DE3210283A1 - Polyethers, their preparation, and their use as lubricants - Google Patents

Abstract

Polyethers prepared by polymerisation of a C8-28-1,2-epoxy alkane and tetrahydrofuran in the presence of a hydroxyl compound are particularly suitable as lubricants for gearboxes.

Description

Polyethers, their manufacture and their use as

Lubricants The invention relates to new polyethers, their production and their use as lubricants, particularly as lubricants for power transmissions.

Power gears should work with as little loss as possible in order to achieve a good To achieve transmission efficiency and to keep the heating of the transmission low.

The total losses occurring in a transmission are made up of one another from the friction losses caused by a transfer of motion of the rolling elements rolling on each other and at the same time sliding surfaces arise with high contact pressure and the Splashing and squeezing losses caused by immersing moving machine parts in caused by the oil filling (H. Eiselt, Dissertation TU Dresden 1966 "Contribution for the experimental and computational determination of the seizure resistance of gear drives taking into account the tooth flank friction; Ohlendorf, H. VDI-Z 102, 216-224 (1960), "Power dissipation and heating of cylindrical gears", G. Huber, dissertation Technical University of Munich 1978, investigations into the flank load capacity and efficiency of cylindrical worm gears (Involute screws) ". The crushing losses are especially with fast running Driven considerably.

The ones in power gears with positive motion transmission The lubricants used serve to minimize the friction losses between the surfaces.

At the same time should. a stable lubricating film that spreads through the Rolling motion of the surfaces builds up, separating these surfaces from one another All types of wear and tear (seizure, pitting, slow-speed and greyish wear) to keep it as low as possible.

To build up a sufficiently stable lubricating film in gearboxes To be able to do this, the lubricant must have a minimum viscosity. The more unfavorable the operating conditions are, the greater the viscosity must be selected in order to to avoid unwanted wear. On the other hand, take with increasing Viscosity greatly increases the splash and squeeze losses; this has an undesirable effect Increase in the gear unit temperature as a result.

The hinge qualities of liquid lubricants are adjusted accordingly the function of the lubricant in a power transmission due to the friction behavior under operating conditions (Influence of the Molecular Structure on the Traction Characteristics of Lubrication Fluids, H. Winter and Vojacek, Int. Symp. On Gearing Power Transm., Tokyo 1981), by the viscosity at the operating temperature, by the viscosity-temperature behavior and by the viscosity-pressure coefficient ~) ö, which influences the lubricant film thickness, determines (lubrication technology and tribology 27: 55-57 (1980)).

The friction behavior is determined by the coefficient of friction. she is defined as the quotient of the frictional force resulting from the friction and the contact force between the surfaces.

The coefficient of friction essentially depends on the operating parameter, Circumferential speed of the rolling and sliding surfaces, slip and contact pressure between the two surfaces, the slip being defined as the absolute value of the quotient from the difference between the two circumferential speeds under the greater peripheral speed.

The coefficient of friction should be as low as possible in the entire operating range in order to keep the friction losses low.

The viscosity of the lubricant should be as low as possible, where the minimum viscosity at operating temperature depends on the operating conditions.

The viscosity should depend as little as possible on the temperature. The viscosity index is used as a measure of the temperature dependence of the viscosity (in general VI abbreviated). The viscosity index should be as high as possible.

The lubricants should also be in the systems to be lubricated (e.g. mechanical gears, roller and plain bearings) with those commonly used there Mineral oils must be compatible with a change from the mineral oils to the new ones Lubricants with the remaining residual amounts of mineral oils do not cause complications respectively. They should also be as hydrophobic as possible, since absorbed water is the Favors corrosion. In addition, a high thermal load capacity is desirable.

From J.A. Kokai 50/13 3205 polyalkylene glycol ethers are known which C8-C28-1, 2-epoxy-alkane units and a ratio of carbon to oxygen from 3.5 to 9.5. These known polyalkylene glycol ethers can be used in mixtures can be used with mineral oils as lubricants, however, their lubricating properties not entirely satisfactory in all respects.

This becomes clear from the excessively high spelling numbers.

The polyalkylene-alkylene oxides known from US Pat. No. 3,382,055, the Can be used as additives for lighter lubricating oils also have to high coefficients of friction.

New polyethers have been found that are highly compatible with mineral oils and mineral oil mixable low water absorption, high heat resistance and high viscosity index with very low coefficients of friction at the same time.

The new polyethers can be obtained by polymerizing a 1,2-epoxyalkane, containing 8 to 26 carbon atoms and a tetrahydrofuran in the presence of a Hydroxy compound of the formula (I) H-OR (1) in which R1 is hydrogen, an alkyl radical having 1 to 24 carbon atoms or a hydroxyalkyl radical having 2 to 40 carbon atoms means.

The polyethers obtainable according to the invention include all polyethers with the same structure regardless of the process by which they are made became.

In general, the polyethers according to the invention contain 10 to 98 Parts by weight, preferably 20 to 95 parts by weight, particularly preferably 30 to 90 parts by weight, 1,2-epoxyalkanes and 2 to 90 parts by weight, preferably 5 to 80 parts by weight, in particular preferably 10 to 70 parts by weight, tetrahydrofuran, based in each case on the total amount of all oxacycloalkanes.

The hydroxy compound is generally used in an amount from 0.3 to 95 parts by weight, preferably from 0.8 to 60 parts by weight, particularly preferably from 1.6 up to 50 parts by weight, used.

When using water as the hydroxy compound, that's at the end of the line the amount of water added to the reaction during work-up is generally sufficient.

In a particular embodiment, contain the invention Polyether additionally a lower alkylene oxide component with ethylene oxide and / or Propylene or butylene oxide, the hydroxy compound being monofunctional and once can once be bifunctional.

Preferred polyethers with a lower alkylene oxide component and with a monofunctional hydroxide compound can be obtained by polymerization from 10 to 90 parts by weight of a 1,2-epoxyalkane, 5 to 55 parts by weight of a tetrahydrofuran and 0 to 40 parts by weight of ethylene oxide and / or 0 to 70 parts by weight of propylene or Butylene oxide, at least ethylene oxide or propylene or butylene oxide being used is, and in the presence of a monofunctional hydroxy compound of the formula (II) H-OR2 (11), in which R2 is an alkyl radical with 1 to 24 carbon atoms, and wherein in the polyether the ratio of the number of carbon atoms to the The number of oxygen atoms is 3.2 to 10: 1.

Preferred polyethers with a lower alkylene oxide component and with a bifunctional hydroxy compound are obtainable by polymerizing 10 to 90 parts by weight of a 1,2-epoxyalkane, 5 to 55 parts by weight of a tetrahydrofuran and 0 to 70 parts by weight. Ethylene oxide and / or 0 to 70 parts by weight. Propylene or Butylene oxide, at least ethylene oxide or propylene or butylene oxide being used is, and in the presence of a bifunctional hydroxy compound of the formula (III) 3 H-OR (III), in which R3 is hydrogen or a hydroxyalkyl radical with 2 to 40 carbon atoms means, and wherein in the polyether is the ratio of the number of carbon atoms to the number of oxygen atoms is 3.6 to 10: 1.

The lower alkylene oxide components ethylene oxide, propylene oxide and butylene oxide are according to the invention in an amount of 0 to 70 parts by weight, preferably 5 to 65 parts by weight, particularly preferably 10 to 60 parts by weight, based on the total amount of all oxacycloalkanes are used.

The amounts of the mono- and bifunctional hydroxy compounds correspond in general the amounts of the hydroxy compounds in general.

In the new polyethers according to the invention, which in the presence of a Lower alkylene oxide component and made with monofunctional hydroxy compounds is the ratio of the number of Carbon atoms to the number of oxygen atoms 3.2 to 10, preferably 3.4 to 9.5, in particular preferably 3.6 to 9.0: 1.

In the new polyethers according to the invention, which in the presence of a Lower alkylene oxide component and made with bifunctional hydroxy compounds is the ratio of the number of carbon atoms to the number of Oxygen atoms 3.6 to 10, preferably 3.8 to 9.5, particularly preferably 4.0 to 9: 1.

Preferred polyethers according to the invention which are in the presence of a lower alkylene oxide component and made with monofunctional hydroxy compounds are available By polymerization of 5 to 65 parts by weight. Ethylene oxide and / or propylene or Butylene oxide, 15 to 80 parts by weight of a 1,2-epoxyalkane having 8 to 16 carbon atoms, 10 to 50 parts by weight of a tetrahydrofuran and in the presence of a monofunctional one Compound of the formula (IV) H-OR4 (1V) in which 4 R is an alkyl radical having 1 to 18 carbon atoms means, and wherein in the polyether is the ratio of the number of carbon atoms to the number of oxygen atoms is 3.4 to 9.5: 1.

Preferred polyethers according to the invention which are in the presence of a lower alkylene oxide component and made with bifunctional hydroxy compounds available by polymerization of 5 to 65 parts by weight of ethylene oxide and / or propylene or Butylene oxide, 15 to 80 parts by weight of a 1,2-epoxyalkane having 10 to 18 carbon atoms, 10 to 50 parts by weight of tetrahydrofuran and in the presence of a bifunctional hydroxy compound of the formula (V) 5 H-OR (IV) in which 5 R5 is hydrogen or a hydroxyalkyl radical 2 to 18 carbon atoms, where in the polyether the ratio of the number of carbon atoms to the number of oxygen atoms is 3.8 to 9.5: 1.

The hydrocarbon radical of the 1,2-epoxyalkanes according to the invention can be straight-chain or branched and have 8 to 26, preferably 10 to 18, carbon atoms contain. The following 1,2-epoxyalkanes may be mentioned as examples: 1,2-epoxy-octane, 1,2-epoxy-nonane, 1,2-epoxidecane, 1,2-epoxy-undecane, 1,2-epoxy-dodecane, 1,2-epoxy-tetradecane, 1,2-epoxy-hexadecane and 1,2-epoxy-octadecane.

In a particular embodiment of the present invention is it is possible to use up to 70 mol% of the 1,2-epoxy alkane (C8-C26) by a To replace glycidyl esters of a C5-C26 neoalkanoic acid. Neoalkanoic acids can preferably be replaced with 8 to 24 coal material atoms are used in the form of their glycidyl esters will.

According to the invention, tetrahydrofuran encompasses in addition to the unsubstituted one Tetrahydrofuran also tetrahydrofurans, which have 1 to 4, preferably 1 or 2, lower alkyl radicals are substituted. Lower alkyl radicals can be straight-chain or branched Be hydrocarbon radicals and contain 1 to about 6 carbon atoms. For example the following tetrahydrofurans may be mentioned: 2-methyltetrahydrofuran, 3-methyl-tetrahydrofuran, 4-methyltetrahydrofuran, 5-methyl-tetrahydrofuran, 3- or 4-isopropyl-tetrahydrofuran, 3,4-diisopropyl-tetrahydrofuran, 2,3,4-tributyl-tetrahydrofuran and 2,3,4,5-tetramethyl-tetrahydrofuran. Unsubstituted tetrahydrofuran is preferred.

The hydroxy compounds according to the invention can be both monofunctional as well as bifunctional hydroxy compounds.

According to the invention, monofunctional hydroxy compounds can be alcohols be, the alkane radical of the alcohol being straight-chain or branched and 1 to 24, preferably 1 to 18, carbon atoms. The monofunctional connection can be both a primary, secondary and tertiary alcohol.

Examples are the following monofunctional hydroxy compounds called: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.-butanol, tert-butanol, Allyl alcohol, hexanol and 2-ethylhexanol.

Bifunctional hydroxy compounds according to the invention can be water or Be dihydroxyalkanes, the alkane radical being straight-chain or branched and 2 may contain up to 40, preferably 2 to 18, carbon atoms. The hydroxyl groups can be both at the ends and in the middle of the alkane.

Preferred bifunctional compounds are terminal dihydroxyalkanes Hydroxyl groups. Examples are the following bifunctional compounds named: water, 1,2-ethanediol, 1 ~ 2 propanediol, 1 ~ 3 propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol. Preferred bifunctional hydroxy compounds are Water, 1,2-ethanediol and 1,4-butanediol.

If water is used, the reaction mixture is preferred only comes into contact with the water in the work-up and cleaning phase.

The new polyethers according to the invention have an osmotically determined one Molecular weight in the range from about 400 to about 10,000, preferably in the range from about 600 to about 4000.

The new polyethers according to the invention have a kinematic at 40.degree Viscosity from 5 to 3000 mm2 / s, preferably from 20 to 500 mm2 / s.

The viscosity index of the new poly of the invention ether generally ranges from 150 to 220.

The preparation of the new polyethers according to the invention can according to known polymerization processes take place (Angew. Chem. 72, 927-934 (1960)).

The process for producing the new polyethers is characterized that you have 10 to 98 parts by weight of a 1,2-epoxyalkane having 8 to 26 carbon atoms and 2 to 90 parts by weight of tetrahydrofuran in the presence of a hydroxy compound of Formula (I) H-OR (I) in which R1 is hydrogen, an alkyl radical with 1 to 24 carbon atoms or a hydroxyalkyl radical having 2 to 40 carbon atoms is polymerized.

The process according to the invention is generally carried out in the temperature range from -20 to 1200C, preferably from 0 to 80 ° C, particularly preferably from 20 to 60 ° C, carried out.

In general, the process according to the invention is carried out for a Pressure from 0.5 to 50 bar, preferably from 1 to 10 bar, particularly preferably from 1.5 to 2 bar, through.

i S process according to the invention is generally carried out in the presence of a Polymerization starter carried out.

Al ívmerisationsstarter for the method according to the invention can the polymerization initiators customary for polyether production can be used (Angew.

Chem. 72, 927-934 (1960)). For example, there are the following polymerization initiators named: Lewis acids, such as boron trifluoride and its adducts (boron trifluoride diethyl ether, Boron trifluorotetrahydrofuranate), aluminum chloride, iron (111) chloride, tin (IV) chloride, Titanium tetrachloride, tin chloride and antimony pentachloride.

Preferred polymerization initiator for the process according to the invention is boron trifluoride or boron trifluoride tetrahydrofuranate.

The polymerization initiator for the process according to the invention is generally in an amount from 0.001 to 5.0% by weight, preferably from 0.01 to 1.0 % By weight, based on the total reaction mixture, is used.

The method according to the invention can be carried out, for example, as follows are: One of the starting materials, preferably tetrahydrofuran, is placed in the reaction vessel and optionally the alcohol, and adds the polymerization initiator.

The other reaction components are passed into the reaction mixture a. By regulating the rate of initiation, the process in the temperature range according to the invention are maintained.

After the end of the polymerization, work-up is carried out in the customary manner Way, for example by washing with water and subsequent drying.

The polyethers according to the invention can be used, for example, as lubricants, but can also be used as heat transfer oils.

It is possible to use the polyethers according to the invention alone as lubricants to use or to mix them with other lubricants known per se. Other Examples of lubricants are: mineral oils with lubricating viscosity, polyethers from Polyethylene oxide and polypropylene oxide types, ester lubricating oils of the diester, polyester or neopentyl polyol type and phosphoric acid ester.

The lubricants according to the invention can also contain customary additives, such as viscosity index improvers, pour point depressants, dispersants, overbased Dispersants, detergent additives, antioxidants, wear reducers, extreme pressure additives, Corrosion inhibitors, anti-foaming agents, etc.

The polyethers according to the invention are compatible with the known, customary ones Lubricants, so that an alternate use without cleaning the lubricant System is possible. They are also largely unrestrictedly miscible with the per se known lubricants.

The polyethers according to the invention surprisingly show in the Combination of all properties one excellent suitability as Lubricant that cannot be achieved by the lubricants known per se.

The lubricants according to the invention can preferably be used to reduce the friction in mechanical transmissions with power transmission through positive locking, in particular Worm gears and hypoid gears, roller and slide bearings and systems for paper and plastic calenders are used.

Examples Example 1 In an approx. 1 liter three-necked flask you place a Mixture of 86.4 g tetrahydrofuran (not more than 0.02 g water), 1.9 g anhydrous Methanol and 9.7 g of boron trifluoride tetrahydrofuranate and heated to about 350C. A mixture of 585 g of 1,2-epoxidecane and 36.5 g of anhydrous methanol is then added dropwise at such a rate that a reaction temperature of about 550C is maintained (dropping time approx. 270 minutes). After 1 hour of post-reaction time at 55 to 60 ° C it is cooled, a solution of 16.2 g of soda in 82 g of water is added, and the temperature is raised to 1000C high, leave the mixture at this temperature for 1 hour, then increase the temperature to 1400C and the water is distilled off. After cooling to about 900C and again Adding about 15 g of water is heated to 100 Torr within 3 hours 1800C high, then leave the mixture at these conditions for 2 hours and press the approx. 1000C hot oil from a pressure filter.

Yield: approx. 743 g (79.4% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 12.9% by weight 1,2-epoxyalkanes: 87.1% by weight pour point: -48 to -50 ° C OH number: approx. 77, molecular weight calculated from this approx. 729 osmotic molecular weight: 570 elemental analogs: 73.80% C 12.98% H 13.22% 0 Kinematic viscosities at 37.80 C: 55.5 mm2 / s 98.9 ° C: 8.88 mm2 / s Viscosity index (extension): 150 Example 2 In a manner analogous to Example 1, a mixture of 108 g of absolute tetrahydrofuran, 2.4 g of anhydrous methanol and 12; 2 g of boron trifluoride tetrahydrofuranate submitted, heated to 30 ° C. and then one from 487.7 g of 1,2-epoxidodecane, 365.6 g of 1,2-epoxidecane and 45.6 g of anhydrous methanol existing mixture was added dropwise within 5 hours, so that the reaction temperature is about 550C. After 1 hour of post-reaction time at 55 to 60 ° C., work-up is carried out in an analogous manner to example 1.

Yield: 813 g (85.1% of Theroie).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 11.2% by weight 1,2-epoxyalkanes: 88.8% by weight pour point: -27 to -28 ° C OH number: 65, Molecular weight calculated from this approx. 863 Elemental analysis: 74.40% C 12.85% H 12.75% 0 Kinematic viscosities at 37.80C 66.9 mrn2 / s 98.90C 11.0 mm2 / s viscosity index (Extension): 168 Example 3 In a manner analogous to the example 1 is a mixture of 108 g of absolute tetrahydrofuran, 2.4 g of anhydrous methanol and 12.2 g boron trifluoride tetrahydrofuranate, heated to 30 to 350C and thereafter one consisting of 975.5 g 1,2-epoxidodecane and 45.6 g anhydrous methanol Mixture is added dropwise within 6 hours, so that the reaction stone temperature is approx. 600C. After a post-reaction time of 2 hours at 60 ° C., in an analogous manner to Example 1 worked up.

Yield: 1050 g (92.8% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 10.0% by weight 1,2-epoxyalhane: 90.0% by weight pour point: -17 to -180C OH number: 61.5, Molecular weight calculated therefrom 912. Elemental analysis: 74.93% C 11.84% H 13.23 % 0 2 Kinematic viscosities at 37.8 ° C 69.4 mm 98.90C 10.8 mm2 / s viscosity index (Extension): 156 Example 4 A mixture of 173.9 g absolute tetrahydrofuran and 10.5 g boron trifluoride tetrahydrofuranate, heated to 40 ° C. and then a mixture of 1202.5 g for 7.5 hours 1,2-t: po:.: Idodecane and 186.1 g of absolute tetrahydrofuran were added dropwise so that a reaction temperature of 550C. After a post-reaction time of 1 hour at 550 ° C., the procedure is analogous to the example 1 worked up.

Yield: 1254 g (80.9% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 23.0% by weight 1,2-epoxyalkanes: 77.0% by weight pour point: -17 to -180C flash point: 252 up to 2530C OH number: 23 to 24, molecular weight calculated therefrom approx. 4775 osmotic Molecular Weight: 2100 Elemental Analysis: 75.16% C 12.92% H 11.92% 0 Kinematic Viscosities at 37.80C 460.9 mm2 / s 98.9 ° C 56.7 mm2 / s Viscosity index (extension): 200 Viscosity-pressure coefficient: 14 / m / N. 10 9 7 Friction coefficient: 0.030 Example 5 In analogy to Example 4, a mixture of 377.5 g of absolute tetrahydrofuran and 13.8 g boron trifluoride tetrahydrofuranate, heated to 40 ° C. and then a mixture of 781.2 g of 1,2-epoxidodecane and 404.1 g of absolute for 10 hours Tetrahydrofuran was added dropwise so that a reaction temperature of 45 sets up to 500C. After post-reacting for 1 hour at 45 to 50 ° C., the procedure is analogous to the example 1 worked up.

Yield: 1004 g (64.2% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 50.0% by weight 1,2-epoxyalkase: 50.0% by weight pour point: -34 to -350C OH number: 15 to 16, molecular weight calculated from this approx. 7200 osmotic molecular weight: 1600 Elemental analysis: 72.62% C 12.51% H 14.86% O 2 kinematic viscosities at 37.8 ° C 913.3 mm 98.90 C 113.7 mm2 / s Viscosity index (extension): 234 Example 6 In analogy to Example 4, a mixture of 528.3 g of absolute tetrahydrofuran is used and 16.5 g boron trifluoride tetrahydrofuranate, heated to 40 ° C. and then a mixture of 468.7 g of 1,2-epoxidodecane and 565.5 g of absolute for 6.5 hours Tetrahydrofuran was added dropwise so that a reaction temperature of 45 to 50.degree After 1 hour of post-reaction at 45 to 500C, the procedure is analogous to Example 1 worked up.

Yield: 982 g (62.8% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 70.0% by weight 1,2-epoxyalkase: 30.0% by weight Pour point: -21 to -220C OH number: 11, molecular weight calculated from this approx.

10,200 osmotic molecular face: 1,500 elemental analysis: 70.48 % C 12.25% H 17.27% 0 2 Kinematic viscosities at 37.80C 2272 mm 98.9 ° C 255.3 mm2 / s Viscosity index (extension): 264 Example 7 In analogy to Example 1, a mixture of 108 g of absolute tetrahydrofuran, 2.4 g of anhydrous methanol and Submitted 12.2 g of boron trifluoride tetrahydrofuranate, heated to 300C and this one Mixture of 487.7 g of 1,2-epoxidodecane 551.3 g of a mixture of neoalkanoic acid glycidyl esters (average molecular weight 245) and 45.6 g of anhydrous methanol within 11 hours added dropwise, so that a reaction temperature of approx.

45 to 500C. After 2 hours of post-reaction time at 45 to 500C is worked up analogously to Example 1.

Yield: 1015 g (84.9% of theory).

Composition of the oxacycloalkanes used: Tetrahydrofuran: 9.4% by weight 1,2-epoxyalkanes: 90.0% by weight (including the neoalkanoic acid glycidyl esters).

The "1,2-epoxyalkanes" thus contain 47 mol% of glycidyl neoalkanoate.

Pour point: -37 to -380C OH number: 78, molecular weight calculated therefrom approx. 720 osmotic molecular weight: 600 elemental analysis: 70.88% C 12.07% H 17.05% 02 Kinematic viscosities at 37.8 ° C 98.1 mm / s 98.90C 11.3 viscosity index (Extension): 111 Example 8 In analogy to Example 4, a mixture of 541.8 g absolute tetrahydrofuran and 18.0 g boron trifluoride tetrahydrofuranate, heated to 45 ° C. and then 773.5 g of 1,2-epoxidodecane, 232.2 g for 10 hours absolute tetrahydrofuran and 24.5 g of about 36 carbon atoms per molecule containing dialcohol is added dropwise, so that a reaction temperature of 45 sets up to 500C. After a post-reaction time of 1 hour, work-up is carried out.

Yield: 1100 g Composition of the oxacycloalkanes used: Tetrahydrofuran: 50.0% by weight 1,2-epoxyalkanes: 50.0% by weight pour point: -16 ° C OH number: 22 to 23, calculated molecular weight approx. 4990 osmotic molecular weight: 1660 Elemental Analysis: 72.59% C 12.16% H 15.34% O Kinematic Viscosity at -37.80C 895.6 mm; / s 98.9 ° C 125.9 mm viscosity index (extension): 255 Viscosity-pressure coefficient: 11 L / N. 10 9 / friction coefficient: 0.033 example 9 In analogy to example 1, a mixture of 900 g of absolute tetrahydrofuran, 1.3 g of anhydrous n-butanol and 13.5 g of boron trifluoride tetrahydrofuranate are presented, heated to 450C and for this purpose a mixture of 24.1 g of n-butanol with 600 g of 1,2-epoxidecane added dropwise within 11 hours so that a reaction temperature of approx. 45 to 500C. After a post-reaction time of 2 hours at 45 ° to 50 ° C., the mixture is worked up.

Yield: 1163 g Composition of the oxacycloalkanes used: Tetrahydrofuran: 59.0% by weight 1,2-epoxyalkanes: 41.0% by weight pour point: -150C OH number: 19:20, derived molecular weight approx. 2880 osmotic molecular weight: 1260 Elemental analysis: 70.54% C 12.16% H 17.30% 0 Kinematic viscosity at 37.8 ° C 878.3 mm2 / s 98.90C 106.1 mm2 / s Viscosity index (extension): 227 Viscosity-pressure coefficient: 14 z m / N. 10 9 7 friction coefficient: 0.032 Example 10 In one Airtight, approx. 2 l shaking flask made of thick-walled glass with the possibility of internal cooling, 119.9 g of anhydrous tetrahydrofuran, 2.17 g of anhydrous methanol and 13.05 g of a boron trifluoride-tetrahydrofuran adduct presented and heated to about 400C. Then with good shaking and if necessary Cooling a mixture consisting of 250.3 g ethylene oxide, 286.0 g propylene oxide, 329.4 g g of 1,2-epoxidecane and 41.25 g of anhydrous methanol are pumped in so that the reaction temperature does not rise above 550C. After the addition has ended, the mixture is left to react for 1 hour.

After a short gas purging with nitrogen to remove volatile substances Starting materials are given to a solution of 30.6 g of anhydrous soda in 153.6 g of water closed, heats to 100 ° C. while passing a weak stream of nitrogen through, then slowly up to 1400C and holds at this temperature for 2 hours. Through these measures residual tetrahydrofuran and low molecular weight volatile cyclic oligomers removed.

After another addition of water, the reaction mixture is cooled and separates the polyether.

In the polyether, the starting components are in the following proportions contain: 10.6 parts by weight of tetrahydrofuran 25.8 parts by weight of ethylene oxide 29.6 parts by weight of propylene oxide and 34.0 parts by weight of epoxidecane Molecular weight: 830 (from OH number) Molecular weight: 620 (osmotic) Pour point: -58 to -590C Kinematic Viscosity at 40 ° C: 59.8 mm2 1000C: 10.88 mm2 Viscosity index: 193 For testing the mineral oil compatibility was 10 parts by weight of the polyether at 1000C with 90 Parts by weight of a paraffinic mineral oil (ASTM classification: ASTM-D2226; 104; B, density at 150C 0.888 zg / cm3 7; Viscosity at 500C 87.4 Lamm2 ~ / and at -2-1000C 14.3 / mm /; Composition: 3% aromatic hydrocarbons, 32% naphthenic Hydrocarbons and 65% paraffinic hydrocarbons) mixed intensively. After standing for 2 weeks, a clear solubility was checked. The sample according to the example 10 gives a clear solution; it is therefore compatible with mineral oil.

The frictional behavior of the polyether was determined in a two-disc friction test stand L6.8? as a function of the contact pressure FN, the peripheral speed of the pulley V1 and the slip s = (V1-V2) / V1.

The lubricant is supplied with an injection temperature of 500C between the test disks injected.

The washers are made of a material that complies with DIN 17006 100 Cr6 is described. Both discs have a diameter of 80 mm, one disc is designed as a cylinder, the other as a spherical cutout.

The arithmetic mean roughness of the disks Ra is approx. 0.085 μm.

In Figures 1 to 4, the dependence of the coefficient of friction on slip, shown by the contact pressure and the peripheral speed.

The measurement results shown in the following figures were obtained from the following operating conditions are determined (in brackets the corresponding Hertzian Compression): Fig. 1 FN = 125 N (750 N / mm2) Fig. 2 FN = 400 N (1100 N / mm2) Fig. 3 FN = 1000 N (1500 N / mm) Fig. 4 FN = 2000 N (1890 N / mm2) 2 Fig. 5 FN = 4080 N (24000 N / mm In the individual figures 1 to 5, the designations correspond to the following Disk peripheral speeds: 1 V = 0.42 m / s 2 0.84 m / s 3 2.10 m / s 4 4.19 m / s 5 8.38 m / s 6 12.57 m / s The results show the same in the entire investigation area particularly low coefficients of friction.

In the test according to Almen-Wieland (Swiss archive, Annales Suisses, M. Brunner and R. Pedrini, Part 1, June 1955, No. 6, pages 169 to 177; Part 2, August 1955, No. 8, pages 251 to 257), the polyether according to Example 10 shows a Welding force greater than 18,000 N; at a frictional force of more than 3500 N and a temperature of 1160C the machine blocked, but welded not.

The Reichert frictional wear test at 15 N load results with the Polyether according to Example 1 has a wear mark of 11.3 mm and a specific one Load capacity of 26.7 MPa (Schmierungstechnik (1960) No. 5, E. Kadmer and H. Danninger).

The one required to describe the lubricating film-forming properties The viscosity-pressure coefficient is determined by the effective thickness of the lubricating film in the rolling contact in a test device (Schmierungstechnik und Tribologie, 27, (1980) 2, pages 55-57) has been determined.

The following values were obtained: coefficient of friction 0.030, viscosity-pressure coefficient 13 (m2 / N 10 9) Example 11 This example is analogous to the example 10 with presentation of a mixture consisting of 108 g absolute tetrahndrofuran, 2.4 g of absolute methanol and 14.5 g of boron trifluoride tetrahydrofuranate and with the addition a mixture consisting of 66 g of ethylene oxide, 577.2 g of a technical 1,2-epoxidodecane and 45.6 g of absolute methanol.

Composition: 14.4 parts by weight of tetrahydrofuran, 8.8 parts by weight of ethylene oxide 76.8 parts by weight of 1,2-epoxidodecane molecular weight about 640 (from OH number) molecular weight 530 (osmotic) pour point -220C Kinematic viscosity at 37.80C 47.1 mm2 / s 98.90C 8.10 mm / s Viscosity index: 157 The ratio of the number of carbon atoms to the number of oxygen atoms is 7.80: 1.

The product is also compatible with mineral oils.

12 This example is analogous to example 10 using a Mixture consisting of 135 g of absolute tetrahydrofuran and 2.8 g of absolute methanol and 16.4 g of boron trifluoride tetrahydrofuranate and adding a mixture consisting of from 312.9 g of ethylene oxide, 376.1 g of propylene oxide, 425.7 g of a technical 1,2-epoxidodecane and 51.5 g of absolute methanol under the same reaction and work-up conditions manufactured.

In the polyether, the starting components are in the following proportions contain: 25.0 parts by weight of ethylene oxide 30.1 parts by weight of propylene oxide 34.1 parts by weight 1,2-epoxidodecane 10.8 parts by weight tetrahydrofuran Molecular weight: about 900 (from OH number) Molecular weight 650 (osmotic) pour point: -45 to -460C 2 Kinematic viscosity at 37.80C 63.8mm 98.90C 11.6mm2 / s Viscosity index: 191 The ratio of the number of carbon atoms to the number of oxygen atoms is 3.81: 1.

The product is also compatible with mineral oils.

Viscosity pressure coefficient: 3 -2 / N. 10 9 in example 13 In the A mixture of 324 g of absolute tetrahydrofuran, 5.55, is placed in the reaction vessel g absolute butanol and 8.1 g boron trifluoride tetrahydrofuranate upstream and metered in External cooling a mixture of 468 g of 1,2-epoxidecane, 324 g of 1,2-butylene oxide and 105.5 g of absolute butanol so that a reaction temperature of 27 to 330C is maintained will. After about 2 hours of post-reaction at 30 ° C., work-up is carried out analogously to Example 1.

In the polyether, the starting components are in the following proportions contain: 29.0 parts by weight of 1,2-butylene oxide 42.0 parts by weight of 1,2-epoxidecane and 29.0 Parts by weight of tetrahydrofuran Molar weight: 1060 (calculated from the OH number) Molecular weight: 700 (osmotic) pour point: -500C Kinematic viscosity at 37.80C 103.3 mm2 / s Nn 26.0 mm2 / s viscosity index: 177 The ratio of the number of Carbon atoms to the number of oxygen atoms are 5.34: 1.

The product is also compatible with mineral oils.

Example 14 In an airtightly closed shaking vessel with a capacity of approx. 2 l from thick-walled glass with the option of internal cooling, 259.6 g of water-free Tetrahydrofuran and 15.6 g of boron trifluoride-tetrahydrofuran adduct and placed on 400C heated. Then a monomer mixture is pumped with shaking and possibly cooling, consisting of 278.0 g tetrahydrofuran, 129.9 g propylene oxide, 217.1 g ethylene oxide and 495.5 g of 1,2-epoxidodecane so that the temperature does not rise above 550C.

After the addition has ended, the mixture is left to react for 1 hour.

After a short gas purging with nitrogen to remove volatile substances Starting materials are added to a solution of 30.6 g of anhydrous soda in 153.6 g of water closed, heats to 100 ° C. while passing a weak stream of nitrogen through, then slowly up to 1400C and holds at this temperature for 2 hours. By this measure residual tetrahydrofuran as well as low molecular weight volatile cyclic oligomers removed.

In the polyether, the starting components are in the following proportions contain: 15.7 parts by weight ethylene oxide 9.4 parts by weight propylene oxide 36.0 parts by weight 1,2-epoxidodecane and tetradecane 39.0 parts by weight of tetrahydrofuran Molecular weight: 4315 (from OH number) Molecular weight: 1200 (osmotic) pour point: -39 to -400C; Flash point: 2470C Kinematic viscosity at 4Q ° C 50.2 mm2 / s mm 75.8 inm2 / s Viscosity index: 229 Ratio of the number of carbon atoms to the number of oxygen atoms: 4.58: 1.

To test the mineral oil compatibility, 10 parts by weight of the Polyethers at 1000C with 90 parts by weight of a paraffin-base mineral oil (ASTM classification ASTM-D 2226 104 B; Density at 150C 0.888 / g / m37; Viscosity at 500C 87.4 / mm2 / sec7 and at -2 1000C 14.3 / mm / sec7; Composition: 3% aromatic hydrocarbons, 32% naphthenic hydrocarbons and 65% paraffinic hydrocarbons) intensely mixed. After standing for 2 weeks, a clear solubility was checked. The rehearsal after el # i! 14 gives a clear solution; so she is compatible with mineral oil.

Example 15 This example is analogous to example 14 under the template a mixture consisting of 145.8 g of absolute tetrahydrofuran, 1.7 g of 1,4-butanediol and 9.4 g of boron trifluoride tetrahydrofuranate and adding a mixture consisting of 178.2 grams of absolute tetrahydrofuran, 149.2 grams of ethylene oxide, 196.8 grams of propylene oxide, 924.7 g of 1,2-epoxidodecane and 32.1 g of 1,4-butanediol under the same reaction and work-up conditions carried out. Thus 34.6 mol of oxacycloalkanes are added per mole of 1,4-butanediol.

Yield: 939 g In the polyether, the starting components are as follows Fractions contain: 15.0 parts by weight of ethylene oxide 19.8 parts by weight of propylene oxide 32.6 Parts by weight of 1,2-epoxidodecane 32.6 parts by weight of tetrahydrofuran Molar weight approx. 2100 (from OH number) molecular weight 1200 (osmotic) pour point -390C; Flash point 197 to 198 CC Kinematic viscosity at 37.8 ° C 313.3 mm2 to 98.9 ° C 42.8 mm2 / s Viscosity index: 202 The ratio of the number of carbon atoms to the Number of oxygen atoms is 4.19: 1.

The product is according to the test method described in Example 10 also compatible with mineral oils.

Example 16 <Comparative Example) This comparative example is analogous to example 14 with presentation of a mixture consisting of 162 g of absolute Tetrahydrofuran, 5.6 g 1,4-butanediol and 10.5 g boron trifluoride tetrahydrofuranate and adding a mixture consisting of 198 g of absolute tetrahydrofuran, 240 g Ethylene oxide, 359.9 g propylene oxide, 239.5 g 1,2-epoxidodecane and 106.9 g 1,4-butanediol, carried out under the same reaction and work-up conditions. Per mole of 1,4-butanediol so 14.3 mol of cyclic ethers ("oxacycloalkanes") are added (average molecular weight of the oxacycloalkanes 67.1).

In the polyether, the starting components are in the following proportions contain: 20.0 parts by weight of ethylene oxide, 30.0 parts by weight of propylene oxide 20.0 parts by weight of 1,2-epoxidodecane and tetradecane, 30.0 parts by weight of tetrahydrofuran Molecular weight approx. 1060 (from OH number) Molecular weight 710 (osmotic) pour point -40 to -41QC; Flash point 195 to 1960C 2 Kinematic viscosity at 37.8 ° C 146.1 mm / s 98.90C 20.0 mm2 / s Viscosity index: 168 In relation to the number of carbon atoms in the number of oxygen atoms is: 3.39.

The product is not compatible with mineral oils.

Claims (10)

Claims 1) Polyether, obtainable by polymerizing a 1,2-epoxyalkane containing 8 to 26 carbon atoms and a tetrahydrofuran in the presence of a hydroxy compound of the formula (I) H-OR (I) in which R1 is hydrogen, an alkyl radical with 1 to 24 carbon atoms or a hydroxyalkyl radical with 2 means up to 40 carbon atoms. 2) polyether according to claim 1, characterized in that one 10 to 98 parts by weight of the 1,2-epoxyalkane and 2 to 90 parts by weight of a tetrahydrofuran begins. 3) Polyether according to Claims 1 and 2, obtainable by polymerization from 10 to 90 parts by weight of a 1,2-epoxyalkane, 5 to 55 parts by weight of a tetrahydrofuran and 0 to 70 parts by weight of ethylene oxide and / or 0 to 70 parts by weight of propylene or Butylene oxide, at least ethylene oxide or propylene or butylene oxide being used is, and in the presence of a monofunctional hydroxy compound of the formula (II) H-OR2 (II) in the R is an alkyl radical with 1 to 24 carbon atoms means, and wherein in the polyether is the ratio of the number of carbon atoms to the number of oxygen atoms is 3.2 to 10: 1. 4) Polyether according to Claims 1 and 2, obtainable by polymerization from 10 to 90 parts by weight of a 1,2-epoxyalkane, 5 to 55 parts by weight of a tetrahydrofuran and 0 to 70 parts by weight. Ethylene oxide and / or 0 to 70 parts by weight. Propylene or Butylene oxide, at least ethylene oxide or propylene or butylene oxide being used is, and in the presence of a bifunctional hydroxy compound of the formula (III) H-OR (III) in R3 is hydrogen or a hydroxyalkyl radical with 2 to 40 carbon atoms means, and wherein in the polyether is the ratio of the number of carbon atoms to the number of oxygen atoms is 3.6 to 10: 1. 5) Process for the production of polyethers, characterized in that that a 1,2-epoxyalkane, the alkylene radical containing 8 to 26 carbon atoms, and tetrahydrofuran in the presence of a hydroxy compound the formula (I) H-OR (1) in which R1 is hydrogen, an alkyl radical with 1 to 24 carbon atoms or a hydroxyalkyl radical having 2 to 40 carbon atoms is polymerized. 61 The method according to claim 5, characterized in that the hydroxy compound in an amount of 0.3 to 90% by weight, based on the total reaction mixture, is used. 7) Method according to claims 5 and 6, characterized in that that it is carried out in the temperature range from -20 to 1000C. 8) Lubricants containing polyethers according to Claims 1 to 4. 9) Use of polyether according to Claims 1 to 4 in lubricants for power transmission. 10) Use of polyethers according to Claims 1 to 4 in a mixture with mineral oils as lubricants.