Alkylated diphenyl ether compound and lubricating oil containing said compound

Abstract

A compound of the formula (2) ##STR00001##
wherein R.sup.3 is a hydrocarbon group having 12 or 14 carbon atoms which is mainly composed of any one of 1-methylundecyl, 1-ethyldecyl, 1-dodecyl, 1-methyltridecyl, 1-ethyldodecyl and 1-tetradecyl, and 30 to 40 mole % of the total benzylic carbons of R.sup.3 being quaternary, R.sup.4 is a branched hydrocarbon group having 16 to 20 carbon atoms, 42 to 100 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 being quaternary, m and n are each a real number of 1.0m2.0, 1.0n2.0 and 2.0m+n3.0.

Claims

1. A mixture consisting essentially of compounds having the formula (2) ##STR00012## wherein R.sup.3 is a hydrocarbon group having 12 or 14 carbon atoms, and 30 to 40 mole % of the total benzylic carbons of R.sup.3 being quaternary, R.sup.4 is a branched hydrocarbon group having 16 to 20 carbon atoms, 42 to 100 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 being quaternary, m and n are each a real number of 1.0m2.0, 1.0n2.0 and 2.0m+n3.0, and monoalkylated diphenyl ether in an amount of about 0.1 to 5 mole % of the mixture.

2. A mixture consisting essentially of compounds having the formula (2) obtained by an addition reaction of diphenyl ether derivative of the formula (3) and a branched -olefin of the formula (1) or its corresponding branched alkyl halide ##STR00013## wherein R.sup.1 and R.sup.2 are the same or different and are a hydrocarbon group having 4 to 12 carbon atoms, R.sup.3 is a hydrocarbon group having 12 or 14 carbon atoms, and 30 to 40 mole % of the total benzylic carbons of R.sup.3 being quaternary, R.sup.4 is a branched hydrocarbon group having 16 to 20 carbon atoms, 42 to 100 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 being quaternary, m and n are each a real number of 1.0m2.0, 1.0n2.0 and 2.0m+n3.0, and monoalkylated diphenyl ether in an amount of about 0.1 to 5 mole % of the mixture.

3. The mixture as defined in claim 1 wherein the total of a ratio of the carbon at benzyl position of each R.sup.3 and R.sup.4 being quaternary is 45 to 95 mole %.

4. The mixture as defined in claim 1 wherein 50 to 90 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 is quaternary.

5. The mixture as defined in claim 1 wherein 50 to 65 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 is quaternary.

6. The mixture as defined in claim 1 wherein R.sup.4 is 1-butyl-1-methylheptyl, 1-methyl-1-pentyloctyl, 1-hexyl-1-methylnonyl, 1-heptyl-1-methyldecyl, 1-methyl-1-octylundecyl or 1-decyl-1-methyltridecyl.

7. A lubricating oil containing the mixture of claim 1.

8. A grease containing the mixture of claim 1.

9. A grease composition as defined in claim 8 wherein the grease composition is used for bearing.

10. A mixture consisting essentially of compounds having formula (2) obtained by an addition reaction of diphenyl ether derivative of the formula (4) and an -olefin of the formula (5) or (6) wherein R.sup.3 is a hydrocarbon group having 12 or 14 carbon atoms, and 30 to 40 mole % of the total benzylic carbons of R.sup.3 being quaternary, R.sup.4 is a branched hydrocarbon group having 16 to 20 carbon atoms, 42 to 100 mole % of the total benzylic carbons of each R3 and R4 being quaternary, m and n are each a real number of 1.0m2.0, 1.0n2.0 and 2.0m+n3.0, and monoalkylated diphenyl ether in an amount of about 0.1 to 5 mole % of the mixture.

11. The mixture as defined in claim 1 wherein 2.0m+n2.5.

12. The mixture as defined in claim 11 wherein 2.23m+n2.41.

13. A mixture consisting essentially of compounds having the formula (2) ##STR00014## wherein R.sup.3 is a hydrocarbon group having 12 or 14 carbon atoms which is composed of any one of 1-methylundecyl, 1-ethyldecyl, 1-dodecyl, 1-methyltridecyl, 1-ethyldodecyl or 1-tetradecyl, R.sup.3 further comprises a hydrocarbon group having 12 or 14 carbon atoms wherein the benzylic carbon is quaternary, and 30 to 40 mole % of the total benzylic carbons of R.sup.3 being quaternary, R.sup.4 is a branched hydrocarbon group having 16 to 20 carbon atoms, 42 to 100 mole % of the total benzylic carbons of each R.sup.3 and R.sup.4 being quaternary, m and n are each a real number of 1.0m2.0, 1.0n2.0 and 2.0m+n3.0, and monoalkylated diphenyl ether in an amount of about 0.1 to 5 mole % of the mixture.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is GPC spectrum of Compound 1.

(2) FIG. 2 is .sup.1H-NMR spectrum of Compound 1.

(3) FIG. 3 is GPC spectrum of Compound 2.

(4) FIG. 4 is .sup.1H-NMR spectrum of Compound 2.

(5) FIG. 5 is GPC spectrum of Compound 3.

(6) FIG. 6 is .sup.1H-NMR spectrum of Compound 3.

(7) FIG. 7 is GPC spectrum of Compound 4.

(8) FIG. 8 is .sup.1H-NMR spectrum of Compound 4.

(9) FIG. 9 is GPC spectrum of Compound 5.

(10) FIG. 10 is .sup.1H-NMR spectrum of Compound 5.

(11) FIG. 11 is .sup.1H-NMR spectrum of a model compound.

EXAMPLES

(12) The invention will be described in more detail with reference to the following examples and comparative examples to which, however, the invention is not limited. An alkali neutralizing agent used below is Kyoward 1000 [Mg.sub.4.5.Al.sub.2(OH).sub.13.CO.sub.3. 3.5H.sub.2O] of Kyowa Chemical Industry Co., Ltd.

Example 1

Preparation of Compound 1

(13) To a four-necked flask having 20 liter volume equipped with a stirrer, dropping funnel, thermometer and condenser were placed 8000 g (47.1 moles) of diphenyl ether and 30 g (0.23 mole) of anhydrous aluminum chloride. After dissolving anhydrous aluminum chloride with heating at 100 C., to the mixture was added dropwise a mixture of 4260 g (25.4 moles) of 1-dodecene and 4260 g (21.7 moles) of 1-tetradecene while maintaining the temperature at 100 C. for 4.5 hours to perform an addition reaction. After completion of dropwise addition, the mixture was stirred at 100 C. for 30 minutes, then allowed to cool to 90 C., and thereto added 300 g of alkali neutralizing agent and stirred for 30 minutes. To the mixture was added 100 g of activated clay, stirred at 90 C. for one hour and removed aluminum chloride and other acid substances by-produced by filtration at reduced pressure. Then, the resulting product was distilled at reduced pressure of 2.5 to 3.5 torr at 280 to 324 C., thereby 6440 g of monoalkylated diphenyl ether was obtained.

(14) Next, to a four-necked flask having 10 liter volume equipped with a stirrer, dropping funnel, thermometer and condenser were placed 4500 g (12.8 moles) of monoalkylated diphenyl ether obtained above and 18 g (0.14 mole) of anhydrous aluminum chloride. After dissolving anhydrous aluminum chloride with heating at 110 C., to the mixture was added dropwise 2500 g (8.9 moles) of 2-octyldodecene while maintaining the temperature at 110 C. for 4.5 hours to perform an addition reaction. After completion of dropwise addition, the mixture was stirred at 110 C. for 30 minutes, then allowed to cool to 90 C., and thereto added 180 g of alkali neutralizing agent and stirred for 30 minutes. To the mixture was added 90 g of activated clay, stirred at 90 C. for one hour and removed aluminum chloride and other acid substances by-produced by filtration at reduced pressure. Then, removing unreacted starting material and monoalkylated diphenyl ether by distillation at reduced pressure of 2.5 to 3.5 torr at 250 to 324 C., thereby 4480 g of alkyl diphenyl ether wherein dialkylated diphenyl ether was contained as a main component was obtained. The product (referred to as Compound 1) was 2.23 in alkyl addition number from GPC spectrum (FIG. 1) and .sup.1H-NMR spectrum (FIG. 2). The ratio of the benzylic carbons being quaternary was 53.0 mole %.

(15) GPC

(16) Retention time of monoalkylated diphenyl ether: 42.73644.597 3.35 mole %

(17) Retention time of dialkylated diphenyl ether: 40.26042.736 57.3 mole %

(18) Retention time of trialkylated diphenyl ether: 37.06940.260 39.3 mole %

(19) .sup.1H-NMR (solvent: none, standard substance: none)

(20) Integrated value of =6.57.3 ppm is 1,

(21) integrated value of =2.83.3 ppm is 0.10,

(22) integrated value of =2.22.7 ppm is 0.07,

(23) integrated value of =0.51.9 ppm is 9.80.

(24) GPC system of Shimadzu Corp. was used. The system was as follows. CBM-20A (system controller), DGU-20A3 (online degasser for three channels), LC-20AD (liquid feed unit for high-precision analysis), SIL-20A (auto-sampler), RID-10A (refractive index detector) and SPD-20A (UV-VIS detector).

(25) In the measurement, three KF-803L columns, THF (mobile phase) and SPD-20A (detector) were used. Flow rate was 30 MPa.

(26) .sup.1H-NMR was measured by using a nuclear magnetic resonance device, JNM-ECX400 of JEOL Ltd. at 80 C. without solvent and standard substance.

(27) Chemical shift was obtained by conducting the measurement using the same compound, deuterated chloroform as solvent and TMS as standard substance. This is why peaks of deuterated chloroform overlap with those of benzene ring and precious integrated values are unavailable.

(28) The ratio of each alkyl-adducted compound such as monoalkyl-adducted compound was calculated from each peak area of GPC spectrum. In case a peak is not an independent peak, the ratio was calculated from each peak area obtained by drawing a perpendicular line from valley of neighboring two peaks.

Example 2

Preparation of Compound 2

(29) The experiment was conducted in the same manner as in Example 1 except that 4500 g (12.8 moles) of monoalkylated diphenyl ether obtained in Example 1, 20 g (0.15 mole) of anhydrous aluminum chloride, 2860 g (10.2 moles) of 2-octyldodecene, 200 g of alkali neutralizing agent and 100 g of activated clay were used in a four-necked flask having 10 liter volume to obtain 5050 g of alkyl diphenyl ether wherein dialkylated diphenyl ether was contained as a main component. The product (referred to as Compound 2) was 2.28 in alkyl addition number from GPC spectrum (FIG. 3) and .sup.1H-NMR spectrum (FIG. 4). The ratio of the benzylic carbons being quaternary was 54.3 mole %.

(30) GPC

(31) Retention time of monoalkylated diphenyl ether: 43.44145.191 2.63 mole %

(32) Retention time of dialkylated diphenyl ether: 40.96443.441 57.6 mole %

(33) Retention time of trialkylated diphenyl ether: 36.47440.964 39.8 mole %

(34) .sup.1H-NMR (solvent: none, standard substance: none)

(35) Integrated value of =6.57.3 ppm is 1,

(36) integrated value of =2.83.3 ppm is 0.10,

(37) integrated value of =2.22.7 ppm is 0.07,

(38) integrated value of =0.51.9 ppm is 10.13.

Example 3

Preparation of Compound 3

(39) The experiment was conducted in the same manner as in Example 1 except that 4500 g (12.8 moles) of monoalkylated diphenyl ether obtained in Example 1, 25 g (0.19 mole) of anhydrous aluminum chloride, 3580 g (12.8 moles) of 2-octyldodecene, 250 g of alkali neutralizing agent and 125 g of activated clay were used in a four-necked flask having 10 liter volume to obtain 5980 g of alkyl diphenyl ether wherein dialkylated diphenyl ether was contained as a main component. The product (referred to as Compound 2) was 2.37 in alkyl addition number from GPC spectrum (FIG. 5) and .sup.1H-NMR spectrum (FIG. 6). The ratio of the benzylic carbons being quaternary was 51.8 mole %.

(40) GPC

(41) Retention time of monoalkylated diphenyl ether: 42.77444.616 3.06 mole %

(42) Retention time of dialkylated diphenyl ether: 40.33242.774 50.3 mole %

(43) Retention time of trialkylated diphenyl ether: 37.05540.332 46.6 mole %

(44) .sup.1H-NMR (solvent: none, standard substance: none)

(45) integrated value of =6.57.3 ppm is 1,

(46) integrated value of =2.83.3 ppm is 0.11,

(47) integrated value of =2.22.7 ppm is 0.08,

(48) integrated value of =0.51.9 ppm is 10.73.

Example 4

Preparation of Compound 4

(49) The experiment was conducted in the same manner as in Example 1 except that 400 g (1.14 moles) of monoalkylated diphenyl ether obtained in Example 1, 2.5 g (0.19 mole) of anhydrous aluminum chloride, 360 g (1.60 moles) of 2-hexyldecene, 25 g of alkali neutralizing agent and 12 g of activated clay were used in a four-necked flask having one liter volume to obtain 510 g of alkyl diphenyl ether wherein dialkylated diphenyl ether was contained as a main component. The product (referred to as Compound 4) was 2.41 in alkyl addition number from GPC spectrum (FIG. 7) and .sup.1H-NMR spectrum (FIG. 8). The ratio of the benzylic carbons being quaternary was 54.4 mole %.

(50) GPC

(51) Retention time of monoalkylated diphenyl ether: 42.77343.761 0.4 mole %

(52) Retention time of dialkylated diphenyl ether: 40.85042.773 44.8 mole %

(53) Retention time of trialkylated diphenyl ether: 37.20640.850 54.8 mole %

(54) .sup.1H-NMR (solvent: none, standard substance: none)

(55) Integrated value of =6.57.3 ppm is 1,

(56) integrated value of =2.83.3 ppm is 0.09,

(57) integrated value of =2.22.7 ppm is 0.11,

(58) integrated value of =0.51.9 ppm is 10.29.

Comparative Example 1

Preparation of Compound 5

(59) To the same flask used in Example 1 were placed 1600 g (9.4 moles) of diphenyl ether and 15 g (0.11 mole) of anhydrous aluminum chloride. After dissolving anhydrous aluminum chloride with heating at 110 C., to the mixture was added dropwise a mixture of 1810 g (10.8 moles) of l-dodecene and 1810 g (9.23 moles) of 1-tetradecene under nitrogen stream while maintaining the temperature at 110 C. for 4.5 hours to perform an addition reaction. After completion of dropwise addition, the mixture was stirred at 110 C. for 30 minutes, then allowed to cool to 90 C., and thereto added 68 g of alkali neutralizing agent and stirred for 30 minutes. To the mixture was added 68 g of activated clay, stirred at 90 C. for one hour and removed aluminum chloride and other acid substances by-produced by filtration at reduced pressure. Then, removing unreacted starting material and monoalkylated diphenyl ether by distillation at reduced pressure of 3.0 to 4.0 torr at 250 to 320 C., thereby 6000 g of alkyl diphenyl ether wherein dialkylated diphenyl ether was contained as a main component was obtained. The product (referred to as Compound 4) was 2.82 in alkyl addition number from GPC spectrum (FIG. 9) and .sup.1H-NMR spectrum (FIG. 10). The ratio of the benzylic carbons being quaternary was 37.8 mole %.

(60) GPC

(61) Retention time of monoalkylated diphenyl ether: 43.76645.224 1.8 mole %

(62) Retention time of dialkylated diphenyl ether: 42.15743.766 34.2 mole %

(63) Retention time of trialkylated diphenyl ether: 37.32842.157 64.0 mole %

(64) integrated value of =6.57.3 ppm is 1,

(65) integrated value of =2.83.3 ppm is 0.16,

(66) integrated value of =2.22.7 ppm is 0.17,

(67) integrated value of =0.51.9 ppm is 10.30.

Example 5

Preparation of Heat-Resistant Grease Composition

(68) To a glass vessel were added Compound 1 (230 g) obtained in Example 1 and 70 g of p-toluidine and the mixture was heated at 70 to 80 C. with stirring to obtain Solution A. To an another glass vessel were added Compound 1 (230 g) and 57 g of tolylene diisocyanate and the mixture was heated at 70 to 80 C. with stirring to obtain Solution B. To Solution A in a separable flask was added gradually Solution B over about 30 minutes with stirring. The mixture was heated until 170 C. with stirring for 40 minutes to obtain grease (Composition 1) containing urea compound as a thickener.

Test Example 1

Heat Stability Test

(69) In 30-ml glass beaker was weighed 20 g of each Compounds 1 to 5. Each sample was allowed to place in a thermostatic oven of 200 C. After 10 days or 20 days, the sample was checked for weight, kinematic viscosity and acid value. Change of properties by heat stability test was evaluated based on the values measured before the test.

Test Example 2

Fluidity at Low Temperature Test

(70) Compounds 1 to 9 were checked for pour point according to JIS K2269.

Test Example 3

Lubricity Test

(71) Friction coefficient was measured under a load of 0.98N and while raising the sample temperature from 25 C. to 250 C. by Ball on Plate friction tester using SUJ2 steel as Ball and SK-5 steel as Plate.

(72) Table 1 shows the general properties, Table 2 the results of heat stability test, and Table 3 the results of lubricity test of Compounds 1 to 5. Table 4 shows oil separation of the grease composition prepared in Example 5.

(73) TABLE-US-00001 TABLE 1 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Example 1 Example 2 Example 3 Example 4 Com. Ex.1 alkyl group R.sup.3 + R.sup.4 R.sup.3 + R.sup.4 R.sup.3 + R.sup.4 R.sup.3 + R.sup.4 R.sup.3 alkyl addition 2.23 2.28 2.37 2.41 2.82 mole number Properties 40 C. kinematic 123.2 127.1 134.1 122.6 102.6 viscosity (mm.sup.2/s) 100 C. kinematic 13.96 14.32 14.97 13.98 12.60 viscosity (mm.sup.2/s) viscosity index 111 112 113 112 116 pour point ( C.) 45 4 45 45 45

(74) Table 1 confirms Compounds 1 to 4 of the present invention exhibit low pour point equal to Compound 5 which is a conventional compound.

(75) TABLE-US-00002 TABLE 2 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Example 1 Example 2 Example 3 Example 4 Com. Ex.1 evaporation loss rate (%) 200 C. after 15.7 15.6 14.4 15.3 20.0 20 days viscosity ratio (times) 200 C. after 7.8 7.2 7.0 7.3 8.8 20 days acid value (mgKOH/g) before exam. 0.00 0.01 0.01 0.01 0.01 200 C. after 5.78 5.95 5.57 5.67 7.58 20 days

(76) From the results of Table 2, it is confirmed that Compounds 1 to 4 of the present invention exhibit low evaporation loss rate, low viscosity ratio and low in increase of acid value compared with Compound 5 which is known as a lubricant for high temperature.

(77) TABLE-US-00003 TABLE 3 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Example 1 Example 2 Example 3 Example 4 Com. Ex.1 friction coefficient 0.1605 0.1586 0.1607 0.1610 0.1723 (150 C.)

(78) Table 3 confirms Compounds 1 to 4 of the present invention exhibit low friction coefficient and are suitable for various lubricants compared with Compound 5 which is a conventional compound.

(79) TABLE-US-00004 TABLE 4 Example 5 Composition 1 base oil Compound 1 thickener Urea compound oil separation (100 C., 24 H, % 0.4

(80) Table 4 confirms the grease composition (Composition 1) using Compound 1 of the present invention as a base oil and urea compound as a thickener is less than 1% in oil separation and is practically suitable for grease.

(81) From the above, the present compound exhibits fluidity at low temperature equal to a conventionally well-known and practically used alkylated diphenyl ether. Further, the present compound is low in evaporation amount in heat stability test and is suppressed in increase of acid value compared with a conventional alkylated diphenyl ether which is widely used as a base oil for a lubricant for high temperature and heat-resistant grease.

(82) The base oil for a lubricant for high temperature and heat-resistant grease is most required to be suppressed in increase of acid value. Therefore, the present compound is confirmed to be excellent in heat resistance compared with a conventional alkylated diphenyl ether.

INDUSTRIAL APPLICABILITY

(83) The present compound and composition are not only usable as a base oil for various lubricants such as bearing oil, fluid bearing oil, oil-impregnated bearing oil, oil-impregnated plastics oil, gear oil, engine oil, gas turbine oil, automatic transmission fluid, vacuum pump oil, other machine oil and hydraulic fluid, but also usable as a base oil for grease. Further, the present compound can be added to or used conjointly with other synthetic base oil, and is suitable to expand design width of lubricants. In addition, the present compound is not only usable as lubricants but also as plasticizer, refrigerating oil or the like.