Synthetic Saturated Oils, and Their Production and Use

The atmosphere in a 1.5-liter stainless steel autoclave (20 kg/cm.sup.2 proof) equipped with a stirrer was replaced by nitrogen gas. Thereafter, 300 ml of anhydrous toluene and 136 g of anhydrous isoprene were charged into the autoclave under the stream of nitrogen. The mixture was cooled to -50.degree. C., and 4 ml of a toluene solution containing 0.1 mol/liter of nickel naphthenate, 4 ml of a toluene solution containing 1 mol/liter of ethylaluminum sesquichloride, 4 ml of a toluene solution containing 0.02 mol/liter of triphenyl phosphine and 64 g of propylene were added thereto, followed by polymerization at 60.degree. C. for 6 hours. The polymerization was stopped by adding 10 ml of a 10% solution of isopropanol in toluene under pressure, followed by stirring for 10 minutes. Unreacted propylene and isoprene were purged in a draft, and the reaction mixture was washed for 5 hours with 800 ml of an aqueous hydrochloric acid solution (pH 1.6) in a 2-liter glass flask and allowed to stand. The aqueous layer was removed, and the oily layer was mixed with 800 ml of an aqueous sodium hydroxide solution (pH 12) for 1 hour and allowed to stand. The aqueous layer was removed, and the oily layer was thoroughly mixed with 800 ml of ion-exchanged water for 1 hour and allowed to stand. The aqueous layer was removed, and the oily layer was concentrated under reduced pressure in a rotary evaporator. In this way, 103 g of low molecular weight polyisoprene were obtained as a colorless, transparent liquor having a viscosity of 24 cp at 30.degree. C. The number average molecular weight was 410 on determining by means of a vapor pressure osmometer. The infrared analysis according to the Morero's method showed that the microstructure of the polymer consisted of 42% of the cis-1,4 structure, 35.2% of the trans-1,4 structure, 19.8% of the 3,4 structure and 2.7% of the 1,2 structure. Further, it was confirmed that the value of the 3,4 structure was due to the absorption of the vinylidene group which resulted from the dehydrogenation of one propylene molecule connected to the ends of the polymer chains. Thus, more than 90% of isoprene was polymerized in the 1,4-polymerization form.

Raney nickel R-200 (produced by Nikko Rikagaku Sangyo Co., Ltd.) was activated, followed by deaeration and dehydration, and stored in a Schlenk's tube replaced by nitrogen gas. To a 200-ml stainless steel autoclave were added 5 g of the Raney nickel, 75 ml of the above obtained liquid polyisoprene and 75 ml of cyclohexane, and hydrogen gas was charged therein from a hydrogen bomb until a pressure gauge indicated 25 kg/cm.sup.2. The contents were heated to 150.degree. C. in an oil bath while being mixed, and mixation was further continued at 150.degree. C. under 25 kg/cm.sup.2 for 30 hours so as to complete the hydrogenation. After cooling, the pressure in the autoclave was released to atmospheric pressure, and the catalyst was removed centrifugally to obtain a colorless, transparent liquor. The liquor was concentrated under reduced pressure in a rotary evaporator to remove the solvent, whereby 74 ml of a colorless, transparent liquor having a viscosity of 35 cp at 30.degree. C. were obtained. The liquid polyisoprene thus hydrogenated showed approximately the same NMR and infrared spectrum charts as those of squalane. On comparison of the NMR charts, the ratios represented by: ##EQU1## were 0.39 and 0.40 respectively for squalane and the hydrogenated liquid polyisoprene. Consequently, it became clear that the hydrogenated liquid polyisoprene has almost the same structure as that of squalene.

Fractional distillation of 10 g of the hydrogenated product by the use of a molecular distillation apparatus gave 3.5 g of the first fraction (b.p., lower than 120.degree. C./1 mmHg), 3.2 g of the second fraction (b.p., 140.degree. C./1 mmHg to 250.degree. C./0.2 mmHg) and 3.3 g of the residue. As the first fraction has very slight irritation to skin, it is excluded from this invention.

The atmosphere in a 1,5-liter stainless steel autoclave (20 kg/cm.sup.2 proof) equipped with a stirrer was replaced by nitrogen gas. Thereafter, 300 ml of anhydrous toluene and 136 g of anhydrous isoprene were charged into the autoclave under the stream of nitrogen. The mixture was cooled to -50.degree. C., and 4 ml of a toluene solution containing 0.1 mol/liter of nickel naphthenate, 4 ml of a toluene solution containing 1 mol/liter of ethylaluminum sesquichloride, 20 ml of a toluene solution containing 0.02 mol/liter of triphenyl phosphine and 64 g of propylene were added thereto, followed by polymerization at 60.degree. C. for 6 hours. The polymerization was stopped in the same manner as in Example 1. Removal of the catalyst was also carried out in the same manner as in Example 1, followed by concentration under reduced pressure in a rotary evaporator. In this way, 73 g of low molecular weight polyisoprene were obtained as a colorless, transparent liquor having a viscosity of 983 cp at 30.degree. C. The number average molecular weight was 540 on determining by means of a vapor pressure osmometer. The infrared analysis according to the Morero's method showed that the microstructure of the polymer consisted of 43.6% of the cis-1,4 structure, 36.9% of the trans-1,4 structure, 19.0% of the 3,4 structure and 0.5% of the vinyl structure. Further, it was confirmed that the 3,4 structure was due to the absorption of the vinylidene group which resulted from the dehydrogenation of one propylene molecule connected to the ends of the polymer chains.

Hydrogenation was carried out by replacing the atmosphere in a 200-ml stainless steel autoclave by nitrogen gas, charging 65 ml of the above obtained liquid polyisoprene, 5 g of Raney nickel R-200 as activated and 75 ml of cyclohexane into the autoclave, and mixing the contents at 150.degree. C. for 30 hours while maintaining the hydrogen pressure in the autoclave at 25 kg/cm.sup.2. After cooling, the catalyst was centrifugally removed to obtain a colorless, transparent liquor. The liquor was concentrated under reduced pressure in a rotary evaporator to remove the solvent, whereby 64 ml of a colorless, transparent liquor having a viscosity of 1,050 cp at 30.degree. C. were obtained. The iodine value, the hydroxyl value and the acid value were all zero.

A rotator for a magnetic stirrer was placed in a 500-ml four-necked flask, and the mouths of the flask were equipped with ampoules containing 28.2 g of anhydrous naphthalene, 200 ml of anhydrous tetrahydrofuran, 40 ml of anhydrous isoprene and 1.38 g of metallic lithium, respectively. After completely replacing the atmosphere in the flask by nitrogen gas, the ampoule containing metallic lithium was opened by a magnetic hammer to allow the lithium to fall into the flask. Next, tetrahydrofuran and naphthalene were allowed to fall in the same manner as above. On mixing the contents in the flask at room temperature for 17 hours, a deep green complex of lithium-naphthalene was formed. After cooling to -70.degree. C., isoprene was added, and the mixture was stirred at room temperature for 2 hours, whereby the reaction solution turned to yellow brown. The tetrahydrofuran was removed from the reaction solution under reduced pressure, and then 100 ml of anhydrous n-hexane and 100 ml of cyclohexane were added thereto under the stream of nitrogen gas. After cooling to -40.degree. C., 95 ml of isoprene were added, and polymerization was carried out at 50.degree. C. for 3 hours. The metallic lithium was removed from the product, in the same manner as in Example 1, by washing the reaction mixture with an aqueous hydrochloric acid solution. After neutralization and washing with water, the separated oil layer was concentrated under reduced pressure in a rotary evaporator to give low molecular weight polyisoprene. By the analysis according to the Morero's method, the microstructure of the resulting polymer was found to consist of 85% of the cis-1,4 structure and 15% of the 3,4 structure. The molecular weight determined by means of a vapor pressure osmometer was 760.

In the same manner as in Example 1, 64 g of the thus obtained liquid polyisoprene were hydrogenated in a 200-ml stainless steel autoclave using 5 g of Raney nickel R-200 and 75 ml of cyclohexane. The hydrogenation was carried out at 150.degree. C. for 30 hours with stirring, while keeping the hydrogen pressure in the autoclave at 30 kg/cm.sup.2. After cooling, the catalyst was centrifugally removed to obtain a colorless, transparent liquor. The liquor was concentrated under reduced pressure in a rotary evaporator to obtain 63 g of a colorless and odorless, transparent liquor having a viscosity of 130 cp at 30.degree. C. The iodine value, the hydroxyl value and the acid value of the liquor were all zero.

Preparation of the catalyst, the polymerization and the after-treatment was carried out in the same manner as in Example 3 using 7.05 g of anhydrous naphthalene, 200 ml of anhydrous tetrahydrofuran, 25 ml of anhydrous isoprene and 0.345 g of metallic lithium to give low molecular weight polyisoprene. By the analysis according to the Morero's method, the microstructure of the obtained polymer was found to consist of 88% of the cis-1,4 structure and 12% of the 3,4 structure. The molecular weight determined by means of a vapor pressure osmometer was 2,800.

In the same manner as in Example 1, 64 g of the liquid polyisoprene was hydrogenated at 150.degree. C. for 30 hours using 5 g of Raney nickel R-200 and 75 ml of cyclohexane while keeping the hydrogen pressure at 30 kg/cm.sup.2. After cooling, the reaction mixture was centrifuged in order to remove the catalyst, and concentrated under reduced pressure in a rotary evaporator to obtain 63 g of a colorless, transparent liquor. The liquor was colorless and odorless and had a viscosity of 3,600 cp. The iodine value, the hydroxyl value and the acid value of the liquor were all zero.

The comparison of physical properties between squalene and the hydrogenated low molecular weight polyisoprene (second fraction obtained in Example 1) is shown in the following table:

Cold cream containing the hydrogenated polyisoprene in Table 1 were formulated according to the following recipe:

The cold cream thus formulated was the same as that obtained using squalene in place of the hydrogenated polyisoprene in color, odor, long-term stability, non-irritativeness, spread, stiffness and touch.

Lipstick containing the same hydrogenated polyisoprene as in Example 5 was formulated according to the following recipe:

The lipstick thus formulated exhibited the same luster and spread as those of the lipstick formulated using squalene in place of the hydrogenated polyisoprene.

Hygienic cream containing the same hydrogenated polyisoprene as in Example 5 was formulated according to the following recipe:

The hygienic cream thus formulated exhibited the same spread and smoothness as those of the hygienic cream formulated using squalene in place of the hydrogenated polyisoprene.

Low molecular weight polyisoprene was prepared under completely the same conditions of polymerization and after-treatment as in Example 1 in order to check the reproducibility, whereby 103 g of a colorless, transparent liquor having a viscosity of 18 cp at 30.degree. C. were obtained. On determining the molecular weight by means of a vapor pressure osmometer, the number average molecular weight was 390.

Hydrogenation of the liquid polyisoprene was carried out under completely the same conditions as in Example 1. After completion of the hydrogenation, the reaction mixture was cooled and the pressure was released to atmospheric pressure. The catalyst was centrifugally removed to obtain a colorless, transparent liquor. In order to remove the solvent, the liquor was concentrated under reduced pressure in a rotary evaporator, whereby 74 ml of a colorless, transparent liquor were obtained. The viscosity was 30 cp at 30.degree. C. The liquid polyisoprene thus hydrogenated exhibited almost the same NMR and infrared spectrum charts as those of squalene. On comparison of the NMR charts, the ratios represented by: ##EQU2## were 0.39 and 0.40 respectively for squalene and the hydrogenated liquid polyisoprene. Consequently, it became clear that the hydrogenated liquid polyisoprene has almost the same structure as that of squalene.

Fractional distillation of 10 g of the hydrogenated product by the use of a molecular distillation apparatus gave 3.1 g of the first fraction (b.p., lower than 190.degree. C./1 mmHg) and 6.9 g of the residue. The viscosity of the residue was compared with that of squalene and of the polymer of octene-1 as shown in Table 2.

As seen from Table 2, the hydrogenated polyisoprene as a lubricating oil has a high viscosity index and is a free flowing, low viscous liquid even at extremely low temperatures. This means that the hydrogenated polyisoprene passes the standards of the lubricating oil for jet engines specified by the American Military Standards. Thus, the lubricating oil of the present invention has almost the same flowing property as that of squalene and is very superior as a lubricating oil for jet engines. The polymer of octene-1 is inferior to the lubricating oil of the present invention in viscosity index and flow point. Particularly, the viscosity at -40.degree. C. of the octene-1 polymer is close to the upper limit of the said Standards, which clearly means that the polymer has a very poor viscosity performance at low temperatures.

Table 3 shows that the synthetic lubricating oil comprising the hydrogenated polyisoprene of the present invention is much superior as a lubricating oil for precision machines to commercially available products selected from those which are best as a synthetic lubricating oil for precision machines.

The above commercially available product are in use for public telephones, watches, electric power meters and various equipments and are regarded as important as a lubricating oil having a particularly superior viscosity performance at low temperatures. However, the lubricating oil of the present invention is much superior to those commercial products in that performance. For example, the oil has a viscosity of as low as 510 centistokes even at -40.degree. C., while those commercial products solidify at -37.5.degree. C. Further, the oil of the present invention has a viscosity index of 140, which means that the oil is superior to those commercial products in the viscosity performance.

The octene-1 polymer as described for comparison in Table 2 was synthesized by the following method:

In a 2,000-ml four-necked flask, 200 ml of ethyl ether were charged, and 17 g of aluminum chloride were dissolved in the ether. Thereafter, 3.1 g of lithium hydride was added to prepare a catalyst, and a large proportion of ethyl ether was removed under reduced pressure. To the flask were added 800 ml of octene-1 and 25 g of titanium tetrachloride, and the reaction was carried out at 100.degree. to 200.degree. C. for 4 hours. After completion of the reaction, ammonia gas was blown into the reaction solution, and the resulting precipitates were filtered off to remove the catalyst. The resulting reaction solution was distilled under reduced pressure to remove the unreacted octene-1 and the dimers thereof. Hydrogenation was then carried out at 150.degree. C. and at a hydrogen pressure of 20 kg/cm.sup.2 using Raney nickel catalyst. After the hydrogenation, the catalyst was removed to obtain 490 g of the oligomer. The content of tri- to pentamers in the oligomer was 80%.