CA1056408A - Hydrogenated olefine oligomers - Google Patents
Hydrogenated olefine oligomersInfo
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- CA1056408A CA1056408A CA231,058A CA231058A CA1056408A CA 1056408 A CA1056408 A CA 1056408A CA 231058 A CA231058 A CA 231058A CA 1056408 A CA1056408 A CA 1056408A
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Abstract
ABSTRACT
Oligomerising propylene using a Friedel Crafts catalyst at a temperature in the range -10 to 80°C and hydrogenating the oligomer so obtained to produce oils useful as hydraulic fluids.
Oligomerising propylene using a Friedel Crafts catalyst at a temperature in the range -10 to 80°C and hydrogenating the oligomer so obtained to produce oils useful as hydraulic fluids.
Description
1056~08 The invention i8 concerned with the production of paraffinic base oils especially those that are used in hydraulic systems with mechanical transmission, in hydraulic shock-absorbers etc.
For a liquid to be useful as a hydraulic fluid it must have a fairly high boiling point, a8 low a freezing point as possible, a high viscosity index and good lubricating properties. The sealing joints, in hydraulic transmission systems are usually made with elastomers 80 it is important that the fluid be practically inert in relation to the particular elastomers with which it is brought into contact. In particular the fluid must not affect the mechanical properties of these materials nor must it cause excessive swelling or contraction of the elastomer.
Use is sometimes made of fluids based on glycols or glycol polyethers, but these products are costly and their hydrophilic nature is troublesome in certain applications.
It is also known to use both mineral and synthetic hytrocarbon oils. However, hydrocarbon oils must have a low freezing point and a flash point exceeding 100C
in open vessel. In attition the viscosity must be strictly adapted to the partîcular use for which the fluid is intended and since tne range of-viscosities of hydrocarbon bases for the usual hydraulic fluids extends from 2 to 30 cSt at 37.8 & it is difficult to make, by refining crude petroleum distillates, oils that are suitable as bases for hydraulic fluids. It is only at the cost of very intensive refining that a mineral oil is obtained having sufficient inertia and a sufficiently low freezing point in relation to the elastomers.
Ie has also been known for some time that the oils obtained by polymerisation of light olefins can be used as bases for hydraulic fluids. The properties of these ~ynthetic oils, in particular their re~istance to oxidation, are further improved by subjecting them to hydrogenation (R.E. Hatton "Introduction to Hydraulic Fluids" 1962, pages 181 and 182). In addition there , ~ - 2 - ~
.
lOS6408 are many patents relsting to the manu~acture or uses of oils of this type.
Por example French patent no. 794,397 mentioned as long ago a8 1935 the possibility of manufacturing lubricating oils by the polymerisation of light ol~fino, such as propylene ant isobueylene, and the hydrogenation of the polymer obtained. United States patent no. 2,360,446 proposes the use, for lubr~cating internal combustion engines, of a composition containing an oil of thi~ type. The oils discussed have a viscosity exceeding 15.5 cSt at 99.9&.
This patent mæntions that this oil can be made from propylene or isobutylene, by means of polymerisation in the presence of a Friedel Crafts catalyst followed by hydrogenation of the polymer. However, the vi~cosity of these synthetic oils is very variable and fractional distillation has to be carried out to obtain the fraction having the desired flash point and viscosity and the ~ield is often poor. Furthermore these synthetic oils consist of isoparaffinic hytrocarbons whose degree of branching and purity are variable which makes it tifficult to master their swelling properties in relation to elastomers.
French patent no. 1,357,634 proposes a basic oil for hydraulic fluids which gives every satisfaction, in particular as regards its effects on elastomers.
The m~nufacture of t~iA oil is associated with the manufacture of technical trlpropylene and tetrapropylene, in which the oligomerisation of the propylene is carried out, at a tenperature of at least 140 C, on a catalyst based on phosphoric acit, and the oligomers thus obtained subjected to fractional distillation. According to Prench patent no. 1,357,634, by hydrogenating a fraction of these oligomers, whose initial distilling point is in excess of 175C, or a fraction distilling between 200 and 300C, an oil is obtained which i8 perfectly suitable a8 a ba~e for very high quality hydraulic fluids. However this proce~s suffers from the disadvantage that the propylene oligomers that form at a temperature of at least 140C and in contact with phosphoric acid, COnSaln only a small proportion of the required fraction.
:
.
'I`he need for high quality hydraulic fluids i~ constantly increasing while the need for tripropylene and tetrapropylene is static. We have therefore devised a process to obtain a ~uitable oil with a high yield which is not linked with the manufacture of tripropylene or tetrapropylene.
The polymerisation of propylene, isobutylene and n-butenes is regularly carried out in the liquid phase at temperatures of less than 100 C, and even much lower, in the presence of Friedel Crafts catalyst as is mentioned for example in U.K. patent 1148966. This patent also discloses that the mean molecular weight of the polymer obtained depends in particular on the reaction temperature and the activity of the catalyst. With the other factors unchanged, the mean molecular weight of a product is higher the lower the reaction temperature.
The present invention provides a process for the pro-duction of highly paraf'finic basic oils having a flash point excéeding 100 C and the viscosity at 37.8 C within the range of 2 to 30 cSt comprising oligomerising an olefin selected from propylene, isobutylene, n-butenes and mixtures of these olefins in the liquid phase, in the presence of a Friedel Crafts catalyst at a temperature between -10 and 80C, separ-ating the catalyst and the oligomers thus formed and hydro-genating the oligomer or a fraction thereof.
It may be necessary to distil within the temperature range of -10 C to 80 C the reaction temperature may be selec-ted to ensure that an oligomer is obtained which on hydrogen-ation yields an oil of the required viscosity. Thus ou~
process allows production of a desired oil in a high yield although we may distil the oligomer to isolate the fraction having the required viscosity and flash point even in this situation yields are high.
We have found that oligomerisation performed within ~ _4_ . . .
, ~ 105f~408 the temperature range and with the type of catalyst specif-.~
ied above yields oligomers having the required mean molecular weight and viscosity for hydrogenating to produce basic .
oils for hydraulic fluids. Thus, following hydrogenation ~ and fractionation if necessary it is possible to obtain the ,~' desired oil in high yield. The most ~'", ~:, ;' ~ ' ' ,,~,,1 , '' ' ~.
:~' :J
;,.
, ,........................................................................ .
. . .
:, ~, ., .
~, .1 ., .
..
.,,~ .
-4a-.- , , , - .
1056~o8 favoursb1e oligomerisation temperature to obtain a certain oil may be found by e~perimentation within the ra~ge specified.
HydrogenatioD saturates the olefinic bond present in the molecules of the oligomer and is continued until the bromine number of the product is practically Dil and in any csse less than 1. Any conventional hydrogenation process may be used, the conditions of the reaction, in particular the temperature, being regulated 80 that no appreciable decomposition takes place. As a rule, practically no light products are formed if hydrogenatio~ is performed at a t Terature of leu~ tban 220&. Our preferred Dethod i~ to u~e a caealy~t b~ed on nickel, nickel and molybdenum, nickel and tungsten, nickel and cobalt, or a catalyst based on one or more of the oxides of these metals. The appropriate pressure and temperature depend on the activity of the catalyst used. Por instance, hydrogenation can be performed with a catalyst based on nickel and cobalt, at a t¢mperflture from 180 to 220 ~, at a pressure of 10 tc 100 bars. The oil thus obtd ned consists of practically pure isoparaffinic hydrocarbons generally above 99% pure. Furthermore, we find that when the oil is made from propylene it has, in relation to elastomers, a particularly lcw swelling power.
Our preferred process for the oligomerisation of propylene is carried out a8 follows. A reactor provided with stirring and cooling means is used 80 that the reaction mixture may be maintained at the required temperature and the pressure is such that the mixture is liquid, a pressure of 30 bars in the reactor is generally sufficient. In the reactor, the propylene is brought into contact with 0.04 to 0.08~ water and 0.5 to 0.8% anhydrous boron trifluoride. These proportions are expressed by weight in relation to that of propylene. The reaction temperature is generally one between 70 and 80 & and an average reaction time of half an hour is generally sufficient to accomplish the total conversion of the propylene.
10~ 08 The product of the reaction comprises gaseous pro-ducts, mainly boron trifluoride and propane being the chief impurity of the propylene used as raw material; these gaseous products are separated by employing the usual appropriate means that are well known to the technician.
After degassing, the oligomer contains boron and fluorine compounds derived from boron trifluoride which can be eliminated by washing the oligomer with an alkaline solution.
The oligomer is then fractionated by distilling, if necessary, to separate the fraction having the required flash point and viscosity and finally, the oligomer is hydrogenated.
We have found that oil produced has a smaller swelling effect on elastomers than do hydrogenated polypropylenes obtained by other processes.
Although the oil prepared by means of the present pro-cess, from propylene, isobutylene or n-butenes, are most useful as hydraulic ~luids and have a small swelling effect on most elastomers certain elastomers undergo slight shrink-age in contact with this oil. Generally isoparaffinic oil has a greater swelling power the higher its content of impur-ities of the cyclane type. We have surprisingly discovered that a purely isoparaffinic oil brings about an appreciable contraction of certain elastomers, in particular elastomers based on polyurethanes which may be detrimental to the tightness of the joints of hydraulic circuits and that this may be overcome by blending in certain polycyclane oils.
~hus the present invention m.~kes il: pl~S~:i l)lc l,o pl~
pare an oil for hydraulic fluids which has a predetermined swellin~ power, also provides the incorporation with the ~ -6-~5~08 oil produced by the process of the invention of a smallerproportion of a naphthenic oil may be adjusted to confer on the final oil the desired swelling power with the par-ticular elastomer with which it is to be used.
The naphthenic oil used in these blends is preferably a mineral or synthetic oil consisting essentially of satur-ated hydrocarbons whose molecule comprlses several condensed cycles. It is possible to use in the present process any -6a_ 1056~08 naphthenic oil provided th~t its flash point is sufficiently high ant that it is practically free from aromatic hydrocarbons. An oil containing a hi8h proportion of aromatic hydrocarbcns would affect the mechanical properties of the elastomers. The presence of isoparaffinic hydrocarbons in this oil does not entail any drawbacks. The viscosity of the naphthenic oil matters little, provided that the final oil in which It is incorporated, has th~ de8ired viscosity, we prefer to use a naphthenic oil whose viscosity i8 between 10 and 100 cSt at 37.8C.
It is possible to use a naphthenic oil derived from an appropriatc crude petroleum, by means of the usual operations of distilling and refining.
Nevertheless, it is very tifficult in practice to obtain from petroleum a naphthenic oil sufficiently free from aromatic hydrocarbons. ~or this rea80n, a synthetic oil i~ used for preference. We prefer to use a synthetic 4il cona~ n& of cyclanic hydrocarbons whose molecule contains at least three condensed cycles, each with 5 carbon atoms. This type of oil may conveniently be prepared from a fraction of steamcracking naphtha distilling between 80 and 175C. A fraction of naphtha of this kind contains hi8h proportions of cyclopentadiene, dicyclopentadiene and mono or dimethyl derivatives of these cyclodienes. The cyclodienes present in the naphtha may be condensed to polycyclopentadienes by for instance maintaining the naphtha at about 260 & , at a pressure of 12 to 15 bars, for 2 to 4 hours. The product of this reaction may then be hydrogenated after diluting it with an inert solvent to yield the na~hthenic oil. Hydrogenation is performed by any usual means 80 as to saturate the ethylene bond of the molecules of polycyclopentadienes, to form the corresponding polycyclane hytrocarbons. Tbe hydrogenated mixture is finally fractionated by distilling, 80 as to recover the solvent and separate a fraction having the desired flash-point and vigcosity.
The proportion of naphthenic hydrocarbons incorporated with the oil made according to the present invention of our invention may be varied to adjust very accurately the ~welling power of the final blend and as much as 20%
napthenic oil may be used. We have found that the oil manufactured according to the invention from propylene and contsining from 3 to 10%, or better still, from 5 to 8% of its weight of this type of naphthenic oil behaves absolutely satisfactorily in contact with the usual elastomers.
The polycyclane hydrocarbons may be incorporated with the final oil by simple mixing.
Alternatively the appropriate fraction of the oligomer obtained by our process may be mixed with the appropriate proportion of polycyclopentadienes, and hydrogenation the mixture.
The present invention also provide~ oil obtained by the processes described above. It al~o provides hydrocarbon-based hydraulic fluid containing a high proportion of such oils and such a hydraulic fluid consisting of a basic oil and appropriate additives.
The oil may contain other conventional additives such as viscosity index improvers, extreme-pressure additives, anti-wear additives and oxidation inhibitors.
The present invention i8 illustrated but in no way limited by reference to the following examples.
Exa ~
~ basic oil for hydraulic fluids having a viscosity between 16 and 18 cSt at 37.8C was prepared as follows:
Propylene was brought into contact with 0.05% by weight of water and 0~06%
by weight of anhydrous boron trifluoride in a stirred and cooled reactor at a pressure of 20 bars, and a temperature of 30C. The mixture was in the reactor for half an hour. On leaving the reactor, the mixture was expanded from 20 to 1 bar pressures which brought about the evaporation of propane and boron trifluoride, which were thus eliminated. The remain;ng liquid was washed with dilute soda soluti~n and an oli~o~er obtained h~vin~ the follo~in~ char~cteri~tic~:
Distillatio~ (according to the standArd ASTM D-86) Volume distilled (%) Temperature &
Initi~l point 276 30o Flnal point 361 Viscosity at 37.8C 15 cSt Mesn molecular mass 340 Bromine num~er 44 ThiR oligomer wss hytrogenatet on a catalyst based on nickel and cobalt, at 215 & under a hytrogen flow at a pressure of 18 bars ant a speed of 0.25 h 1.
A basic oil for hydraulic fluids was obtsinet by hydrogenation having the Pollowing characteristics:
Viscosity at 37.8 & 16.56 cSt Viscooity ~t 99& 3.20 c5t Viscosity intex 42 Plash point, open vessel (Cleveland) 144C
Density at 15 & 0.819 Freezing point -51C
Bromine number 0.4 Aro~etics content 0.3% by ~eight The yield of final product in relation to the weight of the propylene used exceedet 99%.
A basic oil for bydraulic fluids was prepared having a viscosity between 4 and 6 cSt at 37.8C.
The oligomerisAtion of the propylene was carried out a8 in ~xample 1, with the reactor temperature at 70 C and the yield of oligomer in relation to the _ g _ lOS6408 weight of the propylene used exceeded 99.5% and the characteristics of the oligome!r were:
Viscosity at 37.8C 5.5 cSt Flash point in open vessel (Cleveland) 95C
Mean molecular mass 265 This oligomer was fractionated by distilling so as to isolate the fraction having the desired viscosity and flash point. To do 80, three fractions were separated, a first fraction (7% by volume), mid fraction (79% by volume) and a residue (14%) by volume.
The intermediate fraction (79% by volume) had the required characteristics, viz:
Viscosity at 37.8C 4.8 cSt Plash point in open vessel (Cleveland) 110C
Mean molecular mass 260 Thi~ fraction was hydrogenated by operating as in example 1 except that the temperature was 180C.
The oil (A) was obtained with a yield of 79% by weight in relation to the weight of propylene used and had the following characteristics:
Viscosity at 37.8 & 4.9 cSt Viscosity at 99 C 1.5 cSt Density at 15 & 0.806 Freezing point - 60 C
Cleveland flash point 110C
Bromine number 0.2 Aromatic hydrocarbons 0.2% by weight Distillation (ASTM method D-86):
Volume distilled (%) Temperatures (C) Initial point 237 Final point 326 ~056408 By way of comparison an oil of the same type was prepared by means of a process similar to that of French patent 1357634 in which propylene was oligomerised lgo& in contact with phosphoric acid deposited on kiesel-guhr and the fraction distilling from 200 to 300 & was sepsratet. In this process the yield was 5~ by weight in relation to the weight of propylene used. By hydrogenating this fraction, an oil (B) was obtained which was distinguished from oil (A) by its content of cycloparaffins and its behaviour in relation to elastomers.
The composition of the two oils, determined by mass spectrometry, was as follows:
Oil A Oil B
I~opsraffins 99.7 88.1 Cycloparaffins 0.1 11.3 Aromatics 0.2 0.5 A sample of polyurethane rubber was immersed in each of these oils at 130 & , for 20 days. After this test, the volume of the sample immers2d in oil A had dropped by 6.9%, and that of the sample immersed in oil B had risen by 3.8%.
~xample 3 Two oils were prepared having determined swelling powers, by mixing a naphthenic oil (C) with the oil A defined in e~ample 2.
Oil C was prepared by heating 170 kg of a fraction of naphtha obtained by steam cracking and distilling from 80 to 175C which contained approximately 60%
dimers of cyclopentadiene and methyl-cyclopentadiene in an autoclave, for up to 260C and then held at that temperature for a further 2 hours. The contents of the autoclave are then reduced by distilling until obtaining 100 kg residue was a resinous, very dark brown substance, whose bromine number was 60. It was treated with 500 kg of a hydrocarbon solvent distilling at 150 to 180 & and the ~olution obtained hydrogenated on a basic nickel and tungsten catalyst, ut 240C
under 60 bars, until the bromine number of the product is zero. The product of hydrogenation was distilled to separate the solvent, 40 kg of an oil distilling from 280 to 380C (oil C) and 60 kg residue.
Oil C was practically colourless and had the following characteristics:
Density at 15 & 1.019 Refractive index 1.529 Viscosity at 37.8 & 80.5 cSt Viscosity at 99& 7.2 cSt Bromine number less than 1 ~lash point (Cleveland) 142C
Freezing point -12C
Two mixtures were then prepared, one with 93~ oil A and 7% oil C, the other with B6~ oil A and 14% oil C. These proportions being by Yolume.
A sample of polyurethane rubber was immersed in oil A and in each mixture at 130& for 20 days. The mechanical characteristics of the samples were ~easured before and after each very stringent test, and the Yariation of each characteri~tic was calculated in relative terms (% of initial value).
The following results were obtained:
93Z A 86% A
Oil tested Oil_A 7% C 14% C
Relative variation (%):
of the dule at 100% -.85 - 86 - 84 of the dule at 300% - 81 - 79 - 79 of the breaking loan - 85 - 85 - 83 of the Yolume - 6.90 + 0.5 ~ 2.2 ~ 0.$ ~ 2.7 ) 0.5
For a liquid to be useful as a hydraulic fluid it must have a fairly high boiling point, a8 low a freezing point as possible, a high viscosity index and good lubricating properties. The sealing joints, in hydraulic transmission systems are usually made with elastomers 80 it is important that the fluid be practically inert in relation to the particular elastomers with which it is brought into contact. In particular the fluid must not affect the mechanical properties of these materials nor must it cause excessive swelling or contraction of the elastomer.
Use is sometimes made of fluids based on glycols or glycol polyethers, but these products are costly and their hydrophilic nature is troublesome in certain applications.
It is also known to use both mineral and synthetic hytrocarbon oils. However, hydrocarbon oils must have a low freezing point and a flash point exceeding 100C
in open vessel. In attition the viscosity must be strictly adapted to the partîcular use for which the fluid is intended and since tne range of-viscosities of hydrocarbon bases for the usual hydraulic fluids extends from 2 to 30 cSt at 37.8 & it is difficult to make, by refining crude petroleum distillates, oils that are suitable as bases for hydraulic fluids. It is only at the cost of very intensive refining that a mineral oil is obtained having sufficient inertia and a sufficiently low freezing point in relation to the elastomers.
Ie has also been known for some time that the oils obtained by polymerisation of light olefins can be used as bases for hydraulic fluids. The properties of these ~ynthetic oils, in particular their re~istance to oxidation, are further improved by subjecting them to hydrogenation (R.E. Hatton "Introduction to Hydraulic Fluids" 1962, pages 181 and 182). In addition there , ~ - 2 - ~
.
lOS6408 are many patents relsting to the manu~acture or uses of oils of this type.
Por example French patent no. 794,397 mentioned as long ago a8 1935 the possibility of manufacturing lubricating oils by the polymerisation of light ol~fino, such as propylene ant isobueylene, and the hydrogenation of the polymer obtained. United States patent no. 2,360,446 proposes the use, for lubr~cating internal combustion engines, of a composition containing an oil of thi~ type. The oils discussed have a viscosity exceeding 15.5 cSt at 99.9&.
This patent mæntions that this oil can be made from propylene or isobutylene, by means of polymerisation in the presence of a Friedel Crafts catalyst followed by hydrogenation of the polymer. However, the vi~cosity of these synthetic oils is very variable and fractional distillation has to be carried out to obtain the fraction having the desired flash point and viscosity and the ~ield is often poor. Furthermore these synthetic oils consist of isoparaffinic hytrocarbons whose degree of branching and purity are variable which makes it tifficult to master their swelling properties in relation to elastomers.
French patent no. 1,357,634 proposes a basic oil for hydraulic fluids which gives every satisfaction, in particular as regards its effects on elastomers.
The m~nufacture of t~iA oil is associated with the manufacture of technical trlpropylene and tetrapropylene, in which the oligomerisation of the propylene is carried out, at a tenperature of at least 140 C, on a catalyst based on phosphoric acit, and the oligomers thus obtained subjected to fractional distillation. According to Prench patent no. 1,357,634, by hydrogenating a fraction of these oligomers, whose initial distilling point is in excess of 175C, or a fraction distilling between 200 and 300C, an oil is obtained which i8 perfectly suitable a8 a ba~e for very high quality hydraulic fluids. However this proce~s suffers from the disadvantage that the propylene oligomers that form at a temperature of at least 140C and in contact with phosphoric acid, COnSaln only a small proportion of the required fraction.
:
.
'I`he need for high quality hydraulic fluids i~ constantly increasing while the need for tripropylene and tetrapropylene is static. We have therefore devised a process to obtain a ~uitable oil with a high yield which is not linked with the manufacture of tripropylene or tetrapropylene.
The polymerisation of propylene, isobutylene and n-butenes is regularly carried out in the liquid phase at temperatures of less than 100 C, and even much lower, in the presence of Friedel Crafts catalyst as is mentioned for example in U.K. patent 1148966. This patent also discloses that the mean molecular weight of the polymer obtained depends in particular on the reaction temperature and the activity of the catalyst. With the other factors unchanged, the mean molecular weight of a product is higher the lower the reaction temperature.
The present invention provides a process for the pro-duction of highly paraf'finic basic oils having a flash point excéeding 100 C and the viscosity at 37.8 C within the range of 2 to 30 cSt comprising oligomerising an olefin selected from propylene, isobutylene, n-butenes and mixtures of these olefins in the liquid phase, in the presence of a Friedel Crafts catalyst at a temperature between -10 and 80C, separ-ating the catalyst and the oligomers thus formed and hydro-genating the oligomer or a fraction thereof.
It may be necessary to distil within the temperature range of -10 C to 80 C the reaction temperature may be selec-ted to ensure that an oligomer is obtained which on hydrogen-ation yields an oil of the required viscosity. Thus ou~
process allows production of a desired oil in a high yield although we may distil the oligomer to isolate the fraction having the required viscosity and flash point even in this situation yields are high.
We have found that oligomerisation performed within ~ _4_ . . .
, ~ 105f~408 the temperature range and with the type of catalyst specif-.~
ied above yields oligomers having the required mean molecular weight and viscosity for hydrogenating to produce basic .
oils for hydraulic fluids. Thus, following hydrogenation ~ and fractionation if necessary it is possible to obtain the ,~' desired oil in high yield. The most ~'", ~:, ;' ~ ' ' ,,~,,1 , '' ' ~.
:~' :J
;,.
, ,........................................................................ .
. . .
:, ~, ., .
~, .1 ., .
..
.,,~ .
-4a-.- , , , - .
1056~o8 favoursb1e oligomerisation temperature to obtain a certain oil may be found by e~perimentation within the ra~ge specified.
HydrogenatioD saturates the olefinic bond present in the molecules of the oligomer and is continued until the bromine number of the product is practically Dil and in any csse less than 1. Any conventional hydrogenation process may be used, the conditions of the reaction, in particular the temperature, being regulated 80 that no appreciable decomposition takes place. As a rule, practically no light products are formed if hydrogenatio~ is performed at a t Terature of leu~ tban 220&. Our preferred Dethod i~ to u~e a caealy~t b~ed on nickel, nickel and molybdenum, nickel and tungsten, nickel and cobalt, or a catalyst based on one or more of the oxides of these metals. The appropriate pressure and temperature depend on the activity of the catalyst used. Por instance, hydrogenation can be performed with a catalyst based on nickel and cobalt, at a t¢mperflture from 180 to 220 ~, at a pressure of 10 tc 100 bars. The oil thus obtd ned consists of practically pure isoparaffinic hydrocarbons generally above 99% pure. Furthermore, we find that when the oil is made from propylene it has, in relation to elastomers, a particularly lcw swelling power.
Our preferred process for the oligomerisation of propylene is carried out a8 follows. A reactor provided with stirring and cooling means is used 80 that the reaction mixture may be maintained at the required temperature and the pressure is such that the mixture is liquid, a pressure of 30 bars in the reactor is generally sufficient. In the reactor, the propylene is brought into contact with 0.04 to 0.08~ water and 0.5 to 0.8% anhydrous boron trifluoride. These proportions are expressed by weight in relation to that of propylene. The reaction temperature is generally one between 70 and 80 & and an average reaction time of half an hour is generally sufficient to accomplish the total conversion of the propylene.
10~ 08 The product of the reaction comprises gaseous pro-ducts, mainly boron trifluoride and propane being the chief impurity of the propylene used as raw material; these gaseous products are separated by employing the usual appropriate means that are well known to the technician.
After degassing, the oligomer contains boron and fluorine compounds derived from boron trifluoride which can be eliminated by washing the oligomer with an alkaline solution.
The oligomer is then fractionated by distilling, if necessary, to separate the fraction having the required flash point and viscosity and finally, the oligomer is hydrogenated.
We have found that oil produced has a smaller swelling effect on elastomers than do hydrogenated polypropylenes obtained by other processes.
Although the oil prepared by means of the present pro-cess, from propylene, isobutylene or n-butenes, are most useful as hydraulic ~luids and have a small swelling effect on most elastomers certain elastomers undergo slight shrink-age in contact with this oil. Generally isoparaffinic oil has a greater swelling power the higher its content of impur-ities of the cyclane type. We have surprisingly discovered that a purely isoparaffinic oil brings about an appreciable contraction of certain elastomers, in particular elastomers based on polyurethanes which may be detrimental to the tightness of the joints of hydraulic circuits and that this may be overcome by blending in certain polycyclane oils.
~hus the present invention m.~kes il: pl~S~:i l)lc l,o pl~
pare an oil for hydraulic fluids which has a predetermined swellin~ power, also provides the incorporation with the ~ -6-~5~08 oil produced by the process of the invention of a smallerproportion of a naphthenic oil may be adjusted to confer on the final oil the desired swelling power with the par-ticular elastomer with which it is to be used.
The naphthenic oil used in these blends is preferably a mineral or synthetic oil consisting essentially of satur-ated hydrocarbons whose molecule comprlses several condensed cycles. It is possible to use in the present process any -6a_ 1056~08 naphthenic oil provided th~t its flash point is sufficiently high ant that it is practically free from aromatic hydrocarbons. An oil containing a hi8h proportion of aromatic hydrocarbcns would affect the mechanical properties of the elastomers. The presence of isoparaffinic hydrocarbons in this oil does not entail any drawbacks. The viscosity of the naphthenic oil matters little, provided that the final oil in which It is incorporated, has th~ de8ired viscosity, we prefer to use a naphthenic oil whose viscosity i8 between 10 and 100 cSt at 37.8C.
It is possible to use a naphthenic oil derived from an appropriatc crude petroleum, by means of the usual operations of distilling and refining.
Nevertheless, it is very tifficult in practice to obtain from petroleum a naphthenic oil sufficiently free from aromatic hydrocarbons. ~or this rea80n, a synthetic oil i~ used for preference. We prefer to use a synthetic 4il cona~ n& of cyclanic hydrocarbons whose molecule contains at least three condensed cycles, each with 5 carbon atoms. This type of oil may conveniently be prepared from a fraction of steamcracking naphtha distilling between 80 and 175C. A fraction of naphtha of this kind contains hi8h proportions of cyclopentadiene, dicyclopentadiene and mono or dimethyl derivatives of these cyclodienes. The cyclodienes present in the naphtha may be condensed to polycyclopentadienes by for instance maintaining the naphtha at about 260 & , at a pressure of 12 to 15 bars, for 2 to 4 hours. The product of this reaction may then be hydrogenated after diluting it with an inert solvent to yield the na~hthenic oil. Hydrogenation is performed by any usual means 80 as to saturate the ethylene bond of the molecules of polycyclopentadienes, to form the corresponding polycyclane hytrocarbons. Tbe hydrogenated mixture is finally fractionated by distilling, 80 as to recover the solvent and separate a fraction having the desired flash-point and vigcosity.
The proportion of naphthenic hydrocarbons incorporated with the oil made according to the present invention of our invention may be varied to adjust very accurately the ~welling power of the final blend and as much as 20%
napthenic oil may be used. We have found that the oil manufactured according to the invention from propylene and contsining from 3 to 10%, or better still, from 5 to 8% of its weight of this type of naphthenic oil behaves absolutely satisfactorily in contact with the usual elastomers.
The polycyclane hydrocarbons may be incorporated with the final oil by simple mixing.
Alternatively the appropriate fraction of the oligomer obtained by our process may be mixed with the appropriate proportion of polycyclopentadienes, and hydrogenation the mixture.
The present invention also provide~ oil obtained by the processes described above. It al~o provides hydrocarbon-based hydraulic fluid containing a high proportion of such oils and such a hydraulic fluid consisting of a basic oil and appropriate additives.
The oil may contain other conventional additives such as viscosity index improvers, extreme-pressure additives, anti-wear additives and oxidation inhibitors.
The present invention i8 illustrated but in no way limited by reference to the following examples.
Exa ~
~ basic oil for hydraulic fluids having a viscosity between 16 and 18 cSt at 37.8C was prepared as follows:
Propylene was brought into contact with 0.05% by weight of water and 0~06%
by weight of anhydrous boron trifluoride in a stirred and cooled reactor at a pressure of 20 bars, and a temperature of 30C. The mixture was in the reactor for half an hour. On leaving the reactor, the mixture was expanded from 20 to 1 bar pressures which brought about the evaporation of propane and boron trifluoride, which were thus eliminated. The remain;ng liquid was washed with dilute soda soluti~n and an oli~o~er obtained h~vin~ the follo~in~ char~cteri~tic~:
Distillatio~ (according to the standArd ASTM D-86) Volume distilled (%) Temperature &
Initi~l point 276 30o Flnal point 361 Viscosity at 37.8C 15 cSt Mesn molecular mass 340 Bromine num~er 44 ThiR oligomer wss hytrogenatet on a catalyst based on nickel and cobalt, at 215 & under a hytrogen flow at a pressure of 18 bars ant a speed of 0.25 h 1.
A basic oil for hydraulic fluids was obtsinet by hydrogenation having the Pollowing characteristics:
Viscosity at 37.8 & 16.56 cSt Viscooity ~t 99& 3.20 c5t Viscosity intex 42 Plash point, open vessel (Cleveland) 144C
Density at 15 & 0.819 Freezing point -51C
Bromine number 0.4 Aro~etics content 0.3% by ~eight The yield of final product in relation to the weight of the propylene used exceedet 99%.
A basic oil for bydraulic fluids was prepared having a viscosity between 4 and 6 cSt at 37.8C.
The oligomerisAtion of the propylene was carried out a8 in ~xample 1, with the reactor temperature at 70 C and the yield of oligomer in relation to the _ g _ lOS6408 weight of the propylene used exceeded 99.5% and the characteristics of the oligome!r were:
Viscosity at 37.8C 5.5 cSt Flash point in open vessel (Cleveland) 95C
Mean molecular mass 265 This oligomer was fractionated by distilling so as to isolate the fraction having the desired viscosity and flash point. To do 80, three fractions were separated, a first fraction (7% by volume), mid fraction (79% by volume) and a residue (14%) by volume.
The intermediate fraction (79% by volume) had the required characteristics, viz:
Viscosity at 37.8C 4.8 cSt Plash point in open vessel (Cleveland) 110C
Mean molecular mass 260 Thi~ fraction was hydrogenated by operating as in example 1 except that the temperature was 180C.
The oil (A) was obtained with a yield of 79% by weight in relation to the weight of propylene used and had the following characteristics:
Viscosity at 37.8 & 4.9 cSt Viscosity at 99 C 1.5 cSt Density at 15 & 0.806 Freezing point - 60 C
Cleveland flash point 110C
Bromine number 0.2 Aromatic hydrocarbons 0.2% by weight Distillation (ASTM method D-86):
Volume distilled (%) Temperatures (C) Initial point 237 Final point 326 ~056408 By way of comparison an oil of the same type was prepared by means of a process similar to that of French patent 1357634 in which propylene was oligomerised lgo& in contact with phosphoric acid deposited on kiesel-guhr and the fraction distilling from 200 to 300 & was sepsratet. In this process the yield was 5~ by weight in relation to the weight of propylene used. By hydrogenating this fraction, an oil (B) was obtained which was distinguished from oil (A) by its content of cycloparaffins and its behaviour in relation to elastomers.
The composition of the two oils, determined by mass spectrometry, was as follows:
Oil A Oil B
I~opsraffins 99.7 88.1 Cycloparaffins 0.1 11.3 Aromatics 0.2 0.5 A sample of polyurethane rubber was immersed in each of these oils at 130 & , for 20 days. After this test, the volume of the sample immers2d in oil A had dropped by 6.9%, and that of the sample immersed in oil B had risen by 3.8%.
~xample 3 Two oils were prepared having determined swelling powers, by mixing a naphthenic oil (C) with the oil A defined in e~ample 2.
Oil C was prepared by heating 170 kg of a fraction of naphtha obtained by steam cracking and distilling from 80 to 175C which contained approximately 60%
dimers of cyclopentadiene and methyl-cyclopentadiene in an autoclave, for up to 260C and then held at that temperature for a further 2 hours. The contents of the autoclave are then reduced by distilling until obtaining 100 kg residue was a resinous, very dark brown substance, whose bromine number was 60. It was treated with 500 kg of a hydrocarbon solvent distilling at 150 to 180 & and the ~olution obtained hydrogenated on a basic nickel and tungsten catalyst, ut 240C
under 60 bars, until the bromine number of the product is zero. The product of hydrogenation was distilled to separate the solvent, 40 kg of an oil distilling from 280 to 380C (oil C) and 60 kg residue.
Oil C was practically colourless and had the following characteristics:
Density at 15 & 1.019 Refractive index 1.529 Viscosity at 37.8 & 80.5 cSt Viscosity at 99& 7.2 cSt Bromine number less than 1 ~lash point (Cleveland) 142C
Freezing point -12C
Two mixtures were then prepared, one with 93~ oil A and 7% oil C, the other with B6~ oil A and 14% oil C. These proportions being by Yolume.
A sample of polyurethane rubber was immersed in oil A and in each mixture at 130& for 20 days. The mechanical characteristics of the samples were ~easured before and after each very stringent test, and the Yariation of each characteri~tic was calculated in relative terms (% of initial value).
The following results were obtained:
93Z A 86% A
Oil tested Oil_A 7% C 14% C
Relative variation (%):
of the dule at 100% -.85 - 86 - 84 of the dule at 300% - 81 - 79 - 79 of the breaking loan - 85 - 85 - 83 of the Yolume - 6.90 + 0.5 ~ 2.2 ~ 0.$ ~ 2.7 ) 0.5
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for manufacturing selectively, with a high yield, a highly paraffinic basic oil having a flash-point above 100°C and a viscosity within the range from 2 to 30 Centistokes at 37.8°C comprising:
oligomerising an olefin selected from propylene, isobutylene, n-butenes and mixtures of these olefins, in the liquid phase, in the presence of a Friedel and Crafts catalyst, at a temperature between -10 and 80°C, separating the catalyst and the oligomer and hydrogenating the oligomer or a fraction thereof.
oligomerising an olefin selected from propylene, isobutylene, n-butenes and mixtures of these olefins, in the liquid phase, in the presence of a Friedel and Crafts catalyst, at a temperature between -10 and 80°C, separating the catalyst and the oligomer and hydrogenating the oligomer or a fraction thereof.
2. A process according to claim 1 in which the olefin is propylene and the catalyst comprises from 0.04 to 0.08% by weight of water, from 0.5% to 0.8% by weight of anhydrous boron trifluoride and the oligomerisation is carried out at a temperature in the range 20°C to 80°C.
3. A process according to claim 1 in which the hydrogenation is contin-ued until the bromine number is less than 1.
4. A process according to claim 1 in which hydrogenation is performed using a catalyst based on cobalt and nickel at a temperature from 180°C to 220°C at a pressure from 10 to 100 bars.
5. A paraffinic oil having a flash point above 100°C and a viscosity within the range from 2 to 30 Centistokes at 37.8 C.
6. A blend comprising 80% to 99% by weight of a paraffinic oil accord-ing to claim 5 and 20% to 1% by weight of a naphthenic oil substantially free from aromatic hydrocarbons and having a flash point greater than 100 C.
7. A blend according to claim 6 in which the naphthenic oil has a viscosity between 10 and 100 Centistokes at 37.8°C.
8. A blend according to claim 6 containing from 3 to 10% by weight of the naphthenic oil.
9. A blend according to claim 6 containing from 5 to 8% by weight of the naphthenic oil.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7424784A FR2278758A1 (en) | 1974-07-17 | 1974-07-17 | COMPOSITION OF HYDROCARBON OIL FOR HYDRAULIC FLUIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1056408A true CA1056408A (en) | 1979-06-12 |
Family
ID=9141370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,058A Expired CA1056408A (en) | 1974-07-17 | 1975-07-08 | Hydrogenated olefine oligomers |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS5140384A (en) |
| CA (1) | CA1056408A (en) |
| IT (1) | IT1040939B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294440B2 (en) | 2011-05-16 | 2019-05-21 | Shanghai Chemrun Co., Ltd. | Catalytic system for preparation of high branched alkane from olefins |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5524226Y2 (en) * | 1974-08-23 | 1980-06-10 | ||
| JPS6066781U (en) * | 1983-10-14 | 1985-05-11 | タキロン株式会社 | Drainage |
| US7425591B2 (en) | 2001-10-16 | 2008-09-16 | Exxonmobil Chemical Patents Inc | Elastomeric composition |
| WO2006073198A1 (en) * | 2005-01-07 | 2006-07-13 | Nippon Oil Corporation | Lubricant base oil, lubricant composition for internal combustion engine and lubricant composition for driving force transmitting device |
| JP5114006B2 (en) * | 2005-02-02 | 2013-01-09 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
| JP5087224B2 (en) * | 2005-02-10 | 2012-12-05 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for drive transmission device |
| US8105990B2 (en) | 2006-03-15 | 2012-01-31 | Nippon Oil Corporation | Lube base oil, lubricating oil composition for internal combustion engine, and lubricating oil composition for drive transmission device |
| JP4972353B2 (en) * | 2006-07-06 | 2012-07-11 | Ｊｘ日鉱日石エネルギー株式会社 | Hydraulic fluid composition |
| EP2428553B1 (en) | 2006-07-06 | 2013-05-22 | Nippon Oil Corporation | Lubricating oil composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE781637A (en) * | 1972-04-04 | 1972-07-31 | Labofina Sa | LUBRICATING COMPOSITIONS FOR ROTARY ENGINES. |
| BE781636A (en) * | 1972-04-04 | 1972-07-31 | Labofina Sa | LUBRICATING COMPOSITIONS FOR TWO STROKE ENGINES. |
-
1975
- 1975-07-08 CA CA231,058A patent/CA1056408A/en not_active Expired
- 1975-07-14 IT IT5051675A patent/IT1040939B/en active
- 1975-07-17 JP JP8779975A patent/JPS5140384A/en active Granted
-
1983
- 1983-01-07 JP JP101483A patent/JPS59161495A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294440B2 (en) | 2011-05-16 | 2019-05-21 | Shanghai Chemrun Co., Ltd. | Catalytic system for preparation of high branched alkane from olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1040939B (en) | 1979-12-20 |
| JPS6143400B2 (en) | 1986-09-27 |
| JPS59161495A (en) | 1984-09-12 |
| JPS5140384A (en) | 1976-04-05 |
| JPS6123237B2 (en) | 1986-06-04 |
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