FLUORINE-CONTAINING GREASE COMPOSITION

Abstract: A fluorine-containing grease composition comprising a halogen-containing polyether of the formula: -(CH₂CF₂CF₂0) a -(CHClCF₂CF₂0) b -(CCl₂CF₂CF₂0) c - (CHFCF₂CF₂0) d -(CFClCF₂CF₂0) e -(CF₂CF₂CF₂0) f - (I) wherein a, b, c, d, e and f are each an integer not less than 0 and satisfy the following equations: 2 ≦ a+b+c+d+e+f ≦ 200 and 1 ≦ a+c+d+f and 0.5 to 60% by weight of a fluororesin base in the weight of the whole composition, which has good chemical and heat resistance and is used in a high temperature environment.

Description: FIELD OF THE INVENTION The present invention relates to a fluorine-containing grease composition. More particularly, it relates to a fluorine-containing grease composition comprising a fluorine-containing polyether as a base oil and a fluorine-containing resin. BACKGROUND OF THE INVENTION A grease composition comprising a lubricant oil and, as a thickening agent, fine powder of silica gel, alminium hydroxide or ferric hydroxde dispersed in the oil is commercially available. Since such the grease composition had poor chemical resistance, it cannot be used as a grease for a cock of a chemical equipment with which a corrosive gas such as CF₃Br, Br₂, Cl₂, F₂, HF and ClF₃ contacts. In addition, its heat resistance is poor, it cannot be used in a high temperature environment. To overcome these defects of the grease composition, a grease composition comprising a low molecular weight polymer of trifluorochloroethylene, polyether having branched perfluoroalkyl groups and a fluororesin was proposed (cf. Japanese Patent Publication Nos. 18079,/1954 and 45715/1974). Although the proposed grease composition has better chemical and heat resistance than the above describe one, it still has drawbacks such that the fluorine-containing base oil has high vapor pressure and tend to vaporize at a high temperature or in vacuo so that its application is limited. SUMMARY OF THE INVENTION One object of the present invention is to provide a grease composition having good chemical and heat resistance. Another object of the present invention is to provide a grease composition having low vapor pressure so that it can work for a long time even at a high temperature and/or in vacuo. Accordingly, the present invention provides a fluorine-containing grease composition comprising a halogen-containing polyether of the formula: wherein a, b, c, d, e and f are each an integer not less than 0 and satisfy the following equations: 2 < a+b+c+d+e+f < 200 and 1 < a+c+d+f and 0.5 to 60 % by weight of a fluororesin based on the weight of the whole composition. In the formula (I), the sequence of the repeating units in the parentheses is arbitrary but not restricted to the above sequence. The halogen-containing polyether (I) is a novel polymer and disclosed in EP-A-Publication No. 0148482 published on July 17, 1985). Although the preparation of the polyether (I) is disclosed in detail in the above applications, it is briefly explained. The polyether (I) wherein b, c, d, e and f are 0 (zero) and a is not 0 (zero) is prepared by ring opening polymerization of 2,2,3,3-tetrafluorooxetane preferably in the present of an initiator (e.g. halides of alkali metals or a compound having strong Lewis acidity). The polyether (I) wherein at least one of b, c, d, e and f is not 0 (zero) is prepared by fluorinating and/or chlorinating the polyether (I) wherein b, c, d, e and f are 0 (zero) and a is not 0 (zero) produced in the above manner. Since the polyether (I) used according to the present invention is a straight polymer, it has lower vapor pressure and better chemical and heat resistance and its viscosity is less affected by temperature change than a conventional branched halogen-containing polyether, for example, one comprising following repeating units: and a polymer of the formula: provided that the viscosities are the same. The fluororesin used according to the present invention is a solid one and its examples are polytetrafluoroethylene, a copolymer of tetrafluoroethylene and a comonomer copolymerizable thererwith (e.g. hexafluoropropylene, ethylene and vinyl ether having a fluoroalkyl group), polychlorotrifluoroethylene and a copolymer of chlorotrifluoroethylene and a comonomer copolymerizable therewith. Along them, preferred is polytetrafluoroethylene having a low molecular weight of 5,000 to 800,000, especially 10,000 to 500,000. The term "polytetrafluoroethylene" herein used is intended to include not only a homopolymer of tetrafluoroethylene but also a copolymer of tetrafluoroethylene with not more than 1 (one) % by weight of a modifier such as hexafluoropropylene, perfluoro(alkyl vinyl ether) and chlorotrifluoroethylene. The smaller the particle size of the fluororesin, the better. When the particle size is 10 µm or less, the amount of the resin to be added can be reduced, and the prepared grease composition is smooth and has good distribution property. The content of the fluororesin in the grease composition of the invention is from 0.5 to 60 % by weight based on the weight of the whole composition. When the content is less than 0.5 % by weight, the dropping point of the grease composition is too low and oil separation is too large to be used in a high temperature environment and further the viscosity of the composition greatly varies with temperature change. When the content is larger than 60 % by weight, the grease composition becomes so hard that its preparation is difficult, its distribution property is deteriorated and it tends to solidify at a high temperature. The grease composition can be prepared by a per se conventional method. For example, powdery fluororesin is added to the halogen-containing polyether (I) having a suitable viscosity and agitated or fixed by means of three-roll or kneader to prepare the grease composition. In other method, a dispersion of solid fluororesin in a suitable solvent such as trichlorotrifluoroethane is added to the halogen-containing polyether (I) and homogeneously mixed while removing the solvent under heating and/or evacuating. In addition to the above two essential components, the grease composition of the invention may contain a hydrocarbon base or silicon compound base grease, and particularly a conventional halogen-containing grease. The present invention will be hereinafter explained further in detail by following examples. Examples 1-4 and Comparative Examples 1-2 To a base oil (680 g) shown in Table 1, fine powder of polytetrafluoroethylene (average particle size of 0.3 µm, average molecular weight of about 400,000) or a copolymer of 99.85 % by mole of tetrafluoroethylene and 0.15 % by mole of hexafluoropropylene (average particle size of 0.15 µm, average molecular weight of about 200,000) (320 g) was added and agitated in a kneader for 6 hours to obtain a grease composition. Its physical properties are measured as follows: Acid Resistance The grease composition is immersed in 35 % by weight hydrochloric acid at a room temperature for 16 hours. Then, change of appearance is observed. Alkali Resistance The grease composition is immersed in 10 % by weight aqueous solution of sodium hydroxide at a room temperature for 16 hours. Then, change of appearance is observed. Non-miscible Viscosity Measured according to the specification of JIS (Japanese Industrial Standards) K2560. Evaporation Amount The grease composition (0.25 g) is uniformly applied on a glass plate (26 mm x 76 mm) and kept at 150°C for 7 days. Then, the weight loss is measured. Extreme-Pressure Limit Load Measured by Falex tester. The results are shown in Table 2. Example 4 To the same base oil (700 g) as used in Example 1, polytetrafluoroethylene (300 g, average particle size of 0.1 µm, average molecular weight of about 60,000) dispersed in trichlorotrifluoroethane (1,700 g) at a concentration of 15 % by weight was added and agitated in a universal mixer for 8 hours under heating while removing the solvent by evacuation to obtain a grease composition. Example 5 To the same base oil (850 g) as used in Example 1, polytetrafluoroethylene (150 g, average particle size of 0.1 µm, average molecular weight of about 60,000) dispersed in trichlorotrifluoroethane (1,725 g) at a concentration of 15 % by weight was added and agitated in a universal mixer for 8 hours under heating while removing the solvent by evacuation to obtain a grease composition.

Claims: A fluorine-containing grease composition comprising a halogen-containing polyether of the formula: wherein a, b, c, d, e and f are each an integer equal to or above 0 and satisfy the following equations: and 0.5 to 60 % by weight of a fluororesin based on the weight of the whole composition. A fluorine-containing grease composition according to claim 1, wherein b=c=d=e=f=0 (zero). A flourine-containing grease composition according to claim 1, wherein a=b=c=d=e=0 (zero). A fluorine-containing grease composition according to claim 1, wherein a=b=d=e=f=0 (zero). A fluorine-containing grease composition according to claim 1, wherein the fluororesin is one selected from the group consisting of polytetrafluoroethylene, a copolymer of tetrafluoroethylene and a comonomer copolymerizable thererwith, Polychlorotrifluoroethylene and a copolymer of chlorotrifluoroethylene and a comonomer copolymerizable therewith. A fluorine-containing grease composition according to claim 5, wherein the fluororesin is polytetrafluoroethylene or a tetrefluoroethylene/hexafluoropropylene copolymer.

Inventors: FUKUI, SHOSHIN, SHIMASAKI, SHUHEI, TOHZUKA, TAKASHI
Applicants: DAIKIN INDUSTRIES, LIMITED
Application year: 1985
Main classification: C10M107
IPC codes: C10M105, C10N50, C10N30, C10M107, C10M169