DE2252061A1 - CORROSION-RESISTANT LUBRICATING OIL AND THE METHOD FOR MANUFACTURING IT - Google Patents

Description

Priority: 5th November 1971, USA, No. 196 005

The invention "relates to a synthetic lubricating oil blend and a peculiar method of making it.

The use of synthetic poly- and perhalogenated polymeric materials as lubricating oils, especially in systems that are exposed to extremely high temperatures are well known in the art. A serious one However, the problem which has arisen in connection with these synthetic oils is that it is extraordinary it is difficult to avoid corrosion of the metal parts that are in the presence of moisture with these oils come into contact. Metals that are corrosive to these oils

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dated include steels, copper and aluminum. the Halogenated oils are particularly disadvantageous when they are applied in systems that are constructed from aluminum are. These oils usually detonate when exposed to aluminum at high temperatures under shear conditions stand in touch.

It has therefore already been proposed to incorporate various anti-corrosion agents into the lubricating oils in order to to avoid these difficulties. However, all of these attempts have failed, reflecting in part on one so far lack of understanding of the reasons for the great sensitivity of metals to corrosion in the presence of them halogenated oils. It has recently been found that these oils do indeed cause corrosion of metals in the presence of moisture or act as catalysts for it. Difficulties, that have arisen in the prior art in solving this problem are of such magnitude achieved that attempts to avoid corrosion were carried out in the form that attempts were made to remove moisture completely excluded from environments in which these oils have been applied. It is obvious to a person skilled in the art that efforts to avoid contamination with moisture in these systems require the use of would require very sophisticated and complex monitoring.

There is a further disadvantage of these attempts to prevent corrosion by adding corrosion protection additives in that these materials very often tend to inhibit the lubricity of the oils to which they are added or to impair it in a disruptive manner. In some cases these agents practically lead to the decomposition of the ha-

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logenated polymers that make up the oil.

It is therefore the aim of the invention to make a lubricating oil available, which the corrosion of metals with which it comes into contact, prevented and essentially practically inhibited in the presence of large amounts of moisture. The invention is also based on the object of creating a lubricating oil which has an anti-corrosive effect without that there is a need to add anti-corrosive agents to this oil.

Another object of the invention is a lubricating oil which is anti-corrosive without the need to be present to exclude moisture from systems in which it is applied.

The invention also relates to a peculiar method of making such an anti-corrosive agent effective oil.

These and other objects of the invention are accomplished by means of one achieved new lubricating oil, which is prepared by the inventive method described below.

According to the invention it has been found that a lubricating oil can be produced which is remarkably resistant against any corrosive effect on metals with which it comes into contact in the presence of moisture comes. According to the invention, this highly corrosion-resistant lubricating oil mixture is produced by intimately mixing a synthetic, halogen-containing polymer oil and a fluorocarbon resin, freezing the mixture and thawing the frozen one Product manufactured.

The subject of the invention is thus a highly corrosion-resistant lubricating oil mixture, which is characterized in that

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that it consists of a frozen and thawed mixture composed of a synthetic polymer oil containing a halogen substituent and a fluorocarbon resin.

The invention also relates to a method for producing a highly corrosion-resistant lubricating oil mixture, which is characterized in that one

a) a synthetic polymer oil that has a halogen substituent contains, and a fluorocarbon resin intimately mixed,

b) the mixture freezes to form the solid phase and

c) the frozen mixture to form the anti-corrosive thaws effective lubricating oil again.

The invention is based on the discovery that a new and highly anti-corrosive synthetic halogenated polymer oil mixture from certain components, which as such are relatively highly corrosive to metals in the presence of Moisture are effective, can be produced by the method described above, which involves intimate mixing, Includes freezing and thawing.

The mechanism by which this method gives the oil mixture anti-corrosive properties is not known. not the physical or chemical changes are also known, which take place in the components of the oil mixture to make it anti-corrosive. It "However, it was also found that the mixture of Cl and Fluorocarbon resin should only be subjected to one freeze-thaw cycle. When the thawed mixture is frozen again and is thawed, then all corrosion-resistant properties are lost, which the mixture by the first Freezing cycle have been awarded. Care should therefore be taken to prevent re-freezing the mass after thawing is avoided.

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For the practical implementation of the invention it is essential that that the steps of the method described above are carried out in the precise order given. A material that, by simply mixing the oil and resin components, produced without freezing does not prevent corrosion.

In addition, the mere freezing of the various components, without these being intimately mixed beforehand, there is no change in the anti-corrosive properties of these Components. In addition, the oil and resin must be intimately mixed together before freezing. That Separate freezing and thawing of the ingredients and their subsequent mixing makes the mixture non-corrosive effective.

Any of the well known synthetic halogen containing can be used in practicing the invention polymeric oils can be used. These oils are well known in the art and generally include if also not necessarily fluorinated synthetic polymers with a degree of polymerization sufficient to achieve the to give the resulting liquid a relatively high viscosity. While the most commonly used oils include fluorinated polymers, this term should be understood to mean that the invention is applicable to any synthetic polymeric oil containing fluorine, chlorine, bromine, iodine or contains mixtures of such substituents. Typical examples for these materials are poly (halogenated vinyl halides) , Poly (halogenated ethylenes), poly (halogenated silicones), poly (halogenated ethers) and the like. Examples for these oils are trifluorovinyl chloride polymers, chlorotrifluoroethylene polymers, trifluoropropylmethylpolysilicones, Perfluoroalkyl polyethers and the like. It can be seen that the above examples are suitable

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oils do not represent a limitation of the invention. According to the invention Any synthetic halogenated lubricating oil blend can be substantially non-corrosive to metals be made in the presence of moisture. It is obvious that the choice of a particular oil depends on the intended one Purpose or the system depends in which this oil is to be used.

The synthetic halogenated oils described above are well known and can be made by methods similarly well known in the art. For example, the polymeric chlorotrifluoroethylene oils can be produced by adding the products of the polymerization of Ohio? trifluoroethylene in fractions from oils, fats and Waxes are separated and the products are then pyrolyzed to produce a low boiling halocarbon oil which has a relatively high viscosity and a lower molecular weight than the original polymer Product. The oil, fat and wax fractions can be pyrolyzed individually or in combination. The halogenated Polyvinyl, silicone, polyether oils and the like can can also be made by methods well known in the art.

It has been found that the invention is applicable only when using a fluorocarbon resin. As already stated, are the reasons for the peculiar accessibility of only this type of material, enhancing the anti-corrosive nature of the to promote the oils described above, currently unknown. It should be noted that there are numerous different types of materials have been tested and found to be unsuitable.

The fluorocarbon resin is preferably crushed to a finely divided form and suspended in a liquid

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"For example, a silicone oil that contains the halogenated oil is compatible with which it is intended to be mixed to form a fat-like product. The preferred fluorocarbon resin is polytetrafluoroethylene. One under the designation Dixon 164 by Dixon Corporation, Bristol, Rhode Island produced product has proven to be particularly suitable.

The highly anti-corrosive properties are the oil mixture bestowed by about 3.0 to about 5.0 weight 5 ^, preferably about 4.0% by weight of the fluorocarbon fat with the Oil are mixed, the mixture is frozen to a solid state, and then the frozen mixture is thawed. This information however, it is to be understood that the addition of any amount of the fluorocarbon resin is practical Practice of the invention results in at least some degree of anti-corrosion effect being imparted to the oil.

Any conventional device can be used to mix the oil and fat; it is only necessary that an intimate mixture of the two components is achieved. If desired, to facilitate mixing, the Common emulsifying agents can be added to the components.

The intimate mixture is then solidified by freezing. This may be according to some well known Freezing method. The most common and practical method is to mix the mixture in one against low temperatures to give resistant container and to immerse the container in a cold liquid, such as liquid Nitrogen, liquid argon, neon, liquid oxygen and the like. It is understood, however, that any System that is capable of freezing the oil-resin mixture to generate • sufficiently low temperatures to carry out

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of the frozen can be applied. Eb eats only necessary that the mixture is frozen to a practically completely solid state.

After freezing, the mixture is thawed and exposed Use refurbished. Any customary additives, for example detergents, wetting agents, fillers, can be used and the like conventionally employed in lubricating oil compositions can be added. before The final packaging should check the pH of the mixture can be set to a minimum of 5.1. Bas resulting Product is highly resistant to corrosion in the presence of water.

The invention is illustrated in more detail below with reference to the following specific examples, without that it should be limited to that. In these examples, all parts mean parts by weight.

example 1

229 g of a polychlorotrifluoroethylene oil with a dropping point of -50 ° C, a viscosity of 34 at 37.8 ° C, an initial boiling point of 260 ° C (initial boiling point) and a cloud point of -7.8 ° C were together with 9.16 g a polytetrafluoroethylene resin suspension (Dixon 164-Dixon Corporation, Bristol, Rhode Island) in a commercially available household mixer. The mixture was at a failure rate stirred from 19,000 rpm until the ingredients were completely and intimately mixed with one another. Then became the mixture poured into a container and sealed with a tight-fitting lid. The container was during Submerged completely in liquid nitrogen in a dewar for 1 1/2 hours until the mixture solidified

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Condition was frozen.

The container was removed from the liquid nitrogen and allow the material to thaw undisturbed at room temperature. After thawing, the contents of the container poured into a homogenizer and homogenized. The homogenized mixture was returned to the mixer and it became 0.24 g of a linear lauryl sulfate detergent and 1.2 g of polyisobutylene added as a wetting agent. The mixture was mixed for several minutes to give a ensure complete mixing of the ingredients. The mixture was found to have an average pH 6.7.

The anti-corrosion effect (corrosion resistance) of the oil mixture was tested in the following way: 25 ml of des The oil prepared as in Example 1 above and 2 ml of water were intimately mixed with one another and placed in a test tube given. A clean, low-grade mild steel nail was immersed in the oil and held for 48 hours Allowed to stand at 60 ° C, after which visual observation was made to determine the extent of corrosion. No signs of corrosion were observed. The nail was removed from the oil and visually compared to a similar nail that had not been dipped in the oil. Visually there could be no difference can be found between the nails.

Example 2

40.2 g of a Polytrifluorvinylchlorid-oil having a pour point of -40 ⁰ C, a viscosity of 35 at 37.8 ° C and an initial boiling (initial boiling point) of 100 ° C and 1.6 g of a Polytetrafluorätb ^ ylene suspension (Dixon 164) were mixed according to the procedure described in Example 1

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and worked up.

The oil produced was as in Example 1 on his corrosion protection properties tested. No visual evidence of corrosion was found.

Example 3

220 g of a Trifluorpropylmethylpolysilikonöls with a Viscosity at 37.8 ° C of 25 and an onset of boiling (initial boiling point) of 204j4 ° C and 8.8 g of a polytetrafluoroethylene suspension (Dixon 164) were mixed and worked up according to the procedure given in Example 1.

The oil thus formed was tested as in Example 1 for its anti-corrosive properties. No visual evidence of corrosion was found.

Example 4 -

105 g of a perfluoroalkyl polyether oil with a dropping point of -55 ° C, a viscosity at 37.8 ° C of 36 and an initial boiling point (initial boiling point) of 287 _f 8 ° C and 4.2 g of a polytetrafluoroethylene suspension (Dixon 164) were mixed and processed as in Example 1.

The oil thus formed became as in Example 1 with respect to tested for its anti-corrosive properties. There was no visual evidence of corrosion will.

The following examples show the high level of corrosion resistance the oil mixture according to the invention in the

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same with previously "known oil mixtures.

Example 5

25 ml of the polychlorotrifluoroethylene oil used in Example 1 and 2 ml of water were mixed intimately and placed in a test tube. A nail similar to that in Example 1 was immersed therein and allowed to stand at 60 ° C for 48 hours, after which a visual observation was made to determine the extent of the corrosion. It was found that the nail was severely corroded and pitted was.

Example 6

25 ml of the polytrifluorovinyl chloride oil used in Example 2 were tested according to the method of Example 5 with regard to its anti-corrosive properties. It shows found that the nail used had a thick layer of the corroded metal.

Example 7

The trifluoropropylmethyl polysilicon oil of Example 3 was tested by the method of Example 3 for its properties with regard to corrosion resistance. The one used The treatment severely corroded the nail.

Example 8

The perfluoroalkyl polyether oil according to Example 4 was tested for its corrosion resistance using the method of Example 4. The nail used was badly corroded by the test.

The following examples show the necessity of the freezing stage, to ensure the oils are corrosion-resistant or corrosion-resistant

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to impart protective properties.

Example 9

The procedure of Example 1 was repeated with the exception that the freezing and thawing stages have been omitted. The resulting oil-fat mixture was made according to the procedure of Example 1 tested for its corrosion resistance. The nail used was found to be strong has been corroded.

Example 10

The procedure of Example 2 was repeated with the modification that the oil-fat mixture was not frozen. The resulting product was tested for corrosion resistance according to the method of Example 1, with the result that the nail used in the test was found to be badly corroded.

Example 11

The procedure of Example 3 was repeated with the modification that the freeze and thaw cycle has been omitted. The oil-fat mixture was tested according to the procedure of Example 3 for its properties with regard to corrosion resistance checked. The nail used in the test was severely corroded by the oil-fat-water mixture.

Example 12

The procedure of Example 4 was repeated with the exception of the freeze and thaw steps. The corrosion test according to the example 4 was also repeated, with the result that the nail used was severely corroded.

The Dixon 164 used in the previous examples is a 6O # suspension of polytetrafluoroethylene in a Si

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lemon oil.

The oils according to the invention have numerous uses, "especially in areas where the metal parts that come into contact with the oils are highly sensitive to corrosion are. Exemplary of such systems include those with commonly used petroleum hydrocarbon lubricants are reactive, systems for processing liquid oxygen, hydrogen and other highly reactive materials, plotting and watering devices, valves and shut-off cocks, high-pressure systems, high-performance gear housings, transmissions, Pumping devices, stationary and mobile hydraulic systems such as those used on ships and aircraft, and the like.

The oil is particularly suitable for use in aluminum components containing systems which, under high shear conditions, usually detonate common lubricants cause. The oils according to the invention, on the other hand, are highly resistant to detonation in the presence of aluminum Shear.

The oils according to the invention are therefore particularly used in the plug tool industry, in the high-temperature and corrosion-resistant Oils constantly being used in conjunction with aluminum contain components and systems.

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Claims (9)

- 14 - DA-K 924 PATENT CLAIMS 1. Highly corrosion-resistant lubricating oil mixture, characterized in that it consists of a frozen and thawed mixture of a synthetic polymer oil, containing a halogen substituent, and a: fluorocarbon resin. 2. Process for producing a highly corrosion-resistant Lubricating oil mixture, characterized by the fact that one a) a synthetic polymer oil containing a halogen substituent and a fluorocarbon resin intimately mixed, b) the mixture freezes to form the solid phase and c) thaws the frozen mixture again. 3 · Method according to claim 2, characterized in that a synthetic polymer oil is used which contains chlorine, fluorine, bromine, iodine or mixtures of these substituents as substituents. 309820/0923 - 15 - 4. The method according to claim 2 or 3 ,, characterized g e k e η η-ze refuses to use a synthetic polymer oil containing fluorine as a substituent. 5. The method according to claim 4- characterized by g e k e η η that as a synthetic polymer oil polychlorotrifluoroethylene is used. 6. The method according to claim 4 »characterized by g e k e η η that polytrifluorovinyl chloride is used as the synthetic polymer oil. 7. The method according to claim 4 »characterized in that Trifluörpropylmethylpolysilikon as the synthetic polymer oil is used. 8. The method according to claim 4 »characterized in that a synthetic polymer oil Perfluoroalkyl polyether is used. 9. The method according to any one of claims 2 to 8, characterized in that polytetiafluoroethylene is used as the fluorocarbon resin. , - - 10 «Method according to claim 9, characterized in that g e k e η η - · 309820/09? 3 - 16 - draws that the polytetrafluoroethylene is used in the form of a suspension in a liquid, which The synthetic polymer oil is inert towards and with this is miscible. 309820/09? 3