DE1282826B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

ClOm

German class: 23 c -1/01

Number: 1282 826

File number: P 12 82 826.1-43 (P 34331)

Filing date: May 26, 1964

Opening day: November 14, 1968

The most commonly used viscosity index improvers at present for lubricating oils are the methacrylic acid polymers, e.g. B. Polymethacrylates. aside from that polyisobutylene and polyfumarates are used. These viscosity index improvers improve effective the viscosity index of the lubricating oil and enable the production of a multigrade oil, which is suitable for use in all seasons and a sufficiently low initial viscosity to start in cold weather and still have enough viscosity at higher temperatures these oils have a number of disadvantages, e.g. B. the high manufacturing costs and the tendency to thermal Depolymerization and the limited service life associated with it.

It has now been found that lubricating oils do not have these disadvantages, but rather a high level of effectiveness, excellent compatibility with the oil and its additives and high thermal stability effect and can be manufactured at a relatively lower cost if you use them as viscosity index improvers a block copolymer of oil-soluble hydrocarbon polymer chains, the one Contain number of alternating amorphous and sterically regular segments, with the amorphous and the sterically regular blocks each have a molecular weight of 50,000 to 1,000,000, clogs.

The sterically regular polymer blocks are composed of linear polymer chains, which are essentially composed exclusively of methylene units and branched chains of methylene units or hydrocarbon rings exist, which are arranged in a spatially regular distribution and so give the polymer its stereospecific properties to lend. These sterically regular hydrocarbon polymers are, of course, as are the polymerization processes known for their production.

The sterically regular polymer blocks must have a total molecular weight of between 1,000 and 1,000,000, preferably between about 50,000 and 1,000,000, measured on the basis of the intrinsic viscosity. They must also have certain oil-solubility properties, ie if they were present as a polymer separately from the copolymer, this polymer would have to be insoluble in the oil at a temperature below 0 ° C, preferably below 20 ° C; however, after installation in the block copolymers, it must be increasingly solvatable with increasing temperature, with complete solvation at a Tempe Artur below 150 ° C, preferably below 110 ⁰ C, must occur.

Lubricating oil

Applicant:

Princeton Chemical Research Inc.,

Princeton, N.J. (V. St. A.)

Representative:

Dr.-Ing. A. v. Kreisler, Dr. K. Schönwald,

Dr. Th. Meyer and Dr. J. F. Fues, patent attorneys, 5000 Cologne 1, Deichmannhaus

Named as inventor:

Thomas H. Shepherd, Hopewell, N. J. (V. St. A.)

Claimed priority:

V. St. v. America of May 28, 1963 (283 672),
dated April 3, 1964 (357 294)

In the context of the invention, the term "oil insolubility" denotes a solubility of less than 0.1 weight percent in a paraffinic oil of SAE viscosity number 5w, while full Oil solubility means a solubility of at least 10 percent by weight in a paraffinic oil an SAE viscosity number of 5w. The sterically regular polymer blocks exist

preferably made of isotactic polypropylene and / or polybutene-1 blocks. In addition, you can also other sterically regular polymer blocks that have the properties described above, be used. Examples of such sterically regular polymer blocks are stereospecific polymerized polymers of 4-methylpentene-1, 3-methylbutene-1 and styrene, copolymers of propylene and butene-1, for example 5 to 30 mole percent butene-1, preferably 5 to 20 mole percent Butene-1 contain, stereospecifically polymerized copolymers of propylene and styrene, for example Containing 10 to 40 mol percent, preferably 15 to 30 mol percent styrene, stereospecifically polymerized Copolymers of propylene and ethylene containing 5 to 25 percent ethylene, preferably 10 to 20 mole percent Containing ethylene, stereospecifically polymerized copolymers of ethylene and butene-1, for example 5 to 30 mol percent, preferably 15 to 25 mol percent of butene-1, and isotactic polypentene-1.

809 637/880

The amorphous blocks are amorphous hydrocarbons, but formed from monomer mixtures that the fabric chains that have a total molecular weight of sterically regular and amorphous blocks 1000 to 1000,000, preferably from 50,000 to form.

1 000 000 have and, if they are in the form of a poly- The block used according to the invention

mers exist on their own, at temperatures of 5 copolymers can be obtained directly from mono -— 20 ° C and above, preferably from -30 ° C and mixed mixtures by taking advantage of the difference, would be soluble in oil. The designation of the formed in their respective responsiveness of the amorphous blocks as oil-soluble means a solubility. For example, it is possible with an opportunity of at least 10 weight percent in a mixture of propylene and butene-1. To paraffin-base Isotactic polypropylene is formed as a result of the oil closest to an SAE viscosity number mer5w. the higher reactivity of propylene. There-

As examples of amorphous hydrocarbons, polymerisation of amorphous blocks takes place polymer blocks may be mentioned: copolymers of propene, the amounts of amorphous material being allpylene and butene-1, which gradually combine 30 to 70 mole percent of butene-1 without containing any temperature range, Atactic polybutene-1, copolymers of 15 rectification is required.

Ethylene and butene-1 with 40 to 70 mol percent In general, the polymerization takes place at the beginning

Butene-1, copolymers of propylene and C ₅ -C ₂₀ -tion to form the sterically regular block olefins which contain 30 to 90 mol percent of the higher olefins using finely dispersed stereospecific olefins, copolymers of propylene with shear catalysts, e.g. B. the well-known Ziegler ethylene, which contain 25 to 70 mol percent, preferably 30 ao catalysts, for example from organometallic up to 60 mol percent ethylene, interpolymers see compounds such. B. aluminum trialkyls or of C ₅ -C ₂₀ α-olefins, terpolymers of C ₂ -C ₂₀ -Ct alkylaluminum halides and transition metal olefins, copolymers of ethylene and C ₅ -C ₂₀ -Ct salts, e.g. B. halides or alcoholates, manufactured olefins, which are 30 to 90 mol percent higher olefins. Examples of such catalyst systems include, and Cg-C ^ -ct olefin homopolymers. 25 are aluminum triethyl with titanium or vanadium

The amorphous hydrocarbon tetra- or trichloride, diethylaluminum chloride with material polymer blocks by mixed or interpolymer, titanium or vanadium tetra- or trichloride, lithium ion of the monomers or the monoaluminum tetraethyl used with titanium or vanadium tetramers are best obtained with formation of the steric regular or trichloride, butyl lithium with titanium or Vana-block with one or more different 30 dintetra- or trichloride od. the like. The polymerization "olefins, for example, a molecular weight is in an inert hydrocarbon solution between C ₂ and C ₂₀ manufactured. It is also possible to use medium, ζ. B. n-heptane or n-pentane, under inert gas, the amorphous hydrocarbon polymer blocks of z. B. under nitrogen, at moderate temperatures, the same monomer that is used to form the ste- z. B. between about 30 and 150 ° C, preferably 80 risch regular blocks is used to form below 35 to 120 ° C, at normal pressure or slightly elevated polymerization conditions, with no pressure carried out. The sterically regular polymer used at the beginning, but the required monomers, ζ. B. the butene-1 alone or in a mixture of such amorphous oil-soluble block is formed. with ethylene or propylene, with propylene

With the molecular weights given here and styrene or propylene or ethylene, the oil solubility properties of the sterically regular reactor, for example an autoclave, which contains the above and the amorphous block is the catalyst system described above, ge values that give the blocks as such as independent, whereupon the polymerization would have, for example, polymers that are not bonded to one another. V2 is carried out for up to 1 hour and then continued under the block non-stereospecific conditions used according to the invention. If the work is carried out in two stages, a sation process can be established. This can be done, for example, in the second stage by adding one or more as follows: The sterically regular block of further α-olefins and by increasing the temperature can first be formed by adding the monomer, temperature, e.g. B. to 60 to 130 ° C, triggered. In z. B. butene-1, under the known conditions, in the second stage the temperature in the autodene can be a sterically regular polymer formed 50 klav to a value between about 105 and 115 ° C is polymerized. After the sterically regular increase and the addition of butene-1 in a mixture with moderate polymer blocks of the desired molecule- another olefin, e.g. B. ethylene, propylene, have formed a size, the polymerization is continued under C ₅ -C ₂₀ -a-olefin or mixtures thereof, continued such conditions in which more are continued. After the polymerization reaction is possible with growth of the polymer chain by polymerization 55 formation of the amorphous block of the desired mole with the formation of a structure which is not finished in full size, the reaction becomes regular by Kühsterisch but is amorphous, e.g. B. canceled by len and relaxing the autoclave. Addition of further monomer components under B. is formed by washing with ethyl regular chain. The initial 60 lenglycol and water to remove the remaining stereospecific polymerization and its continuation - catalyst and precipitation of the polymer with formation of the amorphous block can be carried out in the methanol or distilling off the solvent, same reaction zone batchwise or continuously, whereby the polymer remains as residue, The prepared in the manner described can be carried out in two reaction zones

the, where the sterically regular chain continues as a viscosity index the polymerization with the formation of the amor improver with the usual lubricating oils in the usual way phen blocks led into the second reaction zone mixed way. For example, the block will. Preferably, the block copolymers are copolymers of the lubricating oils in amounts of

5 6

0.1 to 30, preferably from 0.3 to 10, in particular table polypenten-1. The last one dissolves in the oil

from 0.5 to 5 percent by weight can be added. about 20 ° C and is completely soluble at 30 ° C, so

All known or customary oils come as oils that are not so desirable for normal lubricating oil

mineral or synthetic lubricating oils, like isotactic polybutene-1, but a very

Question. 5 is a partial component of a block copolymer,

Viscosity index improvers are often used as condensation as viscosity index improvers for use with centered solutions in a base oil, for example low temperatures,
in concentrations between 10 and 70, preferably in order to achieve the highest effectiveness in relation to between 20 and 30 percent by weight, in the viscosity index improvement the oil-soluble trade must be brought, and these solutions will have the minimum length required with io block, the lubricating oil mixed. The base oil of the concentrate around the polymer at a lower temperature, e.g. B. trats can be, for example, a paraffinic oil at -40 ° C to keep in solution. This depends in some cases. be. In connection with, according to the invention, the degree depends on the type of base oil in which the block copolymers used in the manure are used. In general, amorphous hydrocarbon polymer blocks of low-15 should be the molecular weight of the amorphous carbon "olefin, e.g. If, for example, those with up to 4 hydrocarbon polymer blocks contain at least 50% of the molar atoms, the bulking of the base oil can become too high, so that the base oil can be carried by hand, with sterically regular and amorphous segregation of the concentrate being difficult is. ments of about the same length for most

According to a preferred embodiment of the objectives are satisfactory,
Finding it was found that this tendency to

excessive thickening of the base oil of the concentrate example 1
Trats can be avoided if the block copolymer is formed as a terpolymer, which contains additional components in a 1-liter autoclave under dry conditions, which from 0.5 to 25 molar nitrogen form a solution of 1.9 cm ³ ( 15 mmol) dip percent, preferably 1 to 20 mol percent (based on ethylaluminum chloride added in 350 cm ^{3 of} n-heptane, based on the total monomer used) of a higher then 1.5 g of a titanium trichloride catalyst, ren "olefin with 5 to 25, preferably 7 to 15 of the V ₃ moles of aluminum trichloride per mole of titanium tri-carbon atoms is formed. The higher oil chloride contained in the autoclave. The temperature in the polymerization mixture should be set to 50 ° C. before the full temperature. After the formation of the block copolymer and before 50 g of 1-butene had been added to the autoclave, the poly was preferably present for 45 minutes during the formation of the isotactic merization at this temperature. Appropriate higher olefins performed. Then 100 g of a mixture of, for example, n-pentene-1, n-hexene-1, n-heptene-1, 53 mole percent propylene and 47 mole percent butene-1, n-octene-1, n-nonene-1, n-decene -1, n-dodecene-1,35 introduced. The reactor was opened within 30 minutes-1-octadecene and mixtures of -olefins, which are heated to 110 ° C. as a groove and fractions are available for a further 30 minutes, for example C ₅ -C ₇ -, C ₇ -C ₉ - kept this temperature. It then became C ₉ -C _n and C ₁₁ -C ₁₆ olefin fractions. Branched cools and relaxes. The viscous solution in the car olefins, e.g. B. 3-methylbutene-l, 4-methylpentene-l, klav was taken to remove kata-isobutylethylene, neopentylethylene and isoamyl- 40 lysers with ethylene glycol and water can also be used. wash, whereupon the polymer by precipitation with

It is believed that the -olefin was isolated from methanol. After drying in the formation of the terpolymer randomly in or next to a heating cabinet under reduced pressure the isotactic polymer block or in or next to 98 g of polymer. The polymer was in production isotactic and the amorphous polymer blocks 45 men heptane completely soluble and had a distributed. The terpolymer, which as a component has a melt index of 4.0 (190 ° C, load 2160 g). The specific viscosity of a 0.5% solution of the Positioning of pourable concentrated oil solutions of polymers in a mid-continent oil of an SAE-des Polymers without the effectiveness of the polymer viscosity number of 20 was 1.4 at 37.8 ° C as a viscosity index improver. 50 and 1.75 at 99 ° C. The calculation of the ratio

It is assumed that the improvement in the niss gives a value of 1.25 for the effective viscosity index by the speed of the viscosity index improvement according to the invention. In the case of block copolymers used in shear, stability tests were carried out with 1.0% solutions of the polymer in which the amorphous block was initially dissolved in a naphthenic oil at a lower temperature is kept in solution, viscosity index improvers based on meth, while the sterically regular block in the acrylate itself is far superior,
remains substantially unsolvated, but with increasing

Temperature is increasingly solvated in the oil, Example 2

whereby the desired compensation for the natural ⁶ °

Lent decrease in viscosity with increasing temperature The same catalyst as in Example 1 was entry. So it is believed that polypropylene is used on. A mixture containing 18 g of styrene and 40 g Due to its unique oil solubility properties, propylene was placed in the autoclave at 60 ° C th compared to, for example, linear poly- introduced. Then a small sample of the polyethylene was made taken as a sterically regular polymer block for 65 mers. Infrared analysis showed that the purposes of the invention is preferable. Further the polymer contained 16 mole percent styrene. Appropriated sterically regular polymer blocks are finally 100 g of an equimolar mixture, for example isotactic polybutene-1 or isotactic one of propylene and butene-1 introduced. the

The temperature was increased to 100 ° C. within 30 minutes and at this for a further 30 minutes Value held. The polymer was worked up in the same way as in Example 1. Here were 84 g of a polymer with a melt index of 11.9 were obtained. A 10% solution of this polymer in a solvent-refined mid-continent oil SAE 30 showed a value of 1.2 for the effectiveness of the viscosity index improvement.

Example 3

^{A solution of 2.2 cm 3} (20 mmol) of titanium tetrachloride in 250 cm ^{3 of} a pure mineral oil previously treated with molecular sieves was introduced into a 1 liter autoclave under dry nitrogen. After adding a solution of 1 cm ³ (7.5 mmol) of triethylaluminum in 100 cm ^{3 of} n-heptane, the mixture was heated to 180 ° C. over the course of one hour. effective as a viscosity index improver when used as a 10% solution in a common lubricating oil (Texaco Regal Oil B).

⁵ Example 6

The polymerization was carried out in the same manner as described in Example 1 using the the same catalyst system carried out, but a mixture of propylene and butene-1, the Propylene contained in amounts of 25 to 75 mole percent was used as the monomer. In any case an excellent viscosity index improver for lubricating oils was made.

Example 7

The experiment described in Example 5 was repeated with the exception that instead of the

After cooling the autoclave to 50 ° C, 20 mixtures of propylene and butene-1 were a propylene

7.0 cm ³ (52.5 mmol) of triethylaluminum in 50 cm ^{3 of} mineral oil were added. After introducing 250 g of butene-1, the polymerization was carried out for 30 minutes. At this point the pressure had dropped from 3.5 atmospheres to normal pressure. Then 100 g of an equimolar mixture of propylene and butene-1 were introduced, and the polymerization was continued for 45 minutes with the temperature rising to 100 ° C. The autoclave was then fed an ethylene mixture containing about 30 to 60 mole percent ethylene into the second stage polymerization in which the polymerization was carried out at the higher temperature.

Example 8

The experiment described in Example 7 was repeated with the exception that in the second

cools and relaxes. The viscous solution was a 30 step in place of the propylene-ethylene mixture Washed ethylene glycol and water. The heptane α-olefin with an average molecular weight between was distilled off under reduced pressure. A viscous residue was obtained, the 368 g weighed and contained 128 g of polymer. By diluting a sample to a concentration of 1% 35 in a typical mid-continent oil was SAE 10

C ₅ and C _{20 was} used.

Example 9

obtained a solution showing a value of 1.22 for viscosity index improvement.

Example 4

The experiment described in Example 4 was repeated, but instead of 1-octene, a Mixture of ethylene and butene-1, which contained 40 to 70 mole percent of butene-1, introduced. The polymerization was carried out until an amorphous copolymer of ethylene and butene-1 in molecular weight Had made 200,000.

The same catalyst as in Example 1 was used. 100 g of 1-butene were added to the autoclave introduced at 55 ° C. After a polymerization time of 1 hour, unpolymerized Bu- ten-1 blown off, whereupon 60 g of octene-1 were introduced. The temperature rose within 20 minutes increased to 90 ° C and the polymerization continued for a further 40 minutes at this temperature.

The polymer was based on the olefins described in Example 1, which were used in an amount of 30 to 90 molar samples Way worked up. In this case, 132 g of poly- per cent were present and was continued. The polymer obtain. A 10% solution of this polymer in an SAE-10 base oil showed a value of 1.18 for viscosity index improvement effectiveness. 55

Example 5 Example 10

The experiment described in Example 9 was repeated with the exception that the polymerization at the higher temperature of 90 ° C by introducing a mixture of propylene and C ₅ -C ₂₀ - * -

merization of the amorphous block of propylene and higher -olefin was down to molecular weight from 200,000 to 300,000.

Example 11

The experiment described in Example 1 was repeated, the polymerization temperature increasing to 110 ° C increased and the propylene-butene-1 mixture was introduced after that used at the beginning Butene-1 to isotactic polybutene-1 having a molecular weight of about 100,000 had been polymerized. Polymerization at higher temperature was canceled after the amorphous copolymer block of propylene and butene-1 had a molecular weight between about 200,000 and 300,000. The block copolymer formed was The experiment described in Example 1 was repeated, but the one introduced at the beginning Butene-1 mixed with 80 to 95 mole percent propylene and the polymerization of the stereospecific copolymer continued to a molecular weight of about 100,000. The mixture with the larger proportion of butene-1, d. H. 47 mole percent, was then introduced and the polymerization at carried out at a higher temperature until the amorphous polymer block has a molecular weight of 300,000.

Example 12

The experiment described in Example 2 was repeated, the initial stereospecific polymerization being carried out up to a molecular weight of 90,000. The polymerization was then continued at the elevated temperature of 100 ° C. with the introduction of a mixture which consisted in practically equal parts of propylene and an α-olefin having an average molecular weight of C _n -C ₂₀ . The polymerization of the amorphous copolymer was terminated when the molecular weight reached 150,000.

Example 13

A mixture of propylene and ethylene, which contained about 1.0 to 20 mole percent ethylene, was with the catalyst system described in Example 1 at a temperature of about 40 ° C to a Molecular weight of about 20,000 stereospecifically polymerized ao. Then the amount of ethylene was in the gas mixture to about 50% and the polymerization temperature increased to about 90 ° C and the polymerization up to a total molecular weight of formed block copolymers of about 250,000 as continued. The product was made by removing the Purified solvent and washing in methyl alcohol.

Example 14

30th

The experiment described in Example 11 is repeated except that ethylene is used in place of propylene.

Example 15

The experiment described in Example 1 was repeated, but with pentene-1 in place at the beginning of butene-1 to form an isotactic polypentene-1 block instead of the isotactic polybutene-1 block was used. In addition, instead of the amorphous propylene-butene-1 block copolymer an atactic butene-1 block polymer are formed.

Example 16

45

^{A solution of 3.7 cm 3} (30 mmol) of diethylaluminum chloride in 1 liter of heptane is introduced into an autoclave with a capacity of 3.75 liters under dry nitrogen. After adding 3.0 g of a titanium trichloride catalyst which contains Vs moles of aluminum trichloride per mole of titanium trichloride, the temperature is increased to 65.degree. Then 16 g of hexene-1 and immediately thereafter 56 g of butene-1 are introduced. The polymerization is carried out at 65 ° C. for 30 minutes. The reactor is then depressurized, whereupon 60 g of a butene-propylene mixture containing 52 mole percent propylene are introduced. The polymerization is continued for a further 60 minutes at 65 ° C. The autoclave is then emptied and the polymer is precipitated from the viscous heptane solution with isopropanol. After drying, 85 g of polymer are obtained. This polymer has a 10% solution in a paraffinic oil of 100 SUS. a value of 1.23 for the effectiveness of the viscosity index improvement. A 10% solution of the polymer in the same base oil can easily be poured. Hexene-1 makes up 7.9 mole percent of the monomer used.

Example 17

A solution of 5.1 cm ³ (40 mmol) of diethylaluminum chloride in 21 n-heptane was placed in a 3.75 liter autoclave. Comprised, after addition of 4.0 g of titanium trichloride Vs moles of AlCl ₃ per mole of TiCl _3, the temperature was raised to 75 ° C. 50 g of a C ₇ -C ₉ * olefin fraction were then introduced, followed immediately by 200 g of a mixture of butene-1 and propylene containing 52 mol percent propylene. The polymerization was carried out for 2 hours, the pressure in the reactor falling ^{to less than 0.35 kg / cm 2.} The polymer was isolated in the usual way. After drying, 163 g of polymer were obtained. A 10% solution of this polymer in a paraffinic oil of 100 SUS. showed a value of 1.28 for the effectiveness of the viscosity index improvement. A 10 ⁰ / o solution of the polymer in the same base oil was easily pourable. The molecular weight of the polymer was determined by measurements of the viscosity in dilute solution to be 800,000. The C ₇ -C ₉ α-olefin fraction accounted for 10 mole percent of the monomer charge.

Example 18

In a 3.75 liter autoclave, 21 heptane containing 3.0 g of TiCl ₃ · 1/3 AlCl ₃ and 3.75 cm ^{3 of} diethylaluminum chloride was placed under nitrogen. The reactor was closed and the temperature increased to 60 ° C. Then, 4-methylpentene-1 in an amount of 5 g / min and butene-1 in an amount of 2 g / min were pumped into the reactor. After 20 minutes, the addition of 4-methylpentene-1 was stopped. The butene-1 was introduced for a total of 50 minutes. After a further polymerization time of 1 hour, the reaction was terminated by adding methanol. After isolation and drying in the usual manner, 71 g of a block copolymer (copolymer of 4-methylpentene-1 and 1-butene) having a molecular weight of 900,000 were obtained.

A 1% solution of this polymer in a neutral paraffin oil of 100 SUS. shows after 3 days Have a value of 1.99 for the effectiveness of the viscosity index improvement.

Example 19

The experiment described in Example 18 was carried out using styrene instead of 4-methylpentene-1 repeated. The reaction was carried out at 80 ° C. After 2 hours 45 g a block copolymer (copolymer of styrene and butene-1) obtained, which has a value of 1.4 for showed the effectiveness of the viscosity index improvement, measured at the usual temperatures of 38 and 99 ° C. If the effectiveness of the viscosity index improvement from measurements at 99 and 121 ° C was calculated, the value was 1.8, an indication that this copolymer is suitable for use is suitable at temperatures above those normally encountered in automobile engines lie.

Claims (2)

Patent claims: 1. Lubricating oil containing a block copolymer of oil-soluble as viscosity improver .. 809 637/880 11 12 Hydrocarbon polymer chains that have a number 2. Lubricating oil according to claim 1, wherein the of alternating amorphous and sterically regular amorphous segments from polymers of low moderate segments, the amor- «-olefins and from 0.5 to 25, in particular 1 to phen and the sterically regular blocks, each 20 mol percent, of a polymer of an α-olefin a molecular weight of about 50,000 to about 5 with 5 to 25, especially 7 to 15 carbon Have 1,000,000. atoms exist. 809 637 / MO 11.68 © Bundesdruckerei Berlin