alkylene radical having preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 6 to 10 carbon atoms. R may be unsubstituted, but is preferably substituted with a hydroxyl group, and independently has one or two oxygen atoms, one sulfur atom, one carboxamide group, or one It is preferable that a sulfonamide group is sandwiched between the middle cylinders. Preferred R is a cz-ctt alkylene group that has one or two oxygen atoms or sulfur atoms independently sandwiched in the middle and is substituted with a hydroxyl group. be. Most preferred R is an alkylene group of from 6 to 10 carbon atoms substituted by hydroxyl groups and independently intervening with oxygen or sulfur. A preferred substituent for R is a hydroxyl group. In a preferred embodiment, R is a C2-CI & alkylene group substituted with a hydroxyl group, with one or two oxygen atoms or one group selected from sulfur, carboxamide groups and sulfonamide groups sandwiched between them. It is. Rf preferably has a carbon atom number of 4 to 1.
Up to 6, most preferably from 6 to 12 perfluoroalkyl groups. R1 can also be a mixture of the above perfluoroalkyl groups. The term "lower" as used throughout this specification indicates a number of carbon atoms up to 7, preferably up to 4. By the term poly lower alkyleneoxy, we mean poly(lower alkyleneoxy) which is terminated with a hydroxyl group or an alkylene group of C2-(:a,
Preferred poly-C2- having from bond to about 40 alkyleneoxy units, preferably from 3 m to 20 alkyleneoxy units.
C3 alkyleneoxy is meant. The aryl group is preferably a phenyl group or a naphthyl group. The cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group. Preferred azacycloalkyl groups are 2- or 3-
a pyrrolidinyl group such as pyrrolidinyl or 2-13-
or a piperidinyl group, such as 4-piperidinyl, in which the nitrogens are unsubstituted or substituted by lower alkyl groups, especially methyl or ethyl groups. When two adjacent R1, R2, R3 and R4 are bonded to form a bonded ring having 5 to 8 atoms, the atoms of this bonded ring may consist of carbon and/or nitrogen atoms. preferable. Suitable bonded rings, taking together each carbon atom to which R1, R2, R3 and R4 are bonded, include, for example, a benzene ring, a quinoline ring, a benzopiperazine ring, a thiadiazole ring, a thiazole ring, a naphthalene ring. and a bicyclopentadiene ring. Furthermore, three adjacent groups of R1, R2, R3 and R4 can also form a fused ring system such as 7-cenaphthylene together with the benzene ring to which these groups are bonded. Highly preferred are compounds in which R1, R2, R3 and R4 are independently hydrogen, lower alkyl or lower alkoxy; most preferred are compounds in which R2, R2, R
3 and R4 are both hydrogen. A further embodiment of this invention provides formula Ia or I
It is a compound represented by Ia. or in both formulas, R is unsubstituted or a hydroxyl group,
Substituted with a lower alkoxy group or halogen, with one or two of oxygen, sulfur, carboxamide group, sulfonamide group, aminocarbonyl group, aminosulfonyl group, carbonyloxy group, sulfinyl group or sulfonyl group independently interposed It is an alkylene group having up to 16 carbon atoms that can be sandwiched. R1 is a perfluoroalkyl group having 2 to 16 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 16 carbon atoms, and R, -R, each independently represent hydrogen, hydroxyl, or halogen; or an alkyl group, lower alkanoyloxy group, lower alkoxy group or lower alkanoylamino group having up to 10 carbon atoms, each of which is unsubstituted or crt-cto alimyl group, C4-C7 A group substituted with a cycloalkyl group, a cycloalkyl group of Ca-06, a lower alkoxy group, a hydroxyl group, a halogen, a cyano group, or a polylower alkyleneoxy group, or a group substituted with two adjacent R, -R4 groups. The above are joined to form a carbon-bonded ring or a hetero-bonded ring, each consisting of 5-8 atoms, or a mixture thereof. The preferred embodiments mentioned above also apply to the compounds mentioned above. Compounds of formula 1, Ia, (2) or IIa can be obtained by reacting a triazole represented by the following formula (2) with an epoxide represented by the following formula (2). The reaction is optionally carried out in the presence of suitable diluents or solvents such as benzene, methylene chloride, chloroform, acetone, diethyl ether, toluene and the like. Rf, R, R1, R2,
R3 and R4 are as defined above. This reaction can optionally be performed with AlCl3 or BF3 if desired.
It can be carried out in the presence of a Lewis acid such as, preferably at a temperature between about 0°C and about 120°C. Typical known epoxides within the scope of this invention include: C@Fl 7CH2CH2SCH2CH2CH2SCH
(CMx>CM20C) 12Ct bad H2 (4F17S0
2N (CzHs) CHzCH2S (CM mountain 0CR2C)
/: Father ＼H2C＠F17CH2CHISO2NHCH2
CH2CH2SCH2CH(CH3)CH20CH2C
Typical known triazoles within the scope of this invention include: \,〆- The compounds of the present invention can alternatively be produced by reacting a triazole of formula (1) with a compound represented by the following formula (2). Rf-R-X IV In this formula, X is a leaving group, and R4 and R are the same groups as defined above. Suitable leaving groups X include, for example, halogen, especially chlorine, bromine and iodine. The reaction is generally carried out by passing an inert gas, such as air or nitrogen, through the reaction mixture at a temperature between about 0°C and 120°C, or by passing an alkali or alkaline earth metal, a water thereof, carrying out the reaction in the presence of a base such as an oxide, carbonate or bicarbonate;
Alternatively, the reaction can be carried out in the presence of an amine such as ammonia, ammonium hydroxide or triethylamine, with removal of the by-product HX. Suitable compounds of formula (1) include, for example: C6F 13 CM2CR21, Ca F 57CH2
C: R21, C6Ft3CH2CH2Br, Ca
F13CH2CH2(:10CaF17CH2CH2B
r, C6FttCH2CH20CH2CH2Br
, Co F @t CH2CR25O2N HCO2
CH2B r, CeFl) CH2CR2C0NHCH
2CR2By, Co F 17 G) 12 (: R25
02C820H2B r. Ce F tt 5O2B r , Cs F ts 5
O2CI, C6FIsCH2CHzSO2C1, C, F
ISSO2F, C6F 1s CH2CR2GOCI,
C, F, 5COCI, etc. The compounds of this invention are particularly useful as oil-soluble corrosion inhibitors against corrosion of metals by corrosive acids, prines, oxidation and the like. These compounds are suitable for use in compositions containing an oil component which will come into contact with at least one of the metals listed below. The oil component is preferably selected from lubricating oils and hydrocarbon diluents such as toluene, xylene, fuel oil, acetone and the like. Suitable concentrations of compounds of H are from about 0,01 wt. to about 5 wt.2, preferably about 1),011 wt.
to about 0.1 wt. A further embodiment of this invention is a composition containing an oil component and a corrosion inhibiting effective amount of a compound of Formula I and/or ■. Metals whose corrosion is prevented by this invention include, for example, iron, steel, copper, and brass, with steel and iron being preferred. The effectiveness of compounds of formulas 1 and H as corrosion inhibitors is
It is measured by the following procedure. Corrosion test piece [SAE 1010, mild steel, cold rolled,
An abrasive article (1280 grid) was immersed in a 0.4% (wt/wt) toluene solution of this inhibitor sample for 30 minutes at room temperature.The specimen was then slowly pulled out of the solution and placed before weighing. Each weighed specimen was completely immersed in a test corrosive solution of MC (5 g HCl) in a glass jar with a total force of 110 + sf) and dried with room air for 30 minutes at room temperature. held for a period of time. The weight loss after this 4 hour period is measured. The above measurements are performed three times for each inhibitor sample. For a clearer understanding of this invention, the following explicit examples are described. All parts are by weight unless otherwise specified.

[Example 1] Penzotriazole 3.01 g (0,0252%
10. A mixture of 52.04 g of 52.04 g of toluene and toluene was heated to 80° C. until a clear liquid was obtained. Og (0,0229 mol) was added and the reaction mixture was heated to 80 °C for 3 h. Then 0.04 g of etherate of boron trifluoride was added and the reaction mixture was further heated to 80 °C. Heated for 28 hours. Removal of toluene yields a product containing a mixture of two isomers with the following structural structure and , 3, H24-C16, N8.2,
F 43.5 Measured value C%): c 37.3, H2,8
, N8.3, and F42.8.

Example 2 A mixture of 4.37 g (0,0328 mol) of tolutriazole and 77.48 g of toluene was heated to 80° C. until a clear liquid was obtained. 15. Og (0,029 e mol) was added and the reaction mixture was heated to 80 °C for 3 h. Then 0.04 g of etherate of boron trifluoride was added and the reaction mixture was further heated to 80 °C. Heated for 26 hours. Removal of the toluene yielded a product containing a mixture of isomers with the following structure confirmed by 'H-Nuclear Magnetic Resonance. And the results of elemental analysis are: Calculated values (X): C39.8, H3.5, N7.1, F
38.111 measured value C%): C41,2, H34-C
16, N7.5, F37.3.

Example 3J A mixture of 1.57 g (0,0132 mol) of benzotriazole and 24.28 g of toluene was heated to 80° C. until a clear liquid was obtained. 'z was added and the reaction mixture was heated to 80°C for 2
Then 0.04 g of boronic trifuride etherate was added and the reaction mixture heated to 80 °C.
The mixture was heated for an additional 25 hours. Solids precipitated. This solid content was collected by filtration and washed with hexane.
A pale beige product was obtained having the following structure confirmed by H-Nuclear Magnetic Resonance. The results of elemental analysis are: Calculated value m: 03B, 8, H2, 0, N8.1, F 4
8.7 Measured value C%): C3B, 7, H2,0, N8.3
, F 4!1.1 EXAMPLE 4 The compounds of the previous examples were tested as corrosion inhibitors by the method described above. Example Weight Protection rate 2
Loss m%1
2.8 ± 0.6 9'32
3.4 ± 0.1 9
13 24 ± 5 3
8 and protection rate z-(ΔHiki-ΔW8)100/4W. 6 Prefecture is the weight loss of the standard test piece ΔYellow is the weight loss of the coated test piece

Example 51 A mixture of 0.68 g (0,0054 mol) of benzotriazole and 13.40 g of chloroform was
Then 2.69 g of a compound of the following formula was added, heated to 60 °C until a clear liquid was obtained, and the reaction mixture was heated to 60 °C.
0 for 2 hours and 40 minutes. Removal of the chloroform gave a product with the following structure confirmed by 'H-Nuclear Magnetic Resonance. and [Example 81 2.10 g of benzotriazole (0,0178
A mixture of 2.44 g (0,0178 mol) of potassium carbonate and 21.80 g of acetone was heated under reflux. R'CH2CH2I (Rf is C
2-C8-(7) per7 fluoroalkyl group mixture)
9.22 g (0,0180 mol) of acetone and 3
3.40 g of the solution was added and the reaction mixture was heated under reflux for 20 hours. A clear liquid was obtained by filtration. Removal of the acetone resulted in a solid that was added to 0.40 g of hexafluoroxylene. The mixture was heated on a steam bath for 30 minutes, filtered to remove undissolved material and then placed under high vacuum (0.085 mbar). Products. It was a pale brown waxy solid having the following structure confirmed by 1H-nuclear magnetic resonance. and Example 7 The compounds of the previous examples were tested as corrosion inhibitors according to the methods described above. Example Weight Protection rate 11
″ll1z 5 27± 1020 6 24±628

[Example 8J Benzotriazole (7) 1.58 g (0,
0131-T-ru), a compound of the formula Cd1tCH2CH2SCH2CH2CH20C[(2
Cmu H2 7. A mixture of 34.24 g (7) of Og (0,0114 mol) and toluene was heated under reflux (110
Then 0.02 g of etherate of boron trifluoride was added and the reaction mixture was heated under reflux for 45 minutes. Removal of the toluene gave a product containing a mixture of two isomers with the following structure confirmed by 1H-nuclear magnetic resonance. And the results of elemental analysis are: Calculated values (X): C37.0, H2.8, N6.7, F
45.3 Measured value ($'): C37.3, H2.8, N
8.7, F 43.6. Example 3 The compound of Example 8 was tested as a corrosion inhibitor according to the method described above. Example Weight Protection rate [Example 10
] A mixture of 2.09 g (0,0175 mol) of benzotriazole and 22-12 g of toluene is
1.94 g (0,0191 mol) of triethylamine was added to Yfs heated to 80 °C until a clear liquid was obtained, followed by perfluorooctanesulfonyl fluoride in 32.0 g of hexafluoroxylene. A clear solution containing 8.81, (0,0173 mol) of This reaction mixture was heated to 80°C.
Heated for 12 hours. By removing the solvents, 1H-
A product having the following structure confirmed by nuclear magnetic resonance was obtained. [Example 11] 5 g (0,0287 mol) of toluene diisocyanate, 0.05 g (0,00 mol) of triethylamine
05 mol) and 63.72 g of toluene were mixed under nitrogen at room temperature. Cs F t
10.33 g of 3CH2CH2SH was added over 10 min and the reaction temperature reached a maximum of 29 °C. Then the reaction mixture was stirred at room temperature for 30 min. Then 13.68 g of toluene was added into A clear 80°C solution containing 3.42 g (0,0287 mol) of benzotriazole was added over a period of 13 minutes, and the reaction temperature reached a maximum of 28°C. The reaction mixture was stirred at room temperature for 45 minutes, at which point the reaction was complete as confirmed by infrared spectroscopy (lack of the N-C-0 absorption band at 22-70 cm-''). Upon removal of the compounds, a white powder product having the following structure confirmed by 13C-nuclear magnetic resonance was obtained. was tested as a corrosion inhibitor according to the method described above.Example Weight Protection Number -yr
% 1026±437 11 13±481

Claims (1)

[Scope of Claims] (1) A method for preventing corrosion of a metal surface, which comprises treating the metal surface with an effective amount of a compound represented by formula I or II. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I ▲There are mathematical formulas, chemical formulas, tables, etc.▼II [In both formulas, R is a) unsubstituted or substituted with a hydroxyl group, lower alkoxy group, or halogen; oxygen, sulfur,
an alkylene group having up to 16 carbon atoms, including cases in which a carboxamide group, a sulfonamido group, an aminosulfonyl group, an aminocarbonyl group, a carbonyloxy group, a sulfinyl group or a sulfonyl group is sandwiched therebetween; or b) unsubstituted. or substituted with a hydroxyl group, a lower alkoxy group or a halogen, and also substituted with oxygen, sulfur,
Carboxamide group, sulfonamide group, aminocarbonyl group, aminosulfonyl group, carbonyloxy group, sulfinyl group or sulfonylaminoalkylene group or carbonylaminoalkylene group or sulfonyl having up to 16 carbon atoms with or without intervening sulfonyl group; is an aminoaralkylene group or a carbonylaminoaralkylene group, R^f is a C_2-C_1_6 perfluoroalkyl group or a C_4-C_1_6 perfluoroalkoxyalkyl group, and R_1, R_2, R_3 and R_4 are each independently a) hydrogen, halogen or hydroxyl group, or b) an alkyl group, lower alkoxy group, lower alkanoyloxy group or lower alkanoylamino group having up to 10 carbon atoms, each of which is not independently substituted or C_6 -Is the group further substituted with an aryl group at C_1_0, a cycloalkyl group at C_4-C_7, an azacycloalkyl group at C_3-C_6, a lower alkoxy group, a hydroxyl group, a halogen, a cyano group, or a poly-lower alkyleneoxy group, Or two or more of R_1-R_4 are combined and each has 5-8
forms one or more bonded rings consisting of atoms,
Or a mixture of these. (2) The corrosion prevention method according to claim 1, wherein R is the unsubstituted or substituted C_1-C_1_2 alkylene group. (3) The corrosion prevention method according to claim 2, wherein R is the unsubstituted or substituted C_2-C_1_0 alkylene group. (4) The corrosion prevention method according to claim 3, wherein R is the unsubstituted or substituted C_6-C_1_0 alkylene group. (5) The R is a C_2-C_1_6 alkylene group substituted with a hydroxyl group with one or two oxygen atoms or one group selected from sulfur, a carboxamide group, and a sulfonamide group sandwiched between them. A corrosion prevention method according to claim 1. (6) The corrosion according to claim 1, wherein the R is a C_2-C_1_6 alkylene group substituted with a hydroxyl group and independently sandwiching one or two oxygen or sulfur atoms in between. Prevention method. (7) The corrosion prevention method according to claim 1, wherein the substituent in R is a hydroxyl group. (8) R^f is C_4
The corrosion prevention method according to claim 1, wherein -C_1_6 is a perfluoroalkyl group. (9) The corrosion prevention method according to claim 1, wherein R^f is a C_6-C_1_2 perfluoroalkyl group. (10) The corrosion prevention method according to claim 1, wherein at least one of R_1 to R_4 is hydrogen. (11) The corrosion prevention method according to claim 1, wherein R_1-R_4 are each hydrogen. (12) A compound represented by formula Ia or IIa. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ I a ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ IIa [In both formulas, R is a carbon atom that is unsubstituted or substituted with a hydroxyl group, lower alkoxy group, or halogen. An alkylene group or an alkenylene group up to number 16, and the alkylene group has oxygen, sulfur, a carboxamide group, a sulfonamide group, an aminocarbonyl group, an aminosulfonyl group, a carbonyloxy group, a sulfinyl group or a sulfonyl group sandwiched in between. R^f is a C_2-C_1_6 perfluoroalkyl group or a C_4-C_1_6 perfluoroalkoxyalkyl group, and R_1, R_2, R_3 and R_4 are each independently a) hydrogen, halogen or hydroxyl group, or b) an alkyl group, lower alkoxy group, lower alkanoyloxy group or lower alkanoylamino group having up to 10 carbon atoms, each of which is independently unsubstituted or a C_6-C_1_0 aryl group , C_4-C_7 cycloalkyl group, C_3-C_6 azacycloalkyl group, lower alkoxy group, hydroxyl group, halogen, cyano group, or polylower alkyleneoxy group, or adjacent to R_1-R_4 two or more of them are combined to form one or more carbon-bonded rings or hetero-bonded rings each consisting of 5 to 8 atoms, or a mixture thereof. (13) A composition comprising an oily component and a corrosion-inhibitingly effective amount of a compound of formula I and/or II.