JPH03131691A - Additive for lubricant - Google Patents

Abstract

PURPOSE:To provide the subject additive homogeneously dissolved or stably dispersed in lubricants such as lubricating oils or greases, not causing corrosion, not producing sludges and imparting high load resistance, high electric insulation and low hygroscopicity to the lubricants by incorporating a specific fluorinated polyether into the additive. CONSTITUTION:The objective additive comprises a fluorinated polyether of formula I (Rf is a group containing a fluoroalkylpolyether group; X is CF2COO-, C2F4COO- or -CF2CF2-; A is a group containing a polyoxyalkylene group). The fluorinated polyether is preferably a compound of formula II [Y is F, CaF2a+1O (a is 1-3); R is H or 1-20C alkyl; l, m, n, p and q are satisfied with the inequali ties 0<=p<=100, 0<=q<=100, 2<=l+m+n<=200, and l+m>=1].

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to additives for lubricants.

[Prior Art] Conventionally, it has been known to add additives to lubricants such as lubricating oils and greases for the purpose of improving various properties such as load resistance. For example, the following additives are known. However, there are problems with both conventional additives.

- Sulfur-based additives (for example, sulfides such as sulfurized oils and fats, dibenzyl disasulfide, and sulfurized olefins) have the problem of corrosiveness to copper plates.

(2) Chlorinated additives (for example, chlorinated paraffins) have the problem of being highly corrosive in the presence of water.

■Iodine additives are used for metal processing, but they have the problem of being highly corrosive and expensive.

- Phosphorous additives (for example, phosphate, bosphite, etc.) have the problem of being corrosive.

Further, as a perfluoropolyether having high load resistance, the one described in Japanese Patent Publication No. 63-43419 is known. However, even if it is added to, for example, a hydrocarbon-based lubricating oil, separation of the lubricating oil and perfluoropolyether occurs, and the properties of the hydrocarbon-based lubricating oil cannot be improved.

[Problems to be Solved by the Invention] An object of the present invention is to provide an additive that is uniformly dissolved or stably dispersed in lubricants such as lubricating oil and grease, and that improves the properties of the lubricant, particularly its load-bearing performance. It's about doing.

Means for Solving the Problem] The gist of the present invention is the formula: %Formula% (1) [wherein, Rr is a group containing a fluoroalkyl polyether group, and X is -CF v C00Ct F 4 C00- or C
F and CF t-A are groups containing a polyoxyalkylene group. The lubricant additive consists of a fluorine-containing polyether shown in

The fluoroalkyl polyether group is, for example, a repeating unit represented by the formula -c 3F so (a), a repeating unit represented by the formula %formula%(), and a repeating unit represented by the formula CF, O-(C). at least one repeating unit selected from the group consisting of repeating units (a);
or (b). Repeating unit (a
), (b) and (c) is at least three.

-C, P, O- are -CF, CF, CFtO and -CF (
CF, ) CF, O-. -〇、F.

0- is usually -CPICFtO-.

Preferred fluoroalkyl polyether groups include Y(CzFeOh6FIICF, CF,
, CF, 0 fin (d) [Y is a fluorine atom or CaF 2
a++ O (a is 1 to 3), Q, m, n are 2
The number satisfies ≦12+m+n≦2001+m≧1.

] can be mentioned. -CsFsO- is -CFtCF.

CF, O- are preferred.

Note that the above repeating units are arranged randomly.

On the other hand, the polyoxyalkylene group is, for example, at least li selected from the group consisting of 7 repeating units represented by the formula %, a repeating unit represented by a partial formula, H,0, and a repeating unit represented by the formula: The total number of repeating units is 1 to 100.

Cs I-(s O- is -CE'ltC['1tCH
! O--CHCH, O- or -CH, CHO-CH3C
It is H3.

In the present invention, the preferred fluorine-containing polyether has the formula: % formula % [wherein Y is a fluorine atom or Ca F x a+ IO]
(a is 1 to 3), R is the same or different, hydrogen atom, methyl group or ethyl group, Ro is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X is -CF t COOCx F 4COO- or CF
,CF! ρ, m, nSp and q are 0≦p≦ioo, 0≦q≦
100.2≦g+m+n≦200. (A number that satisfies +m≧1.) This is a compound represented by the following formula.

A specific example of a preferable fluorine-containing polyether is F (CF
tCF zcF *O)mCF teFtcOOcl
I tcHt (OCHtcHt) n0cH3 [The average value of m is 9, and the average value of n is 20. The average value of ko[m is 1O1n is 25. ]C11°F (CF, CF, CF, O) CF, CF, C11, C
11, (OCIICIIP) (for m
The average value of Q[m is 20,
The average value of n is 30. ]F(CF, CF, CF, 0
) (CFIICF, CF, 0) CF, CF, C00
m 1 C11=CH-(OCR-CIIt)ooll [The average value of m is 8, the average value of n is 20, and the average value of Lo is 20. ” CI, CH3 F (CF tCF tCF to) mCF tcF
tcOOcllcIlt (OCHCHt) n0
cIItcHtcll tcHs [The average value of m is 1 1, the average value of n is 22 or 50. coF(CFtCFtCFtO)mcF, cFtcOo −
[The average value of m is 11 or the average value of 20.0 is 33. ] -(OCI(, CHI), OCH3 [The average value of g is 20, the average value of -→-n is 1O.

]70FtCFt(OCFtCFtCF-) 0CF
tCF-CHtCHt(OCHtCHx) OCH3
]tn [The average value of m is 10. The average value of n is 20. ].

When adding the additive of the present invention to hydrocarbon-based lubricating oil/grease, in R1-X-A (molecular weight of Rf group)
/(molecular weight of A group) is preferably 2 or less from the viewpoint of solubility.

Examples of lubricants to be added in the present invention are as follows.

Lubricating oils include mineral oils and highly refined mineral oils, including ester-based, polyglycol-based, phenyl ether-based, alkylbenzene-based, silicone-based, etc. There are synthetic oils such as 10 carbon type and poly α-olefin type oils.

In particular, polyglycol-based synthetic oils are preferred because they have excellent compatibility with the additives of the present invention.

Examples of the grease include those in which the base oil is a lubricating oil as described above, and a thickener such as metal soap, bentonite, silica gel, phthalocyanine, polyurea, or fluororesin is blended with the lubricating oil.

The amount of additives added is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight, based on the total of lubricant and additives.
It is. Two or more kinds of additives may be added in combination.

In the production of fluorine-containing polyether, for example, the formula: % formula % (
) by reacting a fluorine-containing compound represented by the formula: O-A with a compound represented by the formula:

The fluorine-containing compound represented by Rf-X-1(r) can be reacted with a compound represented by the formula: "In the above formula, A, Rf and X have the same meanings as above, and M is an alkali metal. ].The reaction is usually carried out at a temperature of 20 to 150°C for 1 to 10 hours.

Regarding the above compounds (e) and Cf),
It is described in detail in Publication No. 43419.

[Effects of the Invention] The lubricant additive of the present invention is uniformly dissolved or stably dispersed in the lubricant, does not generate corrosion or sludge, and provides the lubricant with high load carrying capacity and electrical insulation, as well as low Can provide hygroscopic properties.

[Preferred Embodiments of the Invention] The present invention will be specifically explained below with reference to Preparation Examples, Examples, and Comparative Examples.

Preparation Example 1 Fluorine-containing carboxylic acid F' (CF, CFtCFtO) mC
The average value of F tc F tc OOH[:1m is +1. Polypropylene glycol butyl ether C, Hs CHa HOCHCHl (OCHCHri n0cH!cH, CHI
C.I.

[The average value of n is 48. ] (1) 150 g (50 mmol) of Uniloop MB700 manufactured by Hon Yushi Co., Ltd. was added and mixed. Next, add 5 cc of Todoroki sulfuric acid,
The reaction was carried out at 100°C for 6 hours under M'. The completion of the reaction was confirmed by IR and NMI analysis.

After the reaction was completed, it was washed twice with 50ml of a 2% NaHC:Os aqueous solution. The lower layer was separated and filtered through a filter with a pore size of 0.2 μm. The shown fluorine-containing polyether was obtained.

220g (88%).

'4 Production Example 2 Yield: F as reactant (CF 20 P 10 F to)
The average value of mCF zcFtCOOH[m is ii.

]50 mmol and the average value of [0 is 33. ] F(CF=C
FtCFzO) IcF-CFzCOO [m and 0 have the same meanings as above. ] was prepared.

Preparation Example 3 F (CF tc F ICF to)m as reactant
The average value of c F zcF z COOH[m is 11. 150 mmol astringency [average value of r is 22]. ] p(CFt
CF2CFtO)lThcF,cFzcOo[m and r
has the same meaning as above. ] Prepare 1. Ta.

Preparation Example 4 P (CF tc F *CF to)QCF tcF as reactant
The average value of tCOO)4Eq is 20. ]50
The average value of mimol and [r is 33. ]F(CF,CF,CF2O)QCFtCF,COO-[
q and r have the same meaning as above. ] was prepared.

Example 1 Fluorine-containing polyether F (CF
tCFtCFtO)mcPxcFycOo-CH3CI
−1°CHCHt(OCHCHt)nOcL(tCI(tcH
tc) (:+[The average value of m is l l, the average value of n is 50
It is. ] 7g of Nirasan Uniol D700 (polyoquine propylene glycol manufactured by NOF Corporation) 13
3y and stirred at room temperature using a liquid mixing stirrer to obtain a homogeneous solution. The appearance of the solution was transparent. Regarding the load-bearing properties of this solution, ASTM-D3233A
According to the above, the seizure limit load was measured using a flex tester. The results are shown in the table.

Example 2 Fluorine-containing polyether F (CF
, CF, CF, O) mCF, CF, C0O-C11C1
1, (OCllCH,)oOcl,cH(OC1+,C
11) The average value of oolI[m is 11.0, the average value is 33
It is. '79 Nilasan Yunior D700 13
37 was added with i6 for 1 time and stirred in the same manner as in Example 1 to obtain a transparent homogeneous solution. The seizure limit load was measured for this solution. The results are shown in the table.

Example 3 Fluorine-containing polyether F (CF
tCF, CF, 0) nCFICF, Co.

[The average value of m is l The average value of ISr is 22. ]7
9 was added to Nilasan Uniol D700 133y and stirred in the same manner as in Example 1 to obtain an almost transparent solution with very slight turbidity. The seizure limit load was measured for this solution. The results are shown in the table.

Example 4 Fluorine-containing polyether P (CF
zCFtCFyO)QCFtCFtCOo[The average value of q is 20, and the average value of r is 33. ] 7shi to nilasan・
γ6 was added to Uniol D700 133y and stirred W1 in the same manner as in Example 1 to obtain a transparent solution. The seizure limit load was measured for this solution. The results are shown in the table.

Example 5 The fluorine-containing polyether 1°3j obtained in Preparation Example 2 was added and mixed with Nirasan Uniol 0700 12B, 79 to obtain a transparent solution.13 The seizure limit load was measured for this solution. The results are shown in the table.

Example 6 The fluorine-containing polyether obtained in Preparation Example 2 was added to 104 g of Nirasan Uniol D700 and mixed to obtain a transparent solution.The seizure limit load of this solution was measured. The results are shown in the table.

Example 7 The fluorine-containing polyether 659 obtained in tA Preparation Example was added to and mixed with Nirasan Uniol D700 659, and the transparent solution was prepared as iP2. The seizure limit load was measured for this solution. The results are shown in the table.

Example 8 The fluorine-containing polyether 7 obtained in Preparation Example 1 was added to 133 g of Nissan Unilube MB7 (manufactured by Memoto M11 Miri Co., Ltd., butyl-modified polyoxypropylene glycol), and the same method as in Example 1 was carried out. The mixture was combined to obtain a clear solution. The seizure limit load was measured for this solution. The results are shown in the table.

Example 9 The fluorine-containing polyether 79 obtained in Preparation Example 1 was added and mixed little by little to Albania Grease #2 (Showa NEL Sekiyu Co., Ltd. +, mineral oil based Li grease) L 33y using a mixer to obtain a consistency of 298. got the grease. The seizure limit load of this grease was measured. The results are shown in the table.

Comparative Example 1 F(CFtCF, CFtO)ncFtcF3 [The average value of n is 27. Core 2 Uniall D700 133
9, but it did not dissolve at all.

Comparative example 2 Polyethylene glycol butyl ether C11, CH.

[The average value of n is 50. ] ([''Uniloop M13700 manufactured by Honoura Fats Co., Ltd.) 7g was added to ① Uniloop MB7133y manufactured by Motoura Fats Co., Ltd. to obtain a solution. The seizure limit load was measured for this solution.

The results are shown in the table.

Comparative Examples 3 to 5 Uniol [) 700 (Comparative Example 3), Uniloop M■3
7 (Comparative Example 4) Naki Albany Y Grease #2 (Comparative Example 5)
), the seizure limit load was measured for each. The results are shown in the table.

Comparative Example 6 CI, CH3CH3CH3 HOCIIICII, (OCllCll,)oOcH,
Cl1 (OCH, CH) oOH [average value of 0 is 3] 17
y was added to Uniol D7001339 to obtain a solution. The critical load of this solution was measured. The results are shown in the table.

The solubility in the table was evaluated according to the following criteria.

C...Completely dissolved 1) S ・Partially dissolved

Claims (1)

[Claims] 1. Formula: Rf-X-A (I) [wherein, Rf is a group containing a fluoroalkyl polyether group, X is -CF_2COO-, -C_2F_4COO-, or -CF_2CF_2-], and A is It is a group containing a polyoxyalkylene group. ] A lubricant additive consisting of a fluorine-containing polyether represented by: 2. Fluorine-containing polyether has the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is a fluorine atom or CaF_2_a_+_1O
(a is 1 to 3), R is the same or different, hydrogen atom, methyl group or ethyl group, R^1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X is -CF_2COO-, -C_2F_4COO- or -CF_2CF_2-, l, m, n, p and q are 0≦p≦100, 0≦q≦1
00, 2≦l+m+n≦200, and l+m≧1. ] The lubricant additive according to claim 1, which is represented by: