DE2307470C3 - Process for the production of lubricating oils by the polymerization of α-olefins - Google Patents

Description

It is known that in the mineral lubricating oils to increase the viscosity index so-called viscosity index- » Improvers «can be used which are polymers with a very high molecular weight. she However, during the operation of the engines, the engines depolymerize and, therefore, the oils they contain degrade in terms of both viscosity and viscosity index.

This disadvantage was avoided by using synthetic lubricating oils, which themselves do the Have a characteristic of high viscosity index, which during use, even after long periods of operation, does not fall off. The manufacture of these synthetic oils was mainly done by Polymerization of «-olefins. Initially, both AlCb-type and cationic catalysts were used Catalysts of the type of 'alkyl peroxides, such as di-tert-butyl peroxide, are used.

In this way one obtained oils with relatively high viscosity indices, namely with viscosity indices of up to 125.

On the other hand, catalysts of a coordinative anionic type, namely of the Ziegler type, for example AIÄts and its derivatives, lubricants with viscosity indices above 130. However, these catalysts have the disadvantage

IO

wherein η is an integer not greater than 50 and R "is an alkyl or aryl or cycloalkyl radical, in the presence of an aromatic solvent, a halogenated hydrocarbon solvent, a saturated hydrocarbon solvent and / or cycloparaffin solvent Temperatures in the range from 0 to 200 ^° C. and subsequent catalytic hydrogenation of the product obtained, characterized in that the polymerization is carried out in an atmosphere of dry nitrogen and in the presence of a second cocatalyst which consists of an organometallic aluminum compound of the general formula

AIR-L ₅ CI ₁₁₅ , A1R ' ₂ C1 or AIR'C1 ₂ ,

wherein R 'is an alkyl group, the two cocatalysts being used in a ratio im Range of 60/40 to 90/10, a molar ratio the polyimine compound to the titanium tetrachloride in the range of 1.1 to 1.7 and that Mole ratio of the organometallic aluminum compound to the titanium tetrachloride at 1 holds.

To deliver lubricating oils that have a relatively low viscosity.

In order to overcome these disadvantages, suitable ones have been made Tricks used, such as that described in US-PS 31 13 167, according to which the lubricating oil in two stages is produced, A ratio of the catalyst components is used in the first stage, which enables the recovery of solid polymers, and in a second stage by changing the above-mentioned ratio, liquid polymers are obtained which dissolve the former, where in this way it is possible to obtain oils with the desired viscosity. It can be seen that it is it is a complicated way of working.

Another disadvantage of the catalysts mentioned, which should not be neglected, is that for the Polymerization required time ranging from 8 to 20 hours and predominantly from 16 to 23 hours located.

From DT-OS 20 64 206 it is known to prepare lubricating oils by polymerizing -olefins in the presence of Manufacture of titanium tetrachloride and polyimides. However, this method has the disadvantage that in Must work in the presence of hydrogen.

It has now been found that these synthetic oils with a high viscosity index and a usable Viscosity can be produced without the use of hydrogen, eliminating the risk is that monomers are hydrogenated and can no longer be polymerized further.

The invention therefore relates to a process for the production of lubricating oils by polymerizing pure or mixed «olefins with 9 or 10 carbon atoms, using a catalyst system, the titanium tetrachloride and, as cocatalyst, a polyimine compound of the general formula

40 Al —N ^:

MR"

wherein η is an integer not greater than 50 and R "is an alkyl or aryl or cycloalkyl radical, in the presence of an aromatic solvent, a halogenated hydrocarbon solvent, a saturated hydrocarbon solvent and / or cycloparaffin solvent Temperatures in the range from 0 to 200 ^° C. and subsequent catalytic hydrogenation of the product obtained, which is characterized in that the polymerization is carried out in an atmosphere of dry nitrogen and in the presence of a second cocatalyst which consists of an organometallic aluminum compound of the general formula

u, AIR ' ₂ C1 or AlR'Clj,

wherein R 'is an alkyl group, where the the two cocatalysts used in a ratio in the range from 60/40 to 90/10, a molar ratio of Polyimine compound to the titanium tetrachloride in the range of 1.1 to 1.7 and the molar ratio of the organometallic aluminum compound to the titanium tetrachloride at 1.

The above -olefins with 9 or 10 carbon atoms are, for example, normal - - olefins or

national mixtures of α-olefins, which come from the racking of waxes.
In the above polyimine compound, η is preferably an integer between 4 and 25. This cocatalyst is the same as that used, for example, in the method of DT-OS 20 64 206. The molar ratio of the polyimine compound to the second cocatalyst in the catalyst system used according to the invention, as mentioned above, is in the range from 60/40 to 90/10, depending on the range and the purity of the -olefins in the feed. 80/20. An unrated ratio of the polyimine compound to that

The following α-olefin compositions can according to of the present invention can be used as feed:

_{A) Dece} n- (1)

Linear «olefin content
Specific weight at 2O ⁰ C
Refractive index η
Bromine number g / 100 g

r) Mixture of commercially available C ₉ -Cio «oletins from wax cracking

_ _{0 /}

AV ₂₂ '«7 *

■ »

si £ rss. Α ^ & ΛΑϊ s

irtrS up to 3OcSt and also above at 98.9 ° C to the refractive index π

keep molecular weight

^ The polymerization reaction is preferably un-20 bromine number, g / 100 g

5SS ££ 3SS sa

32

AS

ten times the volume of the olefins fed in

is up to the inventor

example 1

after using pure individual 40 freed Coat for

'"S.TS.wich.sverh.l.nisOldin / Ob.rg.ngsm«, »,,» =, -

Purity of the fed "-
The reaction time can be up to 5 hours. When using the inventive catalyst

In the end, the catalyst was deactivated by adding _iso "" alcohol and then the 'soP ^ro pyMk: ono _{and then} with it

washed with _{neutralization.}

2 & £ 5

the same enmo _m manen KaJaJr »tor η

Maintained lr atmosphere of dry nitrogen

Table I.

Characteristics

method

Specific weight at 20 ⁰ C

Refractive index, ηί °

Kinematic viscosity at 98.9 ° C (210 ⁰ F) cSt

Kinematic viscosity at 37.8 ° C (100 ⁰ F) cSt

Viscosity index

Pour point, ⁰ C

Ramsbottom coking residue, wt%

Neutralization number, mg KOH / g

Iodine number g / 100 g

Molecular weight

It should be noted that the unreacted monomer is practically not hydrogenated and so on can be polymerized.

The 400 ⁰ C + oil was then hydrogenated to complete saturation of the olefinic double bonds.

The hydrogenation was carried out in an autoclave

Table II

ASTM D 1481
ASTM D 1747
ASTM D 445
ASTM D 445
ASTM D 2270
ASTM D 97
ASTM D 524
ASTM D 974
IP 48
Vapor pressure osmometer

400 ⁰ C + oil

0.8337

1.4678

19.14

121.7

140 / A-I88 / B

<-50

0.03

<0.04

40

650

Use of a catalyst based on Pd on aluminum oxide carried out under the following conditions: temperature 220 ^° C., hydrogen pressure 80 kg / cm ² , time 5 hours. The characteristics of the hydrogenated oil are listed in Table 11.

Characteristics

method

400 ⁰ C + hydrogenated oil

specific weight

Refractive index, n'S

Kinematic viscosity at 98.9 ° C (210 ° F) cSt

Kinematic viscosity at 37.8 ° C (100 ° F) cSt

Viscosity index

Pour point, ° C

Ramsbottom coking residue, wt%

Neutralization number mg KOH / g

Iodine number, g / 100g

Molecular weight

Example 2

^{350 cm 3} (259 g) of 97% decene (1), 6.80 cm ^{3 of} a 2nd reactor, equipped with a stirrer, were poured into a dried, vented and flushed 1–1 reactor, equipped with a stirrer, in the following order , 23 nv solution of TiCU, 5.40 cm ^{3 of} a 0.84 m solution of AIÄti, sCli, s and 11.65 cm ^{3 of} a 1 m solution of poly (N-isopropyliminoalane).

The weight ratio of olefins / TiCU was 90. The reduction of TiCU occurred to 70% due to the

Table 111

ASTM D 1481 0.8323 ASTM D 1747 1.4664 ASTM D 445 19.94 ASTM D 445 130.0 ASTM D 2270 139 / A-186 / B ASTM D 97 <-50 ASTM D 524 0.03 ASTM D 974 <0.04 I. P. 48 0.3 Vapor pressure osmometer 670

Polyiminoalane (with a molar ratio of Al / Ti = 1.1) and 30% due to the ÄtAI-sesquichlo-

rids (with an Al / Ti ratio = 1.0). Subsequently

Was stirred at a temperature of 25 ° C. for 5 hours.
After treating the polymerization product, such as

in Example 1, 53 g of dimer and 169 g of des were obtained 400 ° C + oil. The conversion was 85.7% by weight and

the yield of oil 65.2% by weight.

The characteristics of the 400 ° C + oil are in the

Table IH given.

Characteristics

method

400 ° C + oil

Specific weight at 2O ⁰ C.

Refractive Index ^{, Tt 7} S.

Kinematic viscosity at 98.9 ° C (210 ⁰ F) cSt

Kinematic viscosity at 37.8 ° C (100 ⁰ F) cSt

Viscosity index

Pour point, ° C

ASTM D. 1481 0.8301 ASTM D. 1747 1.4667 ASTM D. 445 10.81 ASTM D. 445 62.05 ASTM D. 2270 144 / A-178 / B ASTM D. 97 <-50

The above results show that by changing the Al / Ti ratio with respect to Alan from 1.3 (Example 1) to 1.0 lower viscosity oils will echo.

Example 3 _{() <} .

350 cm ¹ (259 g) of 97% decene (1), 6.80 cm ^{3 of} a 2, 23 m solution of TiCU, 5.40 cm ^{3 of} a 0.84 m solution of AlAt 1.5CI 1.5 and 15.90 cm ^{3 of} a 1.0 m solution of poly (N-isopropyliminoalane) were introduced.

The weight ratio olefins / TiCU was 90. The reduction of the TiCU took place to 70% due to the Polyiminoalane (with a molar ratio Al / Ti = 1.5) and 30% due to the Al-ethyl-sesquichloride (with a molar ratio Al / Ti = 1.0).

It was 5 hours at a temperature of 25 "C

touched.

After treating the polyetherization product as in Example 1 obtained 50 g of dimcres and 173 g of des

400 ⁰ C + oil. The conversion was 86.1 wt ¹ '/' and the yield of oil, 66.8 wt .-%.

The characteristics of the 400 C + oil obtained are given in Table IV.

Table IV
Characteristics

Specific weight at 2O ⁰ C

Refractive index, n'S _noaor mn ° n rSt

Kinematic Viscosity at 98.9 ° C 210 F cS Kinematic Viscosity at 37.8 ° C (100 F) cSt Viscosity Index
Pour point, ⁰ C

ASTM D 1481
ASTM D 1747
ASTM D 445
ASTM D 445
ASTM D 2270
ASTM D 97

0.8345
1.4680
32.5
209.4

138 / a-220 / B

-50

These results show that by changing d « molar ratio Al / T, with respect to the A a of 1.3 (example 1) to 1.5 oils with a higher viscosity can be obtained.

Examples 4 and 5

The procedure was as in Example 1, except that the polymerisation temperature was changed. In a dried, vented and purged 1-th reactor, which was flushed with dry nitrogen, 350 cm '(259 g) 97 / o total decene (l ), 6.80 cm 'of a 2.23 m solution in front of T.CU. 540 cm * of a 0.84 m solution of AlAt ,, ₅ Cl, .5 and 13.80 cm of a 1.0 m solution of poly (N-isoprolyp.m.noalan)

brought in.

As in Example 1, the olefins / TiCU weight ratio was 90 and the TiCU was reduced to 70% through the polyiminoalane (with a molar ratio Al / Ti = 1.3) and 30% through the Al-ethyl-sesquichloride (with a molar ratio

2s nis = 1.0).

The polymerization temperature was 4 5O ⁰ C in Example 80 and in Example 5 ⁰ C. The time in both cases was 5 hours.

The polymerization products were treated as in Example 1. In Example 4, a 58% strength was obtained Conversion and an oil yield of 45%.

In Example 5, the conversion was 55% and the yield of oil was 39%.

The characteristics of the two 400 ⁰ C + oils are listed in Table V.

Table V

Characteristics

Specific weight at 2O ⁰ C
Refractive index, η · ;: η in "η

Kinematic viscosity at 98.9 ° C 2101 I) Kinematic viscosity at 37.8 "C (100 I) viscosity indcx
Sioekpunkt, "C

Method ASTM D 1481
ASTM D 1747
ASTM D 445
ASTM D 445
ASTM D 2270
ASTM D 97

400 "C + oil 400-C + oil Example 4 Example 5 0.8352 0.8368 1.4682 1.4688 76.1 159 516 1130 Ι31 / Λ-238 / Β 127 / A-267 / U -45 -43

The above results / intrinsically that a temperature control xu oils with lower yield _5, and higher viscosity.

Example 6

B. The procedure was analogous to that in Example I, where «α only a solvent connected wai. .

Into a dried, nitrogen-purged vented to wjkejcm with 1 reactor, "ujgerubte" em stirrer, would in the following Reihcnfolgo 350 cm (259 g) of 97% IGCS Deoen- (l) and 330 cm Be ^"ol -.!. J · ⁸ «^. " ^{5 of} a 2.23 mL solution of TICU, 5.40 cm of a 0-4 m solution of AlEt ,, Cl ,,, and 13.80 cm of a 1.0 m solution of l" oly. ( N. | s (»piOpyllnilnmilan) elniiebi mni.

As in Example 1, the olefins / TiCU weight ratio was 90, and the reduction of the TiCl _{4 was} carried out 70% by the polyiminoilane (with an Al / Ti molar ratio of 1.3) and 30% by the Al-methylsesquiechloride (with a molar ratio

Al / Ti - 1.0).
lis was 5 hours at a temperature of 25 "C

touched,

After treatment of the polymer product as in Example I received just 47 grams of Dimcrcs and Ifob grams of oil.

The total winding, related to the fed-in Olefins was 82.2% and the yield was un oil

b4.1% by weight.
The chitrite crystals of the 400 "Ch-OIs obtained are

listed in Table VI.

/ ÜU 630/234

10

Table VI

Characteristics 20 " ¹ C C (210 ° F) cSt method 1481 400 ° C + oil Specific weight at C (100 ° F) cSt ASTM D 1747 0.8318 Refractive index, /? ί! ' at 98.9 ° ASTM D 445 1.4674 Kinematic viscosity at 37.8 ° ASTM D 445 12.34 Kinematic viscosity ASTM D 2270 71.40 Viscosity index ASTM D 97 144 / A-184 / B Pour point, ⁰ C ASTM D <-50

By comparing these results with those of Example 1, it can be seen that the addition of Solvent to the fed olefin reduced the viscosity of the oil, the yield being almost remains unchanged.

Example 7

In this example, as in the following examples, the feed was a mixture of alpha olefins C9-C10 used by wax cracking.

350 cm ³ (260 g) of a mixture of commercially available olefins C9-C10 from "wax cracking" with a content of on

Table VIl

«-Olefins of 87%, 6.80 cm ^{J of} a 2.23 m solution of TiCl ₄ , 5.40 cm ^{3 of} a 0.84 m solution of AlÄti.sCli.s and 13.80 cm ^{3 of} a 1, 0 m solution of poly (N-isopropyliminoalane) introduced.

As in Example 1, the weight ratio was

Olefine / TiCU 90, and the reduction of TiCl _{4 was} carried out to 70% by polyiminoalane (with a molar

Ratio Al / Ti = 1.3) and to 30% by Al-ethylses-

quichloride (with a molar ratio Al / Ti = 1.0).

The mixture was stirred at a temperature of 25 ° C. for 5 hours.

After treating the polymerization product as in Example 1, 1.27 g of dimer and 100 g were obtained 400 ° C + oil obtained. The conversion was 48.8% by weight and the yield of oil was 38.4% by weight.

The characteristics of the 400 ° C + oil thus obtained are shown in Table VII.

Characteristics 20th ° C C. (210 ° F) cSt method D. 1481 400 ° C + oil Specific weight at C. (100 ° F) cSt ASTM D. 1747 0.8422 Refractive index, n'f at 98.9 ° ASTM D. 445 1.4705 Kinematic viscosity at 37.8 ° ASTM D. 445 25.31 Kinematic viscosity ASTM D. 2270 180.9 Viscosity index ASTM D. 97 I36 / A-183 / B Pour point, ° C ASTM <-50

The above results show that even when working with the mixture of commercially available «-Olefins C9-C10 from» wax cracking «die obtained oils have good properties.

The yields are lower than those in Example I, where decene (I) was assumed, due to the in the impurities mentioned.

Example 8

This example corresponds to Example 7, but with the weight ratio olefins / TiCU from 90 to 60 was decreased.

In a dried, vented and flushed with dry nitrogen 1-1 reactor equipped with a stirrer, 350 cm ¹ (260 g) of a mixture of commercial olefins C1-C10 were obtained in the following order by "growth crunching" with a content of 87% olefins, 10.2OcIH ^{1 of} a 2.23 m solution of TiCl ₄ , 8.10 cm ^{3 of} a 0.84 m solution of AIATi. ₅ Cli, j and 20.70 cm ^{3 of} a 1 M solution of poly (N-isopropyliminoalane) introduced. The Gc-

The weight ratio of olefins / TiCU was 60. The reduction of TiCl _{4 was} carried out to 70% by the polyiminoalane (with a molar ratio of Al / Ti - 1.3) and to 30% by aluminum ethyl sesquichloride (with a molar ratio of Al / Ti - LO).

The mixture was stirred at a temperature of 25 ^{° C. for 5 hours.} Nuch treatment of the polymerization product as in Example I there was obtained 39 g dimer and 135 g of 400 ⁰ C + oil.
The conversion was 67% by weight, and the

5S yield of oil 52% by weight.

The characteristics of the oil obtained are shown in Table VIII.

Table VIII 20 ' ¹ C C (210 ° F) cSt method 1481 400 ° C + oil Characteristics C (100 ° F) cSt ASTM D 1747 0.8420 Specific weight at at 98.9 ° ASTM D 445 1.4704 Refractive index, ntf at 37.8 ° ASTM D 445 23.59 Kinematic viscosity ASTM D 2270 169.0 Kinemute viscosity ASTM D 97 I36 / A-179 / B Viscosity inclex ASTM D <-50 Pour point, ⁰ C

By comparing the results with those of Example 7, it can be seen that when working with CrCio-olefins from "wax cracking" the effect of the impurities in the yield can be limited by increasing the amount of the catalyst. The characteristics of the oil remain satisfactory. It should be noted that the monomer involved in the Reaction does not take part, is practically not hydrogenated.

Table IX

The 400 ° C + oil was completely saturated hydrogenated the olefinic double bonds.

The hydrogenation was carried out in an autoclave using a catalyst based on Pd on alumina under the following conditions: temperature 220 ^° C., hydrogen pressure 80 kg / cm ² , time 5 hours. The characteristics of the hydrogenated oil are listed in Table IX.

Characteristics ⁰ C C. (210 ° F) cSt method D. 1481 400 ° C + hydrogen
tes oil Specific gravity at 20 C. (100 ° F) cSt ASTM D. 1747 0.8404 Refractive index, n'S 98.9 ° ASTM D. 445 1.4690 Kinematic viscosity at 37.8 ° ASTM D. 445 24.42 Kinematic viscosity at ASTM D. 2270 176.5 Viscosity index ASTM D. 97 135 / A-179 / B Pour point, ⁰ C ASTM -48

The hydrogenated 400 ° C + oil listed in Table IX was subjected to a shear stability test with a Raytheon sonic oscillator (ASTM D 2603-671) for 15 minutes, whereupon the change in viscosity that occurred at a temperature of 98.9 ° C (210 ⁰ F) measured was calculated. The results are shown in Table X.

Table X

Kinematic viscosity cSt at 98.9 ⁰ C (210 ⁰ F)

at the beginning after the test

Change in

kinematic

viscosity

Hydrogenated synthetic oil 24.42

23.68

-0.74 cSt

From the above data it can be seen that the hydrogenated synthetic oil of Example 8 is good Has resistance to depolymerization.

Examples 9-10

These examples were carried out as in Example 8, the weight ratio of olefins / TiCU being 60, but the ratio of the two cocatalysts for reducing the TiCl ₄ being varied from 70/30 to 80/20.

Under these conditions, the educational concept of the PIA-TiCU complex from 1.3 to 1.2 because otherwise you would get an oil with a fairly high viscosity.

In the usual dried, vented and flushed with dry nitrogen II reactor were in the following order 350 cm ³ (260 g) of the mixture of "wax cracking" coming C "-Cio-olefins with a content of ot-olefins of 87%, 10.2 cm ^{J of} a 2.3 M solution of TiCU, 5.4 cm ^{J of} a 0.84 M solution of AIÄtuClu and 21.8 cm ^{3 of} a 1.0 M solution of Poly- (N -isopropyliminoalane) introduced.
The weight ratio olefins / TiCU was 60.
The reduction of the TiCU takes place to 80% by the Polyiminoulan (with a molar ratio Al / Ti> 1.2) and to 20% by the Al-ethylsesquichlorid (with a molar ratio Al / Ti -> 1.0.

The polymerization temperature was 25 ° C 9 in Example and Example 10 5O ⁰ C. In both Filllcn time was 5 hours ..

The polymerization products were treated as in Example 1. In Example 9 the conversion was 83%

with a yield of 63.5% at 400 ⁰ C + 01. In Example 10, the conversion was 79% with a

Yield of 60% at 400 ° C + oil.

The characteristics of the two 400 ° C + oils obtained are listed in Tubelle XI.

Table Xl

Characteristic !! C (210 "F) cSt method 400 ° C + oil de » 400 "C + oil dos C (IOO ⁰ F) CSt Example 9 Example 10 Specific weight at 20 ° C ASTM D 1481 0.8428 0.8432 Refractive index, «5," ASTM D 1747 1.4708 1.4711 Kinematic viscosity at 98.9 ° ASTM D 445 29.11 36.3 Kinematic viscosity at 37.8 ° ASTM D 445 206.5 255.2 Viscosity Usinclcx ASTM D 2270 136 / A-191 / B 135 / A-202 / B Pour point, "C ASTM D 97 -50 <-50

The results of Example 9, in comparison with those of Example 8, show that it is possible to use the Oil yields obtained from commercial olefins becomes, without a significant change in the characteristics by appropriate variation of both the ratio the cocatalyst and the PIA / TiCU ratio to increase further.

From Example 10 it can be seen that when commercial olefins are used, the increase the temperature has no noticeable influence on the yield and viscosity of the oil produced.

Example 11

This example is similar to example 9. except that the polymerization of the Cg-Cio-olefins was carried out using the cocatalyst AlAt ₂ Cl instead of AlÄii. ', Cli, 5.

In a dried, vented and flushed with dry nitrogen, equipped with a stirrer

Table XIl

1-1 reactor were in the following order 35OCm ³ (260 g) of a mixture of commercially available Gj-Cio-olefins obtained by "wax cracking" containing 87% "olefins, 10.2 cm ^{J of} a 2.23 M solution of TiCl ₄ , 4.25 cm ^{J of} a 1.07 M solution of AlAt ₂ Cl and 21.8 cm 'of a!, Om solution of poly (N-isopropyliminoalane).
The olefins / TiCU weight ratio was 60.
_{80% of the TiCl 4} was reduced by ίο polyiminoalane (with a molar ratio of Al / Ti = 1.2) and to 20% by Al diethyl monochloride (with a molar ratio of Al / Ti = 1.0).

The polymerization temperature was 25 ° C, the time 5 hours. After treatment of the polymerization product as in Example 1, 47 g of dimer and 153 g were obtained 400 ° C + oil.

The conversion was 77% by weight and the yield of oil was 59%.

The characteristics of the oil produced are listed in Table XII.

Characteristics

method

400 ⁰ C + oil

Specific weight at 20 ⁰ C

Refractive index, η ™

Kinematic viscosity at 98.9 ° C (210 "F) cSt

Kinematic viscosity at 37.8 ⁰ C (100 ⁰ F) cSt

Viscosity index

Pour point, ° C

ASTM D. 1481 0.8410 ASTM D. 1747 1.4698 ASTM D. 445 19.49 ASTM D. 445 135.1 ASTM D. 2270 136 / A-175 / B ASTM D. 97 <-50

The results of the above example show that it is possible to convert AlÄti.di.s by AIÄtjCI / u substitute.

Claims (1)

Claim: Process for the production of lubricating oils by the polymerization of pure or mixed olefins with 9 or 10 carbon atoms, using a catalyst system, the titanium tetrachloride and a polyimine compound of the general formula as cocatalyst 1 -N