DE1795425C3 - lubricant - Google Patents

Description

and the second catalyst component of the general formula one consisting of ethylene, propylene and hydrogen Contains input mixture whose polymerization in the presence of a two-component catalyst took place in which the molar ratio of second to first component 2: 1 to 50: 1 amounts to

7. Lubricant according to claim 5 or 6, characterized in that it is a reaction product of one of ethylene, propylene and Contains hydrogen input mixture, its polymerization in the presence of a two-component catalyst took place, the first component being a tri-n-butyl-ortho-vanadate is

8. Lubricant according to one of claims 5 to 7, characterized in that it is a reaction product contains an input mixture consisting of ethylene, propylene and hydrogen, whose polymerization took place in the presence of a two-component catalyst, wherein the second component is an ethyl aluminum dichloride, diethyl aluminum chloride or an ethyl aluminum sesquichloride is.

corresponds to, wherein R ₁ , R ₂ and R _{3 are} C ₁ - to C ₁₄ -alkyl or aryl radicals, R _{4 is} a C ₁ - to C ₁₄ -alk "yl radical, X and Y are bromine, chlorine or iodine, a, b and c is 0 or 1 and d is 1 or 2.

6. Lubricant according to claim 5, characterized in that it consists of a reaction product The invention relates to lubricants, their viscosity index and shear strength by adding certain amorphous ethylene-propylene copolymers are improved.

Lubricating oils containing high molecular weight copolymers are often subject to high levels in practical use Shear stresses that cause viscosity loss and other undesirable effects in the event of mechanical instability of the additive in the oil mixture.

It is known that hydrocarbon polymers and copolymers are produced in the production of hydrocarbon polymers with the help of »Ziegler-Natta« catalysts, products that are in hydrocarbon solvents and oil are partially or wholly soluble and often have a stereospecificity leading to the formation of a crystalline structure exhibit. It is also known that this reaction by adding hydrogen to the to be polymerized monomers can be effectively attenuated.

Ethylene-propylene copolymers are known per se and have been made with the help of many catalyst systems including those of the Ziegler-Natta type. They are generally crystalline, like that copolymers produced in accordance with US Pat. No. 2,327,705 with the catalytic assistance of oxygen, but can also be produced in amorphous form under certain conditions. Known is also that these amorphous ethylene-propylene copolymers especially at molecular weights impart improved viscosity properties to over 50,000 of a lubricating oil. Such copolymers with an ethylene content of 40 to 80% also impart a degree of shear strength to the lubricating oil

The US-PS 2190 918 describes a lubricating oil

addition in the form of an ethylene-propylene copolymer, a catalyst of the Friedel-Krafts type is used for its production. In this way of working An amorphous copolymer may form, but this has a broad molecular weight distribution having.

Also, the ethylene-propylene copolymers described in U.S. Patent No. 26 91647, which are prepared in the presence of a heterogeneous catalyst, have a broad molecular weight distribution, to the molecular weight such as hydrocarbon oil additives used copolymers to 50 000 and above.

From FR-PS 12 87502 are amorphous copolymers known from ethylene and an α-olefin, in the manufacture of which a Ziegler catalyst is used will. In this case, the starting mixture does not contain any hydrogen, while for lowering it molecular weight modifier is used. The pro ao obtained according to the FR-PS Products are solid substances with a higher molecular weight and are not suitable as lubricant additives.

The invention is a lubricant that consists of

(1) lubricating oil as a basic ingredient and

(2) a smaller proportion of ethylene-propylene copolymer as an additive to improve the invention in that they are amorphous and a lower mole weight and a narrow mole weight distribution own.

The new copolymers are prepared in such a way that an inert solvent is used a mixture of ethylene, propylene and hydrogen saturates the solution temperature below room temperature decreases, continuously introduces further amounts of the gas mixture into the solution and slowly introduces it inert solvent is added that uses a Ziegler-Natta catalyst contains. The polymerization then begins and manifests itself in a slow rise in temperature. After the reaction has ended, the copolymer formed is precipitated by adding an alcohol, separated from the Reaktiousgsmisch and dried

According to the invention, gas mixtures of propylene and ethylene in a molar ratio of 0.2 to 10.0: 1.0 provide useful copolymers, and the preferred ratio is between 0.6 to 4.0: 1.0. The addition of hydrogen to the olefins is such that the total gas mixture contains 0.05 to 15.0 and preferably 1 to 10 mol percent hydrogen. According to the invention, aliphatic, aromatic and halogenated hydrocarbons are suitable as inert solvents, ie solvents which do not deactivate the catalyst, the polyhaloalkanes, such as CQ ₄ , CBr ₄ and CH ₂ Cl ₂ , being particularly useful

_{4 22}

to have. Preferred inert solvents are tetra viscosity index properties des Schmiernut- 3o chlorinated carbon, n-heptane, benzene and cyclohexane. by means of reaction temperatures between -40 ° C and 121 ° C

can be used, but it is preferable to work between 1.7 ° C and 21.1 ° C. The useful working pressure range lies between 0 and 21.1 atü and ih d 52 ü hl

consists and is characterized in that it is an amorphous ethylene propylene as component 2

Contains mixed polymer which has an average numerical 35 is preferably kept between 0 and 3.52 atmospheres, cal molar weight below 40,000, in particular from The reaction time usually varies between 10,000 to 40,000, preferably a ■ propylene content of 20 to 70 mole percent and an M _w : M "-Ver-. has a ratio of less than about 5.

A lubricant of the type described, which is an ethylene-propylene copolymer, is preferred according to the invention contains that by reacting an input mixture of ethylene, propylene and hydrogen in an inert solvent in the form of an aliphatic, aromatic or halogenated hydrocarbon under polymerizing conditions has been prepared in the presence of a homogeneous Ziegler-Natta catalyst. If you see such a copolymer for 20 minutes and 2 hours, but it is chosen so that a copolymer of desired molar weight and molar weight distribution arises.

As already mentioned, a characteristic of the new copolymers is that they have a narrow molecular weight distribution, that is to say that the ratio of mean weight / molar weight (M _w ) to mean numerical molar weight (M _n ) in them is less than about 5 is. Particularly strong improvements in terms of viscosity index and shear strength of the lubricating oils blended with them give those, a preferred embodiment of the invention

py j, g g

If lubricating oil is added, a practically shear-forming amorphous copolymer is obtained iölih i b Viki il rih MlGih 20000 bi

solid lubricating oil mixture with improved viscosity index.

The novel copolymers are produced at moderate temperatures and pressures in the presence of hydrogen gas and a solvent-soluble Ziegler-Natta catalyst. Their propylene content is measured by means of nuclear magnetic resonance. Copolymers in the numerical molar weight range from 20,000 to 35,000 are preferably used as lubricating oil additives. The improvement in lubricating oil shear strength is particularly good in the case of copolymers with a narrow molar weight distribution, i.e. those in which the ratio of the mean weight / molar weight to the mean numerical mean numerical molar weight of 20,000 to 35,000, a propylene content of 25 to 55 Mole percent and a tl _w : Ä? _n ratio below about 4.

Of the many Ziegler-Natta catalyst systems, which cause olefin polymerization are basically only those for carrying out the invention for the formation of amorphous ethylene-propylene copolymers leading and among them exclusively those soluble in a solvent (not the heterogeneous) systems.

The Ziegler-Natta catalyst systems used according to the invention therefore consist of two components dissolved in an inert solvent. the

Schem molar weight below 5 and preferably even 65 first component consists of a hydrocarbyl sub 4 lies. Of the well-known, used to improve vanadate (which is also called tricarboxyvanadyl or of

Lubricating oil viscosity index used ethylene-propylene copolymers differ which Vanadyltrihydroxycarboxyd can denote), a Hydroxycarboxyvanadylhalogenid or a Van-

dyl trihalide. It can be seen through the general, naphthenic and asphaltic smear

Formula oils and occurs most strongly with paraffinic

(R ₁ O) O (R ₂ O) ₀ (R ₃ O) CVOX _{3 -} O - S _- C see lubricating oils in the viscosity index range of

z. B. 80 to 110.

define in which R ₁ , R ₂ and R _{3 are} alkyl or aryl 5 The invention is explained in more detail in the following examples of hydrocarbyl radicals having 1 to 14 carbon atoms, X len, without being restricted to them, a halogen atom such as bromine, chlorine or iodine, and

a, b v & ä c means either O or 1. Such example 1

Compounds are, for example, tri-n-butylortho- u _e —t «, ii„ r. „Λ» „.„ „, (,„ „

vanadate, sodium orthovanadate, phenyl orthovanadate,. . D "S." i ~ - "" ~ i _{in the} "_

dat, Tridodecylorthovanadat, Djmetiyldodecylortho- Ethylen-Propylencopolymers

vanadate, diethoxyvanadyl chloride, n-butoxyvanadyl- In a stirred reactor cooled with an ice bath

dichloride, vanadyl trichloride and the like initially became about 500 ml carbon tetrachloride

The second catalyst component consists of introduced, which at 4.4 ° C with a gas mixture of an alkylaluminum halide that was saturated by the 15, 6.8 mol percent of water and the remainder of an ethylene-propylene compound ( R ₄ X (AlY _3-1 , mixed in the molar ratio 1.0: 1.3. Subsequently, further amounts of this

can define, in which R _{4 is} an alkyl radical with 1 to a gas mixture with an input rate of 1000 ml

14 carbon atoms, Y a halogen atom, as introduced per minute. Then 1.5 ml of a

Bromine, chlorine or iodine, and d the number 1 or 2 weight percent solution of diethylaluminum

Such compounds are, for example, nium chloride in heptane and 0.5 ml of a 20 weight

Ethyl aluminum dichloride, diethyl aluminum chloride, percent solution of tri-n-butyl vanadate in

Didodecylaluminum chloride, diisopropylaluminum-heptane were added. The polymerization now continued

bromide, n-hexylaluminum dichloride, di-n-butylaluminum, and the temperature rose over the course of

miniumiodid and mixtures thereof, such as at the approximately 20 minutes of 4.4 ⁰ C to 18.3 ° C. to

Usually called ethylaluminium sesquichloride this time was again the same amount

Mixture of equimolar proportions of ethyl aluminum catalyst, namely 1.5 ml of aluminum and

dichloride and diethyl aluminum chloride. 0.5 ml of the vanadate component solution is added,

The catalyst mixture particularly preferred loading 30 whereby the reaction is continued an additional 10 minutes of tri-n-butylorthovanadat first, ethyl ran until the temperature dropped to 10.0 C ^0. The polymer formed from aluminum dichloride and diethylaluminum chloride was washed with dilute salt or ethylaluminous quichloride as the second grain acid. After stripping off the solution component. It is of course clear to the person skilled in the art that 23.3 g of product were obtained by means of
The closely related homologues of these compounds can also be used with advantage when obtained from infrared spectroscopy. measure - amorphous, possessed a medium numerical

The catalyst system is prepared by adding a molar weight of 29,100, an ~ M _W : M "ratio

the components add to the solvent or below 4 and - by means of nuclear magnetic resonance

the components in a molar ratio of two - determinate »- a propylene content of 44 molpro-

the first component between 2: 1 and 50: 1 40 cents.

mixed. Example 2

amount and minimum amount of hydrogen required, j £ _h . . _ß . j _{{χ M reaction} solvent while on the other hand at high reaction temperature §. _2QQQ ^ ^ _The ρ _ΓΟ ρ _γ1εη . _Α ^ _γ1ε η-tur, large amount of catalyst and as much _{ratio as possible in the} ^ _{be was 0 95 u} $ _{die w} / _sser . Hydrogen copolymers with a lower molar _{concentration of} 4.6 mol%. The catalyst arises. Obviously, with ₅ or _{40 ml of a} 20 weight percent Hep special starting material, the working conditions of _{diethylaluminum} chloride and 3 ml

Modify somewhat in order to obtain a copolymer of spe- _{m 2} oil weight percent heptane solution of trizieUem molar weight. n-butylvLdat. The yield was 123 g of copoly-

The mixing of the copolymers in the lubricating _mer ^ ^ mitüeren numerical mole weight of oil can occur m any known type. A 55 _{24 () 00 a} p _ropy i _{s e} g halt of 37Molproerfahrungsgemaße particularly advantageous addition _and ^ molar weights distribution according to

method then consists ⁱⁿ converting the copolymer in jj.jj = 30 e> r

Dissolve the desired amount in benzene, this solution the "'"'. .

Adding lubricating oil and from the resulting example 3

Mixture eventually strips off the benzene. 60 The effectiveness of the copolymers in the invention

The improvement in viscosity index and shear lubricants in terms of improving strength takes place at low, preferably low, viscosity index and shear strength 0.5 to 5 percent by weight of copolymer was increased by adding 1.5 percent by weight of would give to lubricating oil. Obviously, they can be proven to a lubricating oil approach. the Determine the exact amount to be added which, depending on the type of lubrication, 65 results are summarized in Table I below, desired viscosity index improvement and provided.

required shear strength. The inven- The shear strength was determined using a »Fuel

Darkness-like improvement can be demonstrated in the ppraffini Injector Shear Stability Test (FISST),

as he did in June 1958 at a meeting of the Society of Automotive Engineers by R. Rawson presented paper No. 57 A entitled "Simplified Shear Stability Testing" is described. With this one Test is the shear strength as the percentage

Viscosity loss of the tested oil indicated after a 100 ml sample of the same of the strict Shear stress from pumping through a Bosch fuel injector 20 times had been subjected.

Table I.

approach
No. composition Viscosity
index Viscosity, SSU FISST
⁰ Zo loss of viscosity 99 ⁰ C 37.8 ⁰ C 99 ⁰ C 37.8 ⁰ C 0.0 A. Lubricating oil 114 165 45.1 0.0 1.6 B. Approach A + Co
polymer from
example 1 171 364 68.8 0.0 2.6 C. Approach A + Co
polymer from
Example 2 149 326 61.4 4.0

Example 4

The advantage of moderating the polymerization with hydrogen has been demonstrated in the manner that approximately in the same way as in Example 1, an ethylene-propylene copolymer was prepared, but the input gas did not contain hydrogen. That so

Tables

The amorphous polymer obtained was similar to that of Example 1 by having a number average molar weight of 23,900 and a propylene content of 45 mole percent. Its viscosity index improvement and thickening capabilities were also similar, however, the shear strength was considerably lower as the test results shown below Show table.

approach composition Weight Viscose viscosity , SSU FISST No. percent activity index "/» Loss of viscosity polymer 37.8 ⁰ C 99 ⁰ C 37.8 ⁰ C 99 ° C

B batch A + Co- 1.5 171 364 68.8 0.0 1.6

polymer from Example 1

D approach B + Co- 1.5 173 348 67.5 14.1 10.5

polymer from Example 4

game 2 with a similar ethylene-propylene-co-

Example 5 polymer with a much wider molar weight ratio

division proven. The copolymer properties

The Advantage of Using an Ethylene Pro- and Test Results of the Containing Lubricating Pylene Copolymers with a narrow molar weight distribution 55 oil mixtures are summarized in the table below by comparison of the copolymer according to Beimen.

Table ΠΙ
Copolymer properties

Copolymer

Molecular weight M.

Molecular weight distribution

Example 2
Example

23 22 600 3.0
13.7

10

Table (continued)

Experimental approaches

Approach composition weight viscose viscosity, SSU no. Percentage index

Copolymer

37.8 ⁰ C 99 ⁰ C 37.8 ° C

FlSST

° / o loss of viscosity

99 ° C

C approach A + Co- 1.5 149 326 61.4 4.0 2.6

polymer from Example 1

E approach A + Co- 1.5 171 522 84.7 39.1 28.4

polymer from Example 5

The copolymer according to Example 2, with its significantly lower M _w : M _n ratio, gives the lubricating oil according to the invention a significantly better shear strength than that of Example 5.

Example 6

The shear strength compared to the significantly higher mole weights in the 20 of the present invention. the

Copolymers containing lubricants was identified with copolymer properties and the test results dei

of other polymeric lubricating oil additives as well as lubricating oil mixtures containing them are in the following

with the table of ethylene-propylene copolymers with the existing table.

Table IV
Polymer properties

Polymer no. description percent tatsmdex Molecular weight Others polymer example 1 Amorphous ethylene 29100 44 mole percent Propylene copolymer Propyl. according to the invention Example 2 Amorphous ethylene 23 700 36 mole percent Propylene copolymer Propyl. according to the invention Example 6 M Polymethacrylate ester about »/ 2 million Example 6 N Polymethacrylate ester about 1 million Example 6 O Amorphous ethylene 58 300 47 mole percent Propylene copolymer Propyl. Example 6 P Amorphous ethylene 64 600 30 mole percent Propylene copolymer Propyl. Experimental approaches Approach composition weight viscose Viscosity, SSU FISST No. % Loss of viscosity 37.8 ° C 99 ° C 37.8 ° C 99 ° C

B. Copolymer of 1.5 171 364 68.8 0.0 16 example 1 C. Copolymer of
Example 2 1.5 149 326 61.4 4.0 2.6 F. Polymer of
Example 6 M 2.25 197 264 62.2 18.2 13.8 G Polymer of
Example 6 N 1.8 222 238 62.2 22.6 20.4 H Copolymer of
Example 6 O 1.5 175 671 101.0 41.2 29.3 J Copolymer of
Example 6 P 1.5 181 743 110.6 50.8 28.4

The existing Veraxisjebnisse show eta- 65, but also have a shear strength that S ^ Si ^ ÄiSBESSÄ SAS. ** «Slitting is not only an effective viscosity index improver

Claims (5)

Patent claims: 1. Lubricant consisting of (1) lubricating oil as a basic ingredient and (2) a smaller proportion of ethylene-propylene copolymer as an additive to improve the viscosity index properties of the lubricant, IO characterized in that it is a component 2. Contains amorphous ethylene-propylene copolymer which has an average numerical molar weight below 40,000, in particular from 10,000 to 40,000, preferably a propylene content _{of 20 to 70 mol percent and a Ή ν} : ^ ratio of less than about 5 2. Lubricant according to claim 1, characterized in that it contains an ethylene-propylene mixed ao polymer which has an average numerical molar weight of 20,000 to 35,000, a propylene content of 25 to 55 mol percent and an X? _w : M “ratio of less than about 4 has as 3. Lubricant according to claim 1 or 2, characterized in that it is an ethylene-propylene copolymer contains, by reacting an input mixture of ethylene, propylene and hydrogen in an inert solvent in the form of an aliphatic, aromatic or halogenated hydrocarbon with polymerizing Conditions established in the presence of a homogeneous Ziegler-Natta catalyst has been. 4. Lubricant according to claim 3, characterized in that it is an ethylene-propylene copolymer contains, the reaction of an input mixture of ethylene, propylene and hydrogen in an inert solvent in Form of an aliphatic, aromatic or halogenated hydrocarbon under polymerizing Conditions were established in the presence of a homogeneous Ziegler-Natta catalyst where the propylene and ethylene in the molar ratio of 0.2: 1.0 to 10.0: 1.0 and hydrogen are present in the input mixture at a concentration of 0.05 to 15 mole percent. 5. Lubricant according to claim 3 or 4, characterized in that it is a reaction product contains an input mixture consisting of ethylene, propylene and hydrogen, whose polymerization took place in the presence of a two-component catalyst, the first catalyst component of the general formula (R ₁ O) ₀ (R ₂ O) ₆ (R ₃ OXVOX _3. ^.,