JPH0416459B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to fluorinated compounds and lubricants, and in particular to novel fluorinated compounds that can be used as antiwear additives for lubricants. BACKGROUND OF THE INVENTION It is known to add organic fluorine derivatives to lubricants for the purpose of improving wear resistance. For example, French Patent No. 2520377 proposes adding amines or amino alcohols with polyfluorinated chains. Addition of these compounds improves wear resistance and significantly reduces wear. However, due to the high volatility of these compounds, their effectiveness decreases over time. Therefore,
The use of these compounds is often restricted. Means for Solving the Problems The present inventors have discovered that the above problems can be substantially overcome by using a compound corresponding to the following general formula () as a fluorinated antiwear additive: [where R _F represents a perfluoroalkyl group having 2 to 20 carbon atoms, and X represents one of the following divalent bonds: -(CH ₂ CF ₂ ) _a (CH ₂ ) _b - - CF=CHCH ₂ − −CFHCH ₂ CH ₂ − (here, a represents an integer from 0 to 10, and b represents an integer from 1 to 4
(but equals 2 when a is other than 0) R ₁ represents a hydrogen atom or a straight or branched chain alkyl group having 1 to 12 carbon atoms, R ₂ represents a hydrogen atom or represents a methyl group, and R ₃ represents a straight-chain or branched-chain alkyl group having 1 to 24 carbon atoms]. Particularly preferred compounds of formula () are:
R _F is a linear perfluoroalkyl group having 6 to 16 carbon atoms, and X is -CH ₂ CH ₂ -, -CF=
CHCH ₂ − or −CFCH ₂ CH ₂ − bond with R ₁
A compound in which R ₂ is a hydrogen atom and R ₃ is an alkyl group having 8 to 18 carbon atoms. In the present invention, a single compound of formula () or a mixture of these compounds can be used. For economic reasons, it is particularly advantageous to use technical mixtures of various compounds in which R _F , X and/or R ₃ differ from one another. Generally, compounds of formula () are of formula (): The amino alcohol represented by the following formula (): (However, in the above two general formulas, R _F , R ₁ ,
(same as the above definitions of R ₂ and R ₃ ). The addition of unfluorinated amines to α,β-unsaturated esters or amides has long been known [e.g., J.Chem.Soc. (1970) 343
and p. 469, J. Amer. Chem. Soc. (1949) p. 2533]. These known methods can be applied to the condensation of amino alcohols of formula () with esters of formula (). This condensation is carried out in particular at temperatures of 20 to 120°C, preferably 20 to 80°C. Although it can be carried out without a solvent, it is preferable to carry out the process in a solvent for the ester and amino alcohol used. The solvent is preferably a (C ₁ to _{C 4} ) lower alcohol,
It is also possible to choose among ethers, nitriles and mixtures thereof (especially ether/acetonitrile mixtures). Although the condensation can be carried out satisfactorily without a catalyst, the reaction may be accelerated by adding an acid catalyst such as acetic acid or sulfuric acid. Fluorinated amino alcohol () and ester () are generally used in approximately equimolar amounts, but in the case of an ester () with a low boiling point (for example, methyl acrylate), it is advantageous to use an excess amount of ester as a reaction solvent. be. This excess amount is limited to up to 5 moles per mole of amino alcohol, and after the reaction is removed by distillation under atmospheric pressure or vacuum. Formula () in which R ₃ is a lower (C ₁ - C ₄ ) alkyl group
A compound of formula () in which R ₃ is a long-chain (C ₅ -C ₂₄ ) alkyl group can also be produced by transesterifying the compound with a long-chain alcohol. In a particular embodiment of the invention, the ester ()
The condensation of amino alcohol () and ester () can be carried out in a state in which ester () is insufficient. This shortfall is assumed to be up to half of the theoretical amount. In this case, a mixture is obtained which, in addition to compound (), contains up to 50% of the starting amino alcohol. This mixture can also be used as an antiwear additive for lubricants. Therefore, this mixture is also included in the present invention. Also included in the invention are more complex mixtures obtained from technical mixtures of amino alcohols () and/or esters (). Examples of esters of formula () include methyl, n-butyl, 2 of acrylic acid or methacrylic acid.
Examples include -ethylhexyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-octadecyl, with acrylate being particularly preferred. Amino alcohols () other than compounds in which X is a _-CFHCH2CH2- bond are known substances (e.g. French Patent No. _1532284 and its Additional Patents No. 93170, No. 95059, No. 2102753 and U.S. Pat. (See No. 3535381). These compounds are iodinated derivatives represented by the following formula: R _F - (CH ₂ CF ₂ ) _a (CH ₂ ) _b -I () and the following formula: (However, in the above two formulas, R _F , a, b and R ₁ are the same as defined above.) It can be obtained by condensation with an amino alcohol represented by the following. When using iodides of the R _F −CH ₂ CH ₂ I type, the following formula is generally obtained by condensation: and (However, R' _F is a perfluoro group having one less carbon atom than the R _F group.) A mixture of fluorinated amino alcohols, each represented by: These two amino alcohols can also be separated by gas chromatography if necessary. In addition, using a large excess of amino alcohol (V), saturated amino alcohol (
-a) can also be produced selectively. Similarly, the amino alcohol (V) can be converted into a fluorinated olefin R _F − according to the above-mentioned U.S. Pat. No. 3,535,381.
An unsaturated amino alcohol (-b) can also be selectively produced by condensation with CH= _CH2 . A fluorinated amino alcohol () in which X is a −CFCH ₂ CH ₂ − bond is a fluorinated amino alcohol (
-obtained by hydrogenation of b). This hydrogenation is carried out using a catalyst such as Raney nickel or palladium on carbon at a hydrogen pressure of e.g. It can be carried out preferably in methanol or ethanol). Using this hydrogenation reaction to obtain a mixture of saturated fluorinated amino alcohols, a mixture of fluorinated amino alcohols (-a) and (-b) can also be obtained. The amount of the compound of formula () to be added to the lubricating oil in order to obtain the best antiwear efficiency is preferably at least 0.01%, in particular 0.05 to 0.5%, based on the weight of the lubricating oil. Lubricating oils include mineral oils, synthetic hydrocarbons or glycols, glycol ethers, glycol esters, polyoxyalkylene glycols, their ethers and esters, and esters of monocarboxylic or polycarboxylic acids, monovalent or polyhydric. Synthetic oils belonging to the ester class may be used, but are not limited to those listed here. When a petroleum fraction based on "neutral solvent" for the production of engine oil is used as a lubricant base, the organic fluorine derivative of the present invention and calcium or barium alkyl phenate and Known dispersant cleaning additives such as alkylaryl sulfonates or “grey-free” agents such as succinic acid derivatives
It is advantageous to use it in combination with a dispersant. By adding these dispersion-cleaning additives, the fluorinated additives can be solubilized without compromising the wear resistance of the fluorinated additives and without losing the ability of the dispersion-cleaning additives themselves. can be promoted. By adding the fluorinated derivatives of the present invention to a formulated oil that already contains additives such as zinc alkyl dithiophosphate, it is possible to improve the dispersibility, detergency, corrosion resistance, etc. provided by other additives. Substantially improves body abrasion and increases oil durability without interfering with properties. By using 0.1 to 0.2% of the organofluorine compound of the present invention in place of all or part of the zinc dithiophosphate used as an antiwear additive in internal combustion engine oil formulations, the same as the conventional additives mentioned above can be obtained. or even better wear resistance. Accordingly, the fluorinated additives of the present invention can be used as a replacement for zinc alkyl dithiophosphates in lubricating oils for petroleum or diesel engines or as a separate additive to these lubricating oils. Hereinafter, the present invention will be explained in more detail with reference to Examples and tests, but the present invention is not limited thereto. Note that the percentages below are by weight unless otherwise specified. Example 1 In a 100 ml round bottom flask equipped with a condenser, a fluorinated amino alcohol, _C8F17 - _{CH2CH2 - NH} - _{CH2CH2 -} OH, is added while maintaining constant stirring.
C ₇ F ₁₅ CF=CH−CH ₂ −NH−CH ₂ CH ₂ OH (each
4 g of methyl acrylate in a solution of 20 g of a mixture of 65 mol % and 35 mol %) dissolved in 10 g of ethanol.
Add. After refluxing the mixture for 10 hours, the ethanol and excess methyl acrylate are removed by evaporation under vacuum. The residue (22 g) was analyzed by infrared spectrophotometry (ester band: 1730 cm ^-1 ) and was confirmed to correspond to the following ester: and, The product is an orange liquid, slightly cloudy at room temperature, but completely homogeneous at 60°C. Figures 1 to 3 show the products obtained in Example 1.
These are NMR spectra of ¹ H, ¹³ C, and ¹⁹ F. ^1H
and ¹³ C NMR spectra were measured with a Jeol GX270MHz instrument using CDCl ₃ as a solvent. The NMR spectrum of ¹⁹ F was measured with a Bruker 200MHz instrument using CDCl ₃ as a solvent, and the chemical shifts are determined by the terminal group CF ₃
(δ=0). Example 2 Same fluorinated amino alcohol mixture as Example 1
The temperature of a solution containing 20g of n-butyl acrylate, 5.55g of n-butyl acrylate, and 10g of n-butanol was kept at 100°C for 10 hours.
maintain it. Then, after filtering the reaction mixture,
Evaporate the solvent and excess butyl acrylate under vacuum. The resulting product (23 g) has the formula: and It corresponds to the ester of and is an orange liquid,
Cloudy at room temperature. Figures 4 to 6 show ^{the 1} H, ¹³ C, and ¹⁹ F of the product obtained in Example 2, measured in the same manner as in Example 1.
This is an NMR spectrum. Example 3 Example 2 is repeated, but 0.1 g of acetic acid is added and the reaction mixture is heated for 6 hours. As a result, the same product as above was obtained with a yield of 91%. Example 4 In the same apparatus as Example 1, 10 g of n-butanol
to the same fluorinated amino alcohol mixture as in Example 1.
Add 11.4 g of lauryl acrylate to the solution containing 23.72 g with constant stirring. After heating the mixture to 100° C. for 10 hours, the n-butanol is removed under vacuum and the residue is dissolved in dichloromethane. The solution is filtered and the dichloromethane is removed by evaporation. This gives the formula: and A mixture of esters is obtained. This is a clear orange liquid (32.7g: 93% yield). Example 5 20 g of methyl acrylate and the following formula: C _o F _2o+1 CH ₂ CH ₂ -NH-CH ₂ CH ₂ OH and C _o-1
F2o _-1 CF= _CHCH2 -NH- _CH2CH2OH (where n is 6 _, 8, 10, 12 and 14, and the respective weight percentages are 56.2%, 27.2%, 12.3%, 3.7% and 20 g of a technical mixture of fluorinated amino alcohols (0.6%) are heated at 80° C. for 8 hours with stirring. The above industrial mixture has an average molecular weight of 466, approximately 65 mol% of saturated amino alcohol and unsaturated amino alcohol.
Contains 35 mol%. After evaporating the excess methyl acrylate, the formula: and A mixture of esters is obtained with a yield of 91.3%. This was a clear yellow liquid. The product was characterized by infrared spectrophotometry (ester band: 1730 cm ^-1 ). Example 6 The procedure is as in Example 2, but with C ₈ F ₁₇ and
In place of C ₇ F ₁₅ amino alcohol, Example 5
20 g of the technical mixture of fluorinated amino alcohols described in Example 1 are used, as well as 6 g of butyl acrylate. 24.05g of clear liquid was obtained, which has the formula: and corresponds to the ester of Example 7 In a 100 ml Erlenmeyer flask equipped with a condenser, 7.9 g of 2-ethylhexyl acrylate are added to a solution of 20 g of the technical mixture of fluorinated amino alcohols defined in Example 5 in 10 g of n-butanol.
is added with stirring and the mixture is heated at 80° C. for 8 hours. After removing n-butanol by evaporation under vacuum, a clear yellow liquid was obtained in 95% yield consisting of an ester of the following formula: and Example 8 The operation is carried out as in Example 4, but with C ₈ F ₁₇ and
Technical mixture of fluorinated amino alcohols as defined in Example 5 instead of C ₇ F ₁₅ amino alcohols
Use 20g. As a result, the formula: and A mixture consisting of esters represented by was obtained in a yield of 92%. Example 9 In a flask containing 6.18 g of the technical mixture of fluorinated amino alcohols defined in Example 5,
n-butyl acrylate (1.09g
(corresponding to about 0.65 molar equivalent) and 9 g of methanol are added. The mixture is left stirring at room temperature for 96 hours. After evaporation of methanol, it will be cloudy at room temperature, but about
A product was obtained which became homogeneous at 60°C. This product is
Approximately 60 mol% is of the formula: and This is an ester mixture represented by , and approximately 40 mol % is an unreacted fluorinated amino alcohol mixture. Example 10 Example 9 is repeated, but with n-butyl acrylate
1.42 g (0.847 molar equivalent) was used. the result,
A similar product was obtained in 90% yield. Example 11 (a) Fluorinated amino alcohol: _{C8F17 - CH2CH2} - _NH - _CH2CH2OH (67 mol%) in a stainless steel autoclave _equipped with a magnetically driven stirrer. and C ₇ F ₁₅ −CF=CH−CH ₂ −NH−CH ₂ CH ₂ OH
(33 mol%) and then add 2000 g of a mixture of
99% pure ethanol 1.2 and approximately 60% Raney nickel suspension in 99% pure ethanol 32
g was added. The autoclave is purged three times with 30 bar of nitrogen and three times with 30 bar of hydrogen. The mixture was stirred at a speed of 2000 rpm and maintained at 70 °C while maintaining a pressure of 20 bar.
Hydrogenate for 6 hours and 45 minutes. After cooling the autoclave, releasing pressure, and purging,
The catalyst is filtered and the ethanol is removed by evaporation. As a result, 1940g of a pale yellow solid with a melting point of 51℃
was obtained, and GC analysis revealed that it had the following composition. C ₈ F ₁₇ −CH ₂ CH ₂ −NH−CH ₂ CH ₂ OH: 65.6% C ₇ F ₁₅ −CFH−CH ₂ CH ₂ −NH−CH ₂ CH ₂ OH:
25.4% C ₇ F ₁₅ −CH ₂ CH ₂ CH ₂ −NH−CH ₂ CH ₂ OH: 8.9
% (b) In a 100 ml Erlenmeyer flask equipped with a condenser, add acrylic acid n-
Add 1.87 g of butyl. Heat this mixture to 100℃
After heating for 10 hours, n-butanol and excess butyl acrylate are removed by evaporation.
Dissolve the yellow residue in dichloromethane and
The solution is filtered and the dichloromethane is evaporated. As a result, the formula: and The yellow liquid ester mixture represented by 96
% yield and the characterization was carried out by infrared spectrophotometry (ester band: 1725 cm ^-1 ). Example 12 (a) Similar to Example 11(a), formula: C _o F _2o+1 CH ₂ CH ₂ −NH −CH ₂ CH ₂ OH (67 mol%) and C _o-1 F _2o-1 − CF=CH- _CH2 -NH _{- CH2CH2OH} (33mol%) (However, the weight distribution of fluorine chains is as follows: n % 6 55.7 8 27.2 10 10.15 12 3.9 ≧14 2.9) 2000 g of a technical mixture of fluorinated amino alcohols are hydrogenated at 80° C. for 9 hours. After filtering the catalyst and removing the ethanol by evaporation, a pale yellow semi-liquid, semi-solid product (45
1990g (becomes a complete liquid at ℃) was obtained, and GC
As a result of the analysis, the following results were obtained. C _o F _2o+1 −CH ₂ CH ₂ −NH−CH ₂ CH ₂ OH: 69.3
% C _o-1 F _2o-1 −CFH−CH ₂ CH ₂ −NH−
CH ₂ CH ₂ OH: 18.6% C _o-1 F _2o-1 CH ₂ CH ₂ CH ₂ −NH−CH ₂ CH ₂ OH:
9.8% (b) A mixture of the above saturated fluorinated amino alcohols
2-ethylhexyl acrylate 2.05 per 5.5g
g and heat it to 100° C. for 8 hours. As a result, the formula: and A clear orange liquid consisting of the ester is obtained in 93% yield. Example 13 Example 12(b) is repeated, but instead of 2-ethylhexyl acrylate 3.3 g lauryl acrylate
and 6.87 g of the saturated fluorinated amino alcohol mixture obtained in Example 12(a) were used. The lauryl ester mixture thus obtained (yield: 92%) was in the form of a transparent yellow liquid. Example 14 In a 250 ml Erlenmeyer flask equipped with a condenser, an ether/acetonitrile mixture (3:1)
1.56 g (0.85 molar equivalent) of n-butyl acrylate are added to a solution of 6.73 g of the saturated fluorinated amino alcohol mixture obtained in Example 12(a) in 12 g. The mixture is left stirring at room temperature for 96 hours. The solvent is then removed by distillation under vacuum. As a result, 7.5g of clear yellow liquid was recovered.
It consisted of about 20 mole percent starting saturated fluorinated amino alcohols and about 80 mole percent butyl esters of these amino alcohols. Wear resistance test Mineral oil 200 neutral as base oil
The anti-wear ability of lubricant compositions comprising a Neutral Solvent and a compound with a fluorine chain according to the invention as an additive was determined using a SHELL EP4 ball tester. This testing machine is described in "Annual Book of ASTM Standards" Part 24 (1979), pages 680-688. In this test, one ball with a diameter of 12 mm is rotated at a rotational speed of 1500 rpm over three other fixed balls coated with the lubricant to be tested. While applying a load of 40 or 70 daN using a lever mechanism, push the three fixed balls toward the upper rotating ball housed in the chuck. The anti-wear efficiency of the lubricant is determined by the average diameter of the wear marks on three fixed balls after one hour of operation. Table 1 below summarizes the test results of various fluorinated additives according to the invention, designated Fx. x here corresponds to the number of each example describing the preparation of the fluorinated additive, which was tested in all cases at a proportion of 0.1% by weight.

【table】

Table: Thermal Stability Test In order to test the performance of the additive under conditions similar to those of a real engine, the fluorine compounds according to the invention were gravimetrically analyzed under atmospheric conditions. This test involves passing the sample through an air stream.
Heating at 10/h (2°C/min), 200, 250 and
The weight loss rate (%) at 300°C is recorded. Table 2 below summarizes the results obtained. For comparison, conventional technology (French Patent No. 2520377)
The performance of the following fluorine compounds described in Table 2 is shown at the beginning of Table 2. P1: C ₈ F ₁₇ −C ₂ H ₄ −NH−C ₂ H ₄ OH P2: C _o F _2o+1 −C ₂ H ₄ −NH−C ₂ H ₄ OH (where n is defined in Example 5) )

【table】 [Brief explanation of drawings]

Figures 1 to 3 show the products obtained in Example 1.
These are NMR spectra of ¹ H, ¹³ C, and ¹⁹ F. Fourth
Figures 6 to 6 show ¹ H of the product obtained in Example 2,
This is an NMR spectrum of ¹³ C and ¹⁹ F.

Claims (1)

[Claims] 1. A polyfluorinated compound represented by the following general formula (): [where R _F represents a perfluoroalkyl group having 2 to 20 carbon atoms, and X represents one of the following divalent bonds: -(CH ₂ CF ₂ ) _a (CH ₂ ) _b - - CF=CHCH ₂ − −CFHCH ₂ CH ₂ − (here, a represents an integer from 0 to 10, and b represents an integer from 1 to 4
(or equal to 2 when a is other than 0) R ₁ represents a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms, R ₂ represents a hydrogen atom or represents a methyl group and R ₃ represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms]. 2 R _F is a straight-chain or branched perfluoroalkyl group having 2 to 20 carbon atoms, and R ₂
The compound according to claim 1, wherein is a hydrogen atom. 3 R _F is a straight-chain or branched perfluoroalkyl group having 6 _to 16 carbon atoms, and X is _-CH2CH2- , -CF= _CHCH2- or -
_2. A compound according to claim ₁ , which is a CFHCH2CH2- bond, _R1 and _R2 are hydrogen atoms, and _R3 is an alkyl group having 8 to 18 carbon atoms. 4. A lubricant composition comprising a mixture of the compounds according to claim 1, wherein _4RF , X and/or _R3 are different from each other. 5 50 mol% or more of at least one of the compounds according to any one of claims 1 to 3 and the following general formula (): (However, the definitions of symbols R _F , X and R ₁ are the same as in claim 1.) At least one of the amino alcohols represented by
A lubricant composition composed of a mixture of 50 mol% or less. 6 The following general formula (): At least one type of amino alcohol represented by the following general formula (): (However, in the above two general formulas, R _F , R ₁ ,
(The definitions of R ₂ and R ₃ are the same as in claim 1.) A method for producing a polyfluorinated compound, characterized in that it is condensed with at least one type of acrylic ester represented by: 7. The process according to claim 6, wherein the condensation is carried out in a ( _C1 - _C4 ) lower alcohol at a temperature of 20-100<0>C. 8. An anti-wear additive for lubricants comprising the polyfluorinated compound according to any one of claims 1 to 5 or a mixed composition thereof. 9. A lubricant comprising the polyfluorinated compound according to any one of claims 1 to 5 or a mixed composition thereof. 10. A lubricant according to claim 9, wherein the content of said polyfluorinated compound is at least 0.01% by weight. 11. A lubricant according to claim 9 or 10, further comprising conventional additives.