JP2017523292A - Lubricating method with alkoxylated perfluoropolyether - Google Patents

Abstract

Applying a partially or fully fluorinated, linear or branched polyoxyalkylene chain (chain Rf) having two chain ends to the surface to be lubricated, wherein one or Both chain ends have a hydroxy- or alkoxy-terminated polyoxyalkylene chain (chain Ra) that does not contain fluorine atoms, said chain comprising 4 to 50 fluorine-free oxyalkylene units, said units -CH2CH2O- and -CH2CH (J) O- (wherein J is independently linear or branched alkyl or aryl, provided that both chain ends are -CH2CH2O- Lubricating method, provided that when it has a hydroxy-terminated chain Ra containing only units, the chain Rf must not consist solely of -CF2CF2O- units. Lubricating composition containing a polymer, and methods for preparing the polymers, are disclosed herein. .BACKGROUND

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority from European Application No. 141798677.8 filed on Aug. 5, 2014, the entire contents of which are incorporated by reference for all purposes. Is incorporated herein by reference.

  The present invention relates to lubricating methods, polymers for use in such methods, and lubricating compositions containing such polymers.

  Polyoxyalkylene glycol (hereinafter referred to as “PAG”) is used in a variety of applications such as gear lubrication, transmission systems, air conditioning (A / C) systems, metalworking fluids, and hydraulic fluids. . For this purpose, PAGs can be formulated to improve their performance as aqueous or non-aqueous compositions containing certain additive packages. However, when PAGs are used as base oils in such compositions, it is recognized that they do not give satisfactory performance for applications that require harsh conditions such as high temperatures and extreme friction conditions. Has been.

  (Per) fluoropolyethers (hereinafter referred to as “PFPE”) have also been long known as base oils or additives in some lubricating applications. However, despite their superior performance under harsh conditions, they have little compatibility with minerals and synthetic hydrogenated lubricants, which means that in formulations for conventional lubrication systems Limit the use of.

U.S. Pat. No. 7,230,140 (ASAHI GLASS COMPANY, LIMITED) On August 9, 2005, the formula (I):
_{HO- (CH 2 CH 2 O)} r (CH 2 CH (OH) CH 2 O) p -CH 2 CF 2 O (CF 2 CF 2 O) m CF 2 CH 2 O- (CH 2 CH (OH) CH _{2 O) q (CH 2 CH} 2 O) s -H (I)
(Where:
m is an integer from 3 to 200;
Each of r and s is independent of each other and is an integer of 0 to 100, and each of p and q is independent of each other and is an integer of 0 to 100)
PFPE derivatives have been disclosed.

The derivatives of formula (I) are said to be useful as lubricating oils or coating agents and appear to be less susceptible to degradation and are said to be free from degradation during their use. The PFPE backbone of the derivative of formula (I) is
Comprise only -CF ₂ CF ₂ O- repeat units worth noting; fact, in this document, PFPE derivatives also include _-CF 2 O-units, -OCF ₂ O-units which may cause decomposition or degradation (See column 1, lines 21-25).

Accordingly, the prior art document teaches to improve the stability of the PFPE lubricant by selecting the PFPE chain having no _-CF 2 O-units. This specification specifically includes the formula:
_{HO (CH 2 CH 2 O)} r CH 2 CF 2 O (CF 2 CF 2 O) m CF 2 CH 2 O (CH 2 CH 2 O) s H (Ic)
(Wherein r and s are 1 at the same time)
Preferred compounds and formulas of:
_{HO (CH 2 CH (OH)} CH 2 O) p CH 2 CF 2 O (CF 2 CF 2 O) m CF 2 CH 2 O (CH 2 CH (OH) CH 2 O) q H (Id)
Compounds are disclosed wherein p and q are 1 at the same time. Example 6-1, Example 6-2 and Example 7 illustrate the synthesis of certain compounds compatible with Formula (Ic) and Formula (Id) above. Nevertheless, this prior art does not teach the preparation of compounds conforming to formula (I) having r and s higher than 1.

US Patent Application Publication No. 20062522910 (ASAHI GLASS COMPANY, LIMITED) (November 9, 2006) is represented by the following formula (A):
(A) (X-) _x Y (-Z) _z
[Where:
-X is the following formula (X):
_{HO- (CH 2 CH 2 O)} a (CH 2 CH (OH) CH 2 O) b - (CH 2) c -CF 2 O (CF 2 CF 2 O) d - (X)
(Wherein, a is an integer from 0 to 100, b is an integer from 0 to 100, c is an integer from 1 to 100, and d is an integer from 1 to 200)
A group represented by
-Z is the following formula (Z):
^{_{R F O (CF 2 CF 2}} O) g - (Z)
(Wherein R ^F represents a C _1-20 perfluoroalkyl group or a group having an ether oxygen atom inserted between carbon-carbon atoms of such a perfluoroalkyl group (this group has a —OCF ₂ O— structure). And g is an integer of 3 to 200).
- Y is, (x + z) valent perfluorinated saturated hydrocarbon group or having no -OCF 2 _O-structure, carbon - perfluorinated of having inserted ether oxygen atom between carbon atoms (x + z) atomic values A saturated saturated hydrocarbon group;
-X, Z: x is an integer of at least 2, z is an integer of at least 0, and (x + z) is an integer of 3 to 20, provided that when x is at least 2, The groups represented by X) may be the same or different, provided that when z is at least 2, the groups represented by formula (Z) may be the same or different] It relates to compatible fluoropolyether compounds (see in particular [0015] to [0019]). This document shows that the fluoropolyether compounds (A) are particularly useful as lubricants, especially in the form of solutions with organic solvents (especially [0013] and [0024]), and their molecular structure It does not have a -OCF 2 _O-units in teaches that they do not undergo so much degradation. In fact, in the formula (A), the group Y is an at least trivalent group having no —OCF ₂ O— unit. Thus, this document teaches away from the PFPE lubricant comprising _-CF 2 O-repeating units. Furthermore, this prior art does not teach synthesizing fluoropolyether compounds having two or more ethoxylated units at the chain ends.

U.S. Patent Application Publication No. 2008132664 (ASAHI GLASS COMPANY, LIMITED) (May 6, 2008) is an ether composition comprising a polyether compound (A) and an ether compound (B), especially a lubricant. (See, in particular, [0007] and [0025]). Examples of ether compounds (B) conform to the following formulas (B-4) and (B-5):
(B-4)
_{HOCH 2 CH (OH) CH 2} OCH 2 CF 2 O (CF 2 CF 2 O) d7 (CF 2 O) g2 CF 2 CH 2 OCH 2 CH (OH) CH 2 OH
(B-5)
_{HOCH 2 CH 2 OCH 2 CF 2} O (CF 2 CF 2 O) d8 (CF 2 O) g3 CF 2 CH 2 OCH 2 CH 2 OH.

  In Formula (B-4), d7 is a positive number of at least 1, g2 is a positive number of at least 0, and the average molecular weight of the compound represented by Formula (B-4) is 500-2, 000.

  In Formula (B-5), d8 is a positive number of at least 1, g3 is a positive number of at least 0, and the average molecular weight of the compound represented by Formula (B-5) is 500-2, 000.

The polymer compound (A) contains at least two —CF ₂ CF ₂ O— units and does not contain —OCF ₂ O— units, and this document indicates that such compounds (A) have high chemical stability. It is noteworthy to teach what can be achieved for the presence of Furthermore, compound (B-4) contains only one —OCH ₂ CH (OH) CH ₂ — unit at each end of the PFPE chain, while compound (B-5) contains each chain end of the PFPE chain. Contains only one —OCH ₂ CH ₂ — unit.

U.S. Pat. No. 3,810,874 (MINESOTA MINING AND MANUFACTURING COMPANY) (May 15, 1974) contains the formula:
_{A- [CF 2 -O- (CF 2} CF 2 O) m - (CF 2 O) n -CF 2] A '
Wherein A or A ′ can be —CH ₂ OH, or —CH ₂ OCH ₂ CH (OH) CH ₂ OH; the ratio m / n is 0.2 / 1 to 5/1, (Preferably 0.5 / 1 to 2/1)
A linear multifunctional terminated poly (perfluoroalkylene oxide) compound is disclosed.

  These compounds are said to be suitable for use as lubricants and viscosity index additives for perhalogenated lubricants. However, this document does not disclose or suggest PFPE derivatives having multiple oxyalkylene end units at each end of the PFPE chain.

WO 2013/086264 (DU PONT) (June 13, 2013) states that Fomblin® PFPE lubricant used in the composition of the present invention is in an atomic mass unit of 500-4000. Molecular weight range, general formula:
_{X-CF 2 -O (CF 2} -CF 2 -O) - (CF 2 O) q -CF 2 -X,
Wherein X is —CH ₂ OH, CH ₂ (O—CH ₂ —CH ₂ ) _n OH, CH ₂ OCH ₂ CH (OH) CH ₂ OH, or —CH ₂ O—CH ₂ —piperonyl, May be functionalized PFPE (page 22, lines 4-8).

  This document does not mention or suggest Fomblin® PFPE lubricants terminated with a specific number of ethylene oxide and / or longer oxide units.

WO 2014/090649 (SOLVAY SPECIALTY POLYMERS ITAL SPA) discloses a method for alkoxylating (per) fluoropolyether alcohols. More particularly, the exemplified ethoxylated PFPE diol has the following structure:
_{HO (CH 2 CH 2 O)} p CH 2 CF 2 O (CF 2 CF 2 O) n (CF 2 O) m CF 2 CH 2 (OCH 2 CH 2) p OH
Have

  WO 93/19142 (THE BRITISH PETROLEUM COMPANY PLC) discloses a lubricating oil composition comprising (1) a lubricating base oil and (2) a monofunctional PFPE ester derivative, which comprises PFPE carboxylic acid Can be obtained by reacting with a poly (alkylene oxide) alcohol.

FIG. 1 is a diagram illustrating the results of thermogravimetric analysis (TGA) performed on two polymers according to the present invention.

  Applicants now surprisingly have (chain) fluoropolyesters with two chain ends, one or both chain ends having a finite number of oxyalkylene units containing no fluorine atoms. It has been found that polymers containing ether chains exhibit higher thermal stability, improved lubricating properties (such as lower wear) and improved performance at extreme pressures relative to PAGs. It has also been observed that such polymers are given improved compatibility with PAGs. They are therefore suitable for use in a lubrication method comprising applying a polymer or composition containing them to the surface to be lubricated.

Polymers for use in the method of the present invention comprise a partially or fully fluorinated, linear or branched polyoxyalkylene chain (chain R _f ) having two chain ends, where one or Both chain ends have hydroxy-, alkoxy- or acyloxy-terminated polyoxyalkylene chains (chain R _a ) that do not contain fluorine atoms, said chains comprising 4-50 fluorine-free oxyalkylene units. The units are the same or different from each other and are selected from —CH ₂ CH ₂ O— and —CH ₂ CH (J) O—, wherein J is independently linear or branched alkyl or aryl, Preference is given to methyl, ethyl or phenyl, provided that both chain ends are hydroxy-terminated chains R _a containing only —CH ₂ CH ₂ O— units, the chain R _{f is} provided that not only -CF 2 _CF 2 O- units.

Polymers for use in the methods of the present invention are generically referred to hereinafter as “PFPE-PAG”, more specifically, depending on whether one or both chain ends have a chain R _a. Also referred to as “1- or bifunctional” PFPE-PAG.

  The invention further relates to a lubricating composition comprising PFPE-PAG and a method for preparing PFPE-PAG.

Definitions For the purposes of the present invention, the term “(per) fluoropolyether” stands for “fully or partially fluorinated polyether”.

  The acronym “PFPE” represents (per) fluoropolyether.

  The term “(halo) alkyl” means a hydrocarbon group in which one or more hydrogen atoms can be replaced by one or more halogen atoms, preferably fluorine atoms.

  The indefinite article “a” represents “one or more” unless otherwise specified. A noun equivalent in a plural should be interpreted as including the singular, that is, one or more, unless otherwise specified. For example, the term “compounds” should be interpreted as “one compound” or “one or more compounds” unless otherwise specified.

  Where ranges are indicated, range ends are included.

Typically, a PFPE-PAG for use in the method of the present invention has the following formula (I):
A—O—R _f — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a (I)
(Where:
- R _f is 100～8,000 preferably 300～6,000, more preferably has a number average molecular weight _{M n} in the range of 800 to 3,000, and same or different from each other which may be repeating units Preferably consisting of
(I) -CFXO- (wherein, X is F or CF _3);
(Ii) -CFXCFXO- (wherein, X is the same or different in each occurrence, is F or CF _3, with the proviso that at least one of X is -F),
_{(Iii) -CF 2 CF 2 CW} 2 O- ( wherein each of W differs same or another, is F or H),
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-,
_{(V) - (CF 2)} j -CFZ'-O- [ wherein, j is an integer of 0 to 3, Z 'has the general formula -OR _f' is a group T, then where, R _f ′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are represented by the following: —CFXO—, —CF ₂ CFXO—, —CF ₂ CF ₂ CF ₂ O—, — CF ₂ CF ₂ CF ₂ CF ₂ O— (each X is independently F or CF ₃ ), and T is a C ₁ -C ₃ perfluoroalkyl group] A (per) fluoropolyoxyalkylene chain comprising, preferably consisting of:
- Z is fluorine or CF _3;
-X is 0 or 1, provided that when x is 1, Z is F;
A is — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a, where x and Z are as defined above, or one fluorine atom is 1 A straight-chain or branched C ₁ -C ₄ perfluoroalkyl group which can be substituted by one chlorine atom or one hydrogen atom, provided that when chlorine is present in group A, it is based on the total amount of end groups Subject to a molar amount of less than 2%,
-R _a is a hydroxy-, alkoxy- or acyloxy-terminated polyoxyalkylene chain (chain R _a ) that does not contain a fluorine atom, the chain comprising from 4 to 50 fluorine-free oxyalkylene units, Are the same or different from each other and are selected from —CH ₂ CH ₂ O— and —CH ₂ CH (J) O—, wherein J is as defined above;
However, A is _- a _{(CF 2) x -CFZ-CH} 2 -R a, chain _{R a} are hydroxyl-terminated, and if it contains only _-CH 2 _CH 2 O- units, the chain _{R f} is , —CF ₂ CF ₂ O—requires not to consist only of repeating units)
Fits.

Preferred R _f chains in the PFPE-PAG of formula (I) are the following formulas (a) to (c):
(A)-(CF ₂ O) _n (CF ₂ CF ₂ O) _m (CF ₂ CF ₂ CF ₂ O) _p (CF ₂ CF ₂ CF ₂ CF ₂ O) _q −
Wherein m, n, p, q are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that n is 0 when p and q are simultaneously 0. When m is not 0 and m is other than 0, the m / n ratio is preferably 0.1 to 20; when (m + n) is other than 0, (p + q) / (m + n) is preferably 0 to 0.2. As long as it is)
(B)-(CF ₂ CF (CF ₃ ) O) _a (CF ₂ CF ₂ O) _b (CF ₂ O) _c (CF (CF ₃ ) O) _d −
Wherein a, b, c, d are 0, or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that at least one of a, c and d is 0. None; when b is other than 0, a / b is preferably from 0.1 to 10; when (a + b) is other than 0, (c + d) / (a + b) is preferably from 0.01 to 0.5, More preferably 0.01 to 0.2).
(C)-(CF ₂ CF (CF ₃ ) O) _e (CF ₂ O) _f (CF (CF ₃ ) O) _g −
(Wherein e, f, g are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements; when e is other than 0, (f + g) / e is preferably 0. 0.01 to 0.5, more preferably 0.01 to 0.2)
Is selected from.

PFPE-PAGs of the formula (I), in which the chain R _f conforms to the formula (a) as defined above, are particularly preferred in the process according to the invention.

Typically, in the PFPE-PAG of formula (I), the chain R _a has the following formula (R _a -I):
(R _a -I)-(CH ₂ CH ₂ O) _r (CH ₂ CH (CH ₃ ) O) _s (CH ₂ CH (CH ₂ CH ₃ ) O) _t (CH ₂ CH (Ph) O) _u R ¹
Wherein r, s, t and u are independently selected from 0 and a positive number, r + s + t + u is in the range of 4-50, preferably 4-15, more preferably 4-10, R ¹ Is selected from hydrogen, C ₁ -C ₄ straight or branched alkyl, preferably methyl, and —C (O) R ² , wherein R ² is C ₁ -C ₄ straight or branched (halo) In the case where the chain R _f of the compound (I) contains only a —CF ₂ CF ₂ O— unit and has a chain (R _a -I) in which s, t and u are 0 at both ends. R ¹ is not hydrogen)
Fits.

In one preferred embodiment, in the chain (R _a -I), r is a positive number in the range of 4-15, preferably 4-10, s, t and u are 0 and R ¹ is , Hydrogen or methyl, provided that when the chain R _f of compound (I) contains only —CF ₂ CF ₂ O— units and has chains (R _a -I) at both ends, R ¹ is The condition is that it is not hydrogen.

In another preferred embodiment, r, t and u are 0, s is a positive number in the range of 4-15, preferably 4-10, and R ¹ is selected from hydrogen or methyl.

In another preferred embodiment, r and s are positive numbers, t and u are 0, r + s is in the range of 4-15, preferably 4-10, and R ¹ is hydrogen or methyl Selected from.

_{-CH 2 CH 2 O -, -} CH 2 CH (CH 3) O -, - CH 2 CH (CH 2 CH 3) O- and _-CH 2 CH (Ph) 2 or more O- units, chains ( When present in R _a -I), they can be arranged in blocks or they can be randomly arranged.

According to one preferred embodiment, the PFPE-PAG has the following formula (IA):
R _a —O—CH ₂ —CF ₂ —O—R _f —CF ₂ —CH ₂ —O—R _a (IA)
(Where:
_-Ra is as defined above;
- R _f is conform to the formula (a) as defined above)
Is a bifunctional PFPE-PAG.

According to another preferred embodiment, the PFPE-PAG has the following formula (IB):
A—O—R _f —CF ₂ —CH ₂ —O—R _a (IB)
(Where:
- A is a linear or branched C ₁ -C ₄ perfluoroalkyl group, in which one fluorine atom can be substituted by one chlorine atom or a hydrogen atoms, provided that chlorine Is present in group A, provided that it is in a molar amount of less than 2% relative to the total amount of end groups,
_-Ra is as defined above;
- R _f is conform to the formula (a) as defined above)
Is a monofunctional PFPE-PAG compatible with

  In the method of the present invention, a bifunctional PFPE-PAG of the formula (IA) is preferred.

Preferred groups for PFPE-PAG of formula (I) are those of formula (I *):
A—O—R _f — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a (I *)
(Where:
- R _f is 100～8,000 preferably 300～6,000, more preferably have a number average molecular weight _{M n} in the range of 800 to 3,000, and preferably,
(I) -CFXO- (wherein, X is F or CF _3);
(Ii) -CFXCFXO- (wherein X is the same or different at each occurrence and is F or CF ₃ provided that at least one of X is -F),
_{(Iii) -CF 2 CF 2 CW} 2 O- ( wherein each of W, the same or different from each other, are F or H),
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-,
(V) — (CF ₂ ) _j —CFZ′—O— (where j is an integer from 0 to 3, Z ′ is a group of the general formula —OR _f ′ T, where R _f ′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are represented by the following: —CFXO—, —CF ₂ CFXO—, —CF ₂ CF ₂ CF ₂ O—, — Selected from CF ₂ CF ₂ CF ₂ CF ₂ O— (each X is independently F or CF ₃ , and T is a C ₁ -C ₃ perfluoroalkyl group). A (per) fluoropolyoxyalkylene chain comprising, preferably consisting of, repeating units which may be the same or different from each other,
- Z is fluorine or CF _3;
-X is 0 or 1, provided that when x is 1, Z is F,
- A _{is, (CF 2) x -CFZ-} CH 2 -O-R a, ( wherein, x and Z are either as defined above, or a linear or branched _C 1 -C ₄ perfluorinated An alkyl group (wherein one fluorine atom can be replaced by one chlorine atom or one hydrogen atom, provided that when chlorine is present in the group A, it is relative to the total amount of terminal groups; The molar amount of which is less than 2%)
-R _a is represented by the following formula (R _a -I *):
_{- (CH 2 CH 2 O)} r (CH 2 CH (CH 3) O) s (CH 2 CH (CH 2 CH 3) O) t (CH 2 CH (Ph) O) u R 1 (R a -I *)
(Where:
-R, s, t and u are independently selected from 0 and a positive number, r + s + t + u is a positive number in the range of 4-50, preferably 4-15, more preferably 4-10)
Conforms to
-R ¹ is hydrogen, C ₁ -C ₄ straight or branched alkyl, and -C (O) R ^{2 where} R ² is C ₁ -C ₄ straight or branched (halo) alkyl Provided that, when R ¹ is hydrogen, at least one of s, t and u is selected to be not 0))
Fits.

Preferred R _f chains in the PFPE-PAG of formula (I *) are the following formulas (a *) to (c *):
(A *)-(CF ₂ O) _n (CF ₂ CF ₂ O) _m (CF ₂ CF ₂ CF ₂ O) _p (CF ₂ CF ₂ CF ₂ CF ₂ O) _q −
(Wherein m, n, p, q are 0, or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements, and when m is other than 0, the m / n ratio is preferably 0.1 to 20 and when (m + n) is other than 0, (p + q) / (m + n) is preferably 0 to 0.2);
(B *)-(CF ₂ CF (CF ₃ ) O) _a (CF ₂ CF ₂ O) _b (CF ₂ O) _c (CF (CF ₃ ) O) _d −
Wherein a, b, c and d are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that at least one of a, b and d is 0 Otherwise, when b is other than 0, a / b is preferably 0.1 to 10, and when (a + b) is other than 0, (c + d) / (a + b) is preferably 0.01 to 0.5. , More preferably 0.01 to 0.2));
(C *)-(CF ₂ CF (CF ₃ ) O) _e (CF ₂ O) _f (CF (CF ₃ ) O) _g −
(Wherein e, f and g are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements, and when e is other than 0, (f + g) / e is preferably 0.01 to 0.5, more preferably 0.01 to 0.2)
Is selected from.

A first group of preferred compounds (I *) has the following formula (I * -A):
R _a —O—CH ₂ —CF ₂ —O—R _f —CF ₂ —CH ₂ —O—R _a (I * -A)
(Where:
- R _f are compatible with formula as defined above (a *) ~ formula (c *);
-R _a fits the formula (R _a -I *) as defined above)
Fits.

Preferably, in compound (I * -A), the chain R _f conforms to formula (a *).

The second group of compound (I *) has the following formula (I * -B):
A—O—R _f —CF ₂ —CH ₂ —O—R _a (I * -B)
[Where:
- R _f are compatible with formula as defined above (a *) ~ (c * );
-R _a conforms to the formula (R _a -I *) as defined above, and A is a linear or branched C ₁ -C ₄ perfluoroalkyl group, wherein one fluorine atom is Can be substituted with one chlorine atom or one hydrogen atom, provided that chlorine is present in the group A, provided that it is in a molar amount of less than 2% relative to the total amount of end groups. Is)]
Fits.

Preferably, in compound (I * -B), chain R _f conforms to formula (a *).

  Preferred compounds (I * -A) and (I * -B) are those in which r, t and u are 0, and s is a positive number in the range of 4 to 15, preferably 4 to 10. , And r + s are positive numbers in the range of 4-15, preferably 4-10, and t and u are 0.

Preferably, in compound (I * -A) and compound (I * -B), R ¹ is methyl or C (O) CH ₃ .

  The PFPE-PAG of the formula (I *) represents a further aspect of the present invention.

  The PFPE-PAG for use in the method of the present invention comprises a 1- or bifunctional PFPE alcohol, an alkoxylating agent and 4-50, preferably 4-15, more preferably 4-10 oxyalkylene units. It can be obtained by reacting in an amount such as that obtained at one or both chain ends.

To obtain the PFPE-PAG of formula (I), the 1- or bifunctional PFPE alcohol is represented by the following formula (II):
Y—O—R _f — (CF ₂ ) _x —CFZ—CH ₂ —OH (II)
[Where:
_-Rf , x and Z are as defined above;
- Y _{is, (CF 2) x -CFZ-} CH 2 -OH ( here, x and Z are either as defined above, or linear or branched _C 1 -C ₄ perfluoroalkyl group (here And one fluorine atom can be replaced by one chlorine atom or hydrogen atom, provided that when chlorine is present in the group A, it is less than 2% moles relative to the total amount of terminal groups. Selected on the condition that it is a quantity]
Conforms to
The alkoxylating agent is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide, and mixtures of two or more thereof.

Specifically, the bifunctional PFPE-PAG (IA), in which the chain R _a conforms to the formula (R _a -I) as defined above where R ¹ is hydrogen, has the following formula (II-A):
HO—CH ₂ —CF ₂ —O—R _f —CF ₂ —CH ₂ —OH (II-A)
(Wherein R _f conforms to formula (a) as defined above)
Of the bifunctional PFPE alcohol can be obtained by reacting with ethylene oxide, propylene oxide, 1,2-brylene oxide, styrene oxide, or a mixture of two or more thereof.

A monofunctional PFPE-PAG (IB), in which the chain R _a conforms to the formula (R _a -I) as defined above where R ¹ is hydrogen, is instead represented by the following formula ( II-B):
A—O—R _f —CF ₂ —CH ₂ —OH (II-B)
Wherein R _f conforms to formula (a) as defined above and A is a linear or branched C ₁ -C ₄ perfluoroalkyl group wherein one fluorine atom is 1 Can be substituted with one chlorine atom or one hydrogen atom, provided that chlorine is present in the group A, provided that it is in a molar amount of less than 2% relative to the total amount of end groups. To do)
Of the monofunctional PFPE alcohol can be obtained by reacting with ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, or a mixture of two or more thereof.

Chain _{R a} is, ^{R 1} is _C 1 -C ₄ - conform to the formula _(R a -I) straight or branched alkyl, 1- or 2-functional PFPE-PAG is a chain _{R a} is, ^{R 1} Can be obtained by known methods by alkylation of the corresponding 1- and bifunctional PFPE-PAG, which conforms to the formula (R _a -I) in which is hydrogen.

Chain _{R a} is ^{R 1} is compatible with a -C (O) ^{R 2} as defined above formula _(R a -I), 1-and 2-functional PFPE-PAG is a chain _{R a} Can be obtained by known methods by acylating the corresponding 1- and bifunctional PFPE-PAG, which conforms to the formula (R _a -I) where R ¹ is hydrogen.

PFPE alcohols of formula (II-A) or formula (II-B) are, for example, US Pat. No. 6,509,509 (AUSIMMON SPA) (July 5, 2001), US Pat. No. 6,573,411 (AUSIMINT SPA). ) (November 21, 2002), according to several methods known in the art, such as disclosed in WO 2008/122039 (SOLVAY SOLEXIS SPA) (October 16, 2008). The corresponding PFPE carboxylic acid or ester can be prepared by chemical reduction with a reducing agent such as NaBH ₄ or by catalytic hydrogenation. Precursors of PFPE carboxylic acids or PFPE esters are described in US Pat. No. 3,847,978 (MONTEDISO SPA) (November 12, 1974), US Pat. No. 3,766,251 (MONTEDISO SPA) (October 16, 1973). U.S. Pat. No. 3,715,378 (MONTEDSON SPA) (February 6, 1973), U.S. Pat. No. 3,656,041 (MONTEDISON SPA) (May 23, 1972), U.S. Pat. No. 4,647,413 (MINESOTA). (MINING & MFG) (March 3, 1987), European Patent No. 151877A (MINNESOTA MINING & MFG) (August 21, 1985), US Pat. No. 3,442,942 (MONTEDION SPA) (May 6, 1969), US Pat. No. 5,772,291 (AUSIMTON SPA) (July 7, 1988), US Pat. No. 5,258,110 (AUSIMINT SRL) (November 2, 1993), Or as taught in US Pat. No. 7,132,574 (SOLVAY SOLEXIS SPA (July 11, 2006), for example, by oxypolymerization of fluoroolefins or by ring-opening polymerization of HFPO (hexafluoropropylene oxide). Can be manufactured according to various methods.

  Preferably, a PFPE-PAG for use in the method of the present invention is disclosed in International Patent Application No. WO 2014/090649 (SOLVAY SPECIALTY POLYMERS ITPA) (June 19, 2014). Synthesized according to the process (or method). This method, such as the lithium alloy composition described in 6/19/2014, includes the use of a boron-based catalyst species, wherein the species initially contains a catalytic amount of the corresponding alkoxide of PFPE alcohol. A mixture is prepared and then such a mixture is prepared by contacting with a catalytic amount of boric acid triester of the same PFPE alcohol.

In more detail and with particular reference to the preparation of PFPE-PAG according to the present invention, the method comprises the following steps:
1) separately preparing a mixture [M1] comprising a PFPE alcohol of formula (II) as defined above and a catalytic amount of the corresponding alkoxide (hereinafter “PFPE-alk”);
2) The mixture [M1] is brought into contact with the boric acid triester of the same PFPE alcohol (hereinafter “PFPE-triBor”) in such an amount that the molar ratio of PFPE-alk: PFPE-triBor is at least 1. Obtaining a mixture [M2];
3) contacting the mixture [M2] with a catalytic amount of iodine source to obtain a mixture [M3];
4) treating the mixture [M3] with ethylene oxide, propylene oxide, 1,2-butylene oxide or styrene oxide or a mixture thereof to obtain a mixture [M4] containing PFPE-PAG (I). .

In step 1) of this method, the mixture [M1] is typically prepared by adding a base to the PFPE alcohol of formula (II), reacting the base with the PFPE alcohol and dissolving it in the PFPE alcohol. Prepared by forming PFPE-alk. The base can be selected from metal hydrides or metal hydroxides such as NaOH, KOH, Ca (OH) ₂ , and Mg (OH) ₂ ; according to a preferred embodiment, the base is KOH. Typically, the base is used in an amount such that 1-15%, preferably 2-12%, of PFPE-alk is obtained relative to the PFPE alcohol. Thus, for the purposes of this specification, the expression “catalytic amount of PFPE-alk” shall mean a molar amount in the range of 1-15 mol%, more preferably 2-12 mol%, relative to the PFPE alcohol. Intended. When metal hydroxide is used as the base, the reaction is typically facilitated by heating and the progress of the reaction is confirmed by monitoring the amount of water that is evaporated off the reaction mixture. When a metal hydride is used as the base, the progress of the reaction is confirmed by monitoring the amount of hydrogen that is evaporated off the reaction mixture.

Step 2) can be performed in two different ways. In a first preferred embodiment, a mixture containing PFPE-triBor and PFPE alcohol (hereinafter referred to as the mixture [M _est ]) is prepared and then contacted with the mixture [M1]. Typically, [M _est ] is added boric acid or borate esters (including mono-, di-, and trialkyl esters) and the reagents are added until the reaction is complete, ie, with PFPE alcohol. It is prepared by reacting until PFPE-triBor is obtained in the mixture. Typically, the esterification reaction is carried out by heating under reduced pressure and completion is achieved by evaporating water from the reaction mixture (if boric acid is used) or alcohol (if an alkyl ester of boric acid is used). ) By monitoring the amount. In a second preferred embodiment, PFPE-triBor is prepared in situ, ie by adding a boric acid trialkyl ester as defined above to [M1]; Typically, it is carried out by heating under reduced pressure and the completion of the reaction is confirmed in the same way. The molar ratio between PFPE-alk and PFPE-triBor is at least 1; according to a preferred embodiment, PFPE-alk is used in excess over PFPE-triBor, i.e. the molar ratio is greater than 1. Even more preferably, the molar ratio is at least 2. In fact, it was observed that when a molar ratio of at least 2 was used, the reaction proceeded faster and higher conversions were obtained.

Step 3) of the process is typically carried out by adding a catalytic amount of iodine source to the reaction mixture [M2]. Iodine source, one or more alkali metal iodide or iodide alkaline earth metal (NaI, KI, etc. CaI _2), (such as NH ₄ I) ammonium iodide, elemental iodine, and to combinations thereof Can do. According to a preferred embodiment, the iodine source is KI. The catalytic amount of iodine source is typically equivalent in the range of 0.01-5% relative to the fluoroalcohol.

  Step 4) of this process typically involves mixing 4 to 50, preferably 4 to 15 and more preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide or mixtures thereof into the mixture [M3]. This is done by adding a stoichiometric amount with respect to the PFPE alcohol (II) so as to obtain a degree of alkoxylation in the range of 4-10.

  The alkoxylation reaction is typically performed by adding one or more aliquots of ethylene oxide, propylene oxide or mixtures thereof to the mixture [M3] and monitoring oxide consumption and PFPE-PAG formation. Is called. If ethylene oxide or propylene oxide is used, the reaction is monitored by checking the ethylene oxide pressure in the reactor. The reaction is typically carried out under heating at a temperature usually ranging from 90 to 190 ° C. When ethylene oxide is used as the alkoxylating agent, the reaction is usually carried out at a temperature in the range of 110-160 ° C.

  After the reaction is complete, the resulting PFPE-PAG can be isolated from the mixture [M4] by conventional techniques including extraction and distillation. Usually, the mixture [M4] is cooled to room temperature, then diluted with a fluorinated solvent and then treated with an aqueous solution of an inorganic base (typically carbonate), the organic phase is separated and subjected to distillation. Examples of fluorinated solvents include, for example, Galden® PFPE, hydrofluoroethers (HFE) such as Novec® HFE, hydrofluorocarbons (HFC) such as Vertel® or Fluorinert® And fluoroaromatic solvents such as hexafluorobenzene and 1,3-hexafluoroxylene. Typically, the fluorinated solvent is 1,3-hexafluoroxylene.

The PFPE-PAGs according to the present invention have lubricating properties that they are stable under harsh conditions and that they have a lower coefficient of friction, lower wear, and extremes relative to the PAG. It is advantageous to have improved performance under pressure conditions. In particular, experiments this was done by the applicant, PFPE-PAG of formula (I), in particular those of formula (I-A), the same molecular weight as chain _{R a} of PAG and in PFPE-PAG having the same molecular weight It was further demonstrated that it has a lower coefficient of friction, lower wear and higher extreme pressure load for both the PAG with it. Experiments conducted by the applicant have demonstrated that PFPE-PAGs of formula (I), in particular those of formula (IA), have a higher thermal stability than PAGs having the same molecular weight. .
The PFPE-PAG of the present invention can be used to be a mixture with additional ingredients or additives typically used in the manufacture of lubricating compositions. The present invention is therefore further selected from PFPE-PAGs as defined above, in particular PFPE-PAGs of the formula (I), from those commonly used in further lubricants and / or lubricating compositions. The present invention relates to a lubricating composition comprising a mixture with an additive.

In particular, the composition according to the invention is
(A) a PFPE-PAG of formula (I) as defined above with (b) a lubricating base oil;
(C) thickener;
(D) an additive; and optionally (e) a mixture of one or more solvents.

  Non-limiting examples of lubricating base oils include PFPE, polyalphaolefin (PAO), PAG, mineral oil, silicone oil, polyphenyether, and the like.

  Non-limiting examples of additives include rust inhibitors, antioxidants, heat stabilizers, pour point depressants, antiwear agents (including those for high pressure), dispersants, tracers, dyes, talc, and inorganic Contains filler. Examples of dispersants are, for example, surfactants, preferably nonionic surfactants, more preferably (per) fluoropolyether surfactants and (per) fluoroalkyl surfactants.

  Non-limiting examples of PFPE lubricating base oils such as those disclosed are compounds (1) to (8) as of September 16, 2009 in European Patent Application No. 2100909A (SOLVAY SOLEXIS SPA). Identified.

  Examples of thickeners are talc, silica, boron nitride, polyurea, alkali or alkaline earth metal terephthalates, calcium and lithium soaps and their complexes, and PTFE (polytetrafluoroethylene); among them PTFE is preferred.

  Examples of solvents are fluorinated or partially fluorinated solvents such as Galden® PFPE, Novec® HFE and other organic solvents such as methyl-ethyl-ketone, isopropyl alcohol, butyl acetate, and the like. is there.

  The composition comprising PFPE-PAG of formula (I) and PFPE oil may advantageously be in the form of a grease (composition C-1), i.e. the composition comprises PFPE oil, thickener And PFPE-PAG of formula (I) in an amount ranging from 0.1% to 30% by weight, preferably from 3% to 10% by weight relative to the weight of the composition. Experiments conducted by the Applicant have indeed demonstrated that such compositions exhibit significantly lower wear values than greases that do not contain PFPE-PAG. Thus, the PFPE-PAG of the present invention can act as an antiwear additive for lubricating compositions in the form of grease.

A preferred example of a lubricating base oil mixed with a PFPE-PAG of the present invention is represented by PAG. In particular, experiments carried out by the applicant have shown that PFPE-PAGs of formula (I) according to the invention, in particular PFPE-PAGs of formula (IA), can dissolve PAGs. Accordingly, the present invention further comprises a method of lubrication comprising the step of applying a PFPE-PAG of formula (I) as defined above in admixture with a PAG, and a PAG and optionally with one or more additives It relates to a lubricating composition (composition C-2) comprising, preferably consisting of, a PFPE-PAG of the formula (I) as defined above in mixing. Preferred compositions C-2 are PFPE-PAGs and PAGs of formula (I) as defined above, with a weight in the range of 5-10% relative to the weight of the composition, and optionally 1 It contains, preferably consists of more than one type of additive. Accordingly, the present invention further provides
(A1) PFPE-PAG of formula (I) as defined above, and (a2) PAG, preferably PEG, and optionally (a3) a composition C-2 comprising one or more additives .

  Lubricating compositions C-1 and C-2 can be produced by methods known in the art.

  In the event that the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the description of this application to the extent that the terms may be obscured, this description shall control. .

  The invention is disclosed in more detail in the following experimental section by way of non-limiting examples.

Ingredients and Methods PFPE-PAG referred to in the examples is from Solvay Specialty Polymers Italy S. p. A. And in accordance with the method in the international patent application filed on Dec. 4, 2013 together with EP 2013/074476.

  PEG2000 and PEG400 were purchased from Aldrich (registered trademark) and used as they were.

  Kinematic viscosity measurements were performed at different temperatures according to ASTM D445 “Standard Test Method for Kinetic Visibility of Transparent and Opaque Liquids” (and Calculation of Dynamic Viscosity).

  The viscosity index VI was calculated according to ASTM D2270 “Standard Practice for Calculating Visibility Index from Kinetic Visibility at 40 and 100 ° C.”.

  Kinematic viscosities at different temperatures, which were not measured experimentally, were calculated according to the Ubbelohde-Walther equation in the temperature range of 20 ° C to 100 ° C.

  Friction and wear properties are measured using ASTM D6425 “Standard Test Method for Measuring Friction and and using a ball-on-disk arrangement with a 50 Hz frequency and 1 mm stroke, 30 N preload for 30 N and 2 hours for 300 N. “Wear Properties of Extreme Pressure (EP) Lubricating Oils Usage SRV Test Machine”.

  The pour point of the analytical sample was determined according to ASTM D97 “Standard Test Method for Pour Point of Petroleum Products”.

  The wear on the grease samples was evaluated at 75 ° C. with a load of 40 Kgf (1200 rpm, 1 hour) according to ASTM D2266 “Standard Test Method for Wearable Charistics of Lubricating Grease (Four-Ball)”.

  The extreme pressure characteristics of hydraulic fluids for hydraulic devices, gears and engines under high frequency linear vibration motion are described in ASTM D7421 “Standard Test Method for Determining Extremity Properties of Lubricating Oils-Lubricating Oils High-Frequency Oils Usable High-Frequency Oils-Lifting Oils Using High-Frequency Oils. ) Determined according to “Test Machine 1”.

  All of the tests performed to evaluate the friction and wear properties were conducted under isoviscous conditions for comparison with the same lubricious film layer.

Example 1
formula:
_{H (OCH 2 CH 2) O} r CH 2 CF 2 O (CF 2 CF 2 O) m (CF 2 O) n -CF 2 CH 2 O (CH 2 CH 2 O) r H
A PFPE-PAG with r = 5 and p / q is about 1 and an average molecular weight M _n = 2050 was prepared as indicated above.
The product is a clear liquid at room temperature and has a pour point of −18 ° C.

The calculated kinematic viscosity values are as follows:
At 20 ° C. = 395 cSt;
At 40 ° C. = 137 cSt and at 100 ° C. = 17.5 cSt
(The corresponding viscosity index is equal to 141).

  The SRV test was performed at 70 ° C. in two ways with a kinematic viscosity of the product corresponding to 41 cSt. After the test, the average coefficient of friction was 0.14 ± 0.01, and the measured wear-on-the-ball was 1.0 ± 0.1 mm.

Example 2 (comparative example)
Polyethylene glycol PEG 2000, which has an average molecular weight of 2000 and is a white solid at room temperature, was heated above its melting point (about 50 ° C.) to measure kinematic viscosity. At 100 ° C., the kinematic viscosity was equal to 43.04 cSt.

  The SRV test was performed at 100 ° C. in two ways with the same kinematic conditions as in Example 1 with the kinematic viscosity of the product corresponding to 43.04 cSt. After the test, the average coefficient of friction was 0.20 ± 0.02, and the measured wear on the ball was 1.5 ± 0.1 mm.

Example 3 (comparative example)
Polyethylene glycol PEG400 (average molecular weight = 400) was subjected to SRV testing. PEG 400 has a kinematic viscosity equal to 106.6 cSt at 20 ° C., equal to 40.2 cSt at 40 ° C. and 7.03 cSt at 100 ° C. (the corresponding viscosity index is equal to 136) and is transparent at room temperature It is liquid.

  The SRV test was performed at 40 ° C. in two ways with the kinematic viscosity of the product corresponding to 40.2 cSt under the same isoviscous conditions as in Example 1 and Comparative Example 2. After the test, the average coefficient of friction was 0.20 ± 0.02, and the measured wear on the ball was 1.4 ± 0.06 mm.

In Example 1, Example 2 and Example 3 above, PFPE-PAG is
-PEG having the same molecular weight as the PFPE-PAG of Example 1 (Comparative Example 2);
-Shows a lower coefficient of friction, lower wear and good viscosity index for both the PAG moiety in the PFPE-PAG of Example 1 (Comparative Example 3) and PEG having the same molecular weight. .

Example 4
formula:
_{HO (CH 2 (CH 3)} CHO) s (CH 2 CH 2 O) r CH 2 CF 2 O (CF 2 CF 2 O) m (CF 2 O) n -CF 2 CH 2 (OCH 2 CH 2) r (OCH (CH ₃ ) CH ₂ ) _s OH
A PFPE-PAG with r = 2.5, s = 4.5 and m / n is about 1 and an average molecular weight M _n = 2050 was prepared as indicated above.

  The product is a clear liquid at room temperature with a pour point of -38 ° C.

The kinematic viscosity values are as follows:
At 20 ° C. = 274 cSt,
At 40 ° C. = 98 cSt
And at 100 ° C. = 13.7 cSt
(The corresponding viscosity index is equal to 142).

  The SRV test was performed at 50 ° C. in two ways with a kinematic viscosity of the product corresponding to 63 cSt. After the test, the average coefficient of friction was 0.15 ± 0.004 and the measured wear on the ball was 1.1 ± 0.1 mm.

Example 5
10 g of PEG 400 was added to 200 g of PFPE-PAG of Example 4 in a glass container and kept at room temperature with stirring. After 15 minutes, stirring was stopped and a clear solution was obtained.

Example 6
20 g of PEG 400 was added to 200 g of the product of Example 1 in a glass container and kept at room temperature under stirring. After 15 minutes, stirring was stopped and a clear solution was obtained.

  Examples 5 to 6 show that the PFPE-PAG of the present invention can dissolve PAG.

Example 7
The thermal stability test for the PFPE-PAG of Example 1 was performed by TGA in air (10 ° C./min). At 250 ° C., a 6% weight loss was observed, but at 300 ° C., the corresponding value was 19% (see FIG. 1).

Example 8
The thermal stability test for PEG of Example 2 was performed by TGA in air (10 ° C./min). At 250 ° C., a weight loss of 9.5% was observed, but at 300 ° C., the corresponding value was 34% (see FIG. 1).

  Examples 7 and 8 show that the PFPE-PAGs of the present invention have improved thermal stability over PAGs having the same molecular weight.

Example 9 (comparative example)
A perfluorinated grease was prepared by adding a commercially available PFPE, Fomblin® M30 to the PTFE powder to reach a cone penetration value of 277 mm / 10 inches.

  This grease was subjected to a 4-ball wear test according to the procedure described above. The wear observed on the ball after the test was 1.46 mm + 0.04 mm.

Example 10
To the grease prepared in Example 9, 5% by weight of PFPE-PAG of Example 1 was added and subjected to a 4-ball wear test according to the procedure described above.

  The wear observed on the ball after the test was 0.80 mm + 0.05 mm.

  Examples 9 and 10 show that the PFPE-PAG of the present invention can act as an anti-wear additive for perfluorinated greases.

Example 11
The PFPE-PAG of Example 4 was analyzed under extreme pressure conditions according to ASTM D7421 under the following operating conditions:
-Temperature: 60 ° C (the kinematic viscosity of the sample oil at this temperature was 43 cSt);
-Stroke: 2mm
-Frequency: 50Hz
-Preload: 30 seconds at 50N-Load: 15 minutes at 100N and an increase of 100N every 2 minutes to 2000N.

  The results showed that no seizure occurred at a final load of 2000N.

Example 12 (comparative example)
A commercial base oil (without additives) consisting of polypropylene glycol monobutyl ether having an average molecular weight _Mn of 1400 g / mol was analyzed. The kinematic viscosity values were as follows:
At 20 ° C. = 316 cSt;
At 40 ° C. = 115 cSt and at 100 ° C. = 20.8 cSt
(The corresponding viscosity index is equal to 207).

  The SRV test was performed in two ways at 70 ° C. with a kinematic viscosity of the product corresponding to 44 cSt. After the test, the average coefficient of friction was 0.22 ± 0.001, and the measured wear on the ball was 1.6 ± 0.1 mm.

  The base oil was analyzed under extreme pressure conditions according to ASTM D7421 under the same operating conditions as in Example 11: the results showed that seizure occurred at a load of 1000 N.

  A comparison of Example 11 and Example 12 shows that the presence of the PFPE sequence in PFPE-GAG gives the PAG base oil lubrication properties, low coefficient of friction, low wear and significantly improved extreme pressure properties.

Claims (13)

On the surface to be lubricated, the following formula (I):
A—O—R _f — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a (I)
{In the formula:
- R _f is 100～8,000, during preferably 300～6,000, more preferably have a number average molecular weight _{M n} in the range of 800 to 3,000, and (i) -CFXO- (wherein, X is F or CF ₃ );
(Ii) -CFXCFXO- (wherein X is the same or different at each occurrence and is F or CF ₃ provided that at least one of X is -F),
_{(Iii) -CF 2 CF 2 CW} 2 O- ( wherein each of W differs same or another, is F or H),
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-,
_{(V) - (CF 2)} j -CFZ'-O- [ wherein, j is an integer of 0 to 3, Z 'has the general formula -OR _f' is a group T, then where, R _f ′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are represented by the following: —CFXO—, —CF ₂ CFXO—, —CF ₂ CF ₂ CF ₂ O—, — CF ₂ CF ₂ CF ₂ CF ₂ O— (each X is independently F or CF ₃ ) and T is a C ₁ -C ₃ perfluoroalkyl group]
A (per) fluoropolyoxyalkylene chain comprising, preferably consisting of, repeating units which may be the same or different from each other selected from
- Z is fluorine or _CF 3;
-X is 0 or 1, provided that when x is 1, Z is F;
A is — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a , where x and Z are as defined above, or linear or branched C ₁ -C ₄ perfluoro An alkyl group, wherein one fluorine atom can be replaced by one chlorine atom or one hydrogen atom, provided that when chlorine is present in the group A, it is relative to the total amount of end groups. Subject to a molar amount of less than 2%),
-R _a is a hydroxy-, alkoxy- or acyloxy-terminated polyoxyalkylene chain (chain R _a ) that does not contain a fluorine atom, said chain comprising 4 to 50 fluorine-free oxyalkylene units, units are the same or different from one _{another, -CH 2 CH 2 O -,} - CH 2 CH (CH 3) O -, - CH 2 CH (CH 2 CH 3) O- and _-CH 2 CH (Ph) from O- Selected
However, A _is, - _(CF 2) a x _-CFZ-CH 2 -R _a, chain _{R a} are hydroxyl-terminated, and if it contains only _-CH 2 _CH 2 O- units, the chain _{R f} Is provided that it does not consist only of —CF ₂ CF ₂ O— repeating units}
A method of lubrication comprising the step of applying a polymer compatible with The chain R _f in the polymer (I) is represented by the following formulas (a) to (c):
Selected from the following formulas (a) to (c):
(A)-(CF ₂ O) _n (CF ₂ CF ₂ O) _m (CF ₂ CF ₂ CF ₂ O) _p (CF ₂ CF ₂ CF ₂ CF ₂ O) _q −
Wherein m, n, p, q are 0, or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements, provided that n is not 0 at the same time when p and q are not 0 at the same time. When m is not 0 and m is other than 0, the m / n ratio is preferably 0.1-20, and when (m + n) is other than 0, (p + q) / (m + n) is preferably 0-0. 2)
(B)-(CF ₂ CF (CF ₃ ) O) _a (CF ₂ CF ₂ O) _b (CF ₂ O) _c (CF (CF ₃ ) O) _d −
Wherein a, b, c, d are 0, or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that at least one of a, c and d is 0. When b is other than 0, a / b is preferably from 0.1 to 10, and when (a + b) is other than 0, (c + d) / (a + b) is preferably from 0.01 to 0. 5, more preferably 0.01-0.2));
(C)-(CF ₂ CF (CF ₃ ) O) _e (CF ₂ O) _f (CF (CF ₃ ) O) _g −
(Wherein e, f and g are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements, and when e is other than 0, (f + g) / e is preferably 0.01 to 0.5, more preferably 0.01 to 0.2)
The method of claim 1, wherein the method is selected from: The chain R _a in the polymer (I) is represented by the following formula (R _a -I):
(R _a -I)-(CH ₂ CH ₂ O) _r (CH ₂ CH (CH ₃ ) O) _s (CH ₂ CH (CH ₂ CH ₃ ) O) _t (CH ₂ CH (Ph) O) _u R ¹
[Wherein r, s, t and u are independently selected from 0 and a positive number, r + s + t + u ranges from 4-50, R ¹ is hydrogen, C ₁ -C ₄ linear or branched Alkyl, and —C (O) R ² , wherein R ² is selected from C ₁ -C ₄ linear or branched (halo) alkyl]
Provided that the chain R _f of compound (I) contains only CF ₂ CF ₂ O-units and the chain (R _a -I) at both ends (wherein s, t and u are 0) ), The method of claim 1 or 2, wherein R ¹ is not hydrogen. In the chain (R _a -I), r is a positive number in the range of 4-15, s, t and u are 0, and R ¹ is selected from hydrogen or methyl, provided that the compound (I chain _{R f} of) _comprises only -CF 2 _CF 2 O- units, and when it has a chain _(R a -I) at both ends, ^{R 1} is a not hydrogen, according to claim 3 the method of. In chain (R _a -I), r, t and u are 0, s is a positive number in the range of 4-15, and R ¹ is selected from hydrogen or methyl. The method described. In chain _(R a -I), t and u is a 0, r + s is in the range of 4 to 15, ^{R 1} is selected from hydrogen or methyl, A method according to claim 3. Polymer (I) has the following formula (IA):
R _a —O—CH ₂ —CF ₂ —O—R _f —CF ₂ —CH ₂ —O—R _a (IA)
Wherein R _a is as defined in any one of claims 1, 3, 4 or 6, and R _f conforms to formula (a) as defined in claim 2. )
7. A method according to any one of claims 1 to 6, adapted to Formula (I *)
A—O—R _f — (CF ₂ ) _x —CFZ—CH ₂ —O—R _a (I *)
{In the formula:
- R _f is 100～8,000 preferably 300～6,000, more preferably have a number average molecular weight _{M n} of 800 to 3,000,
(I) -CFXO- (wherein, X is F or CF _3);
(Ii) -CFXCFXO- (wherein X is the same or different at each occurrence and is F or CF ₃ , provided that at least one of X is -F),
_{(Iii) -CF 2 CF 2 CW} 2 O- ( wherein each of W, the same or different from each other, are F or H),
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-,
_{(V) - (CF 2)} j -CFZ'-O- [ wherein, j is an integer of 0 to 3, Z 'has the general formula -OR _f' is a group T, then where, R _f ′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are represented by the following: —CFXO—, —CF ₂ CFXO—, —CF ₂ CF ₂ CF ₂ O—, — CF ₂ CF ₂ CF ₂ CF ₂ O— (each X is independently F or CF ₃ ), and T is a C ₁ -C ₃ perfluoroalkyl group]
A (per) fluoropolyoxyalkylene chain comprising, preferably consisting of, repeating units, which may be the same or different from each other, selected from
- Z is fluorine or _CF 3;
-X is 0 or 1, provided that when x is 1, Z is F;
- A _{is, (CF 2) x -CFZ-} CH 2 -O-R a ( wherein, x and Z are either as defined above, or a linear or branched _C 1 -C ₄ perfluoroalkyl A group (wherein one fluorine atom can be replaced by one chlorine atom or one hydrogen atom, provided that when chlorine is present in the group A, it is relative to the total amount of terminal groups; Subject to a molar amount of less than 2%);
-R _a is represented by the following formula (R _a -I *):
_{- (CH 2 CH 2 O)} r (CH 2 CH (CH 3) O) s (CH 2 CH (CH 2 CH 3) O) t (CH 2 CH (Ph) O) u R 1 (R a -I *)
[Where:
-R, s, t and u are independently selected from 0 and a positive number, r + s + t + u is a positive number in the range of 4-50;
R ¹ is from hydrogen, C ₁ -C ₄ linear or branched alkyl, and —C (O) R ^2, where R ² is C ₁ -C ₄ linear or branched (halo) alkyl. Selected, provided that when R ¹ is hydrogen, at least one of s, t and u is selected if not 0)]
Fits}
Suitable for polymers. The chain R _f is represented by the following formulas (a *) to (c *):
(A *)-(CF ₂ O) _n (CF ₂ CF ₂ O) _m (CF ₂ CF ₂ CF ₂ O) _p (CF ₂ CF ₂ CF ₂ CF ₂ O) _q −
(Wherein m, n, p, q are 0 or an integer selected such that the chain R _f satisfies the above-mentioned number average molecular weight requirements, and when m is other than 0, the m / n ratio is: Preferably, it is 0.1-20, and when (m + n) is other than 0, (p + q) / (m + n) is preferably 0-0.2);
(B *)-(CF ₂ CF (CF ₃ ) O) _a (CF ₂ CF ₂ O) _b (CF ₂ O) _c (CF (CF ₃ ) O) _d −
Wherein a, b, c and d are 0 or an integer selected such that the R _f chain satisfies the above number average molecular weight requirement, provided that at least one of a, c and d is When b is other than 0, a / b is preferably 0.1 to 10, and when (a + b) is other than 0, (c + d) / (a + b) is preferably 0.01 to 0.5, more preferably 0.01 to 0.2).
(C *)-(CF ₂ CF (CF ₃ ) O) _e (CF ₂ O) _f (CF (CF ₃ ) O) _g −
(Wherein e, f and g are 0 or an integer selected such that the R _f chain satisfies the above-mentioned number average molecular weight requirement, and when e is other than 0, (f + g) / e is preferably Is 0.01 to 0.5, more preferably 0.01 to 0.2)
9. A polymer according to claim 8, selected from: The following formula (I * -A)
R _a —O—CH ₂ —CF ₂ —O—R _f —CF ₂ —CH ₂ —O—R _a (I * -A)
(Where:
-R _a conforms to the formula (R _a -I *) as defined in claim 9,
- R _f is conform to the formula (a *) as defined in claim 10)
The polymer of claim 9. The polymer according to claim 10, wherein r, t and u in formula (R _a -I *) are 0 and s is a positive number in the range of 4-15. The polymer according to claim 10, wherein in the formula (R _a -I *), r + s is a positive number of 4 to 15, and t and u are 0. (A) a polymer as defined in any one of claims 8 to 12,
(B) a lubricating base oil;
(C) thickener;
A composition comprising (d) an additive; and optionally (e) one or more mixtures of solvents.

Images