DE2133584A1 - Hydrocarbons - Google Patents

Description

The invention "relates to novel polyolefin oils, consisting essentially of" consist true oligomers of isobutylene. ¹¹ These oligomers have a geminal structure and have cumulative geminal methyl groups. They are described in more detail below. Substantially pure single carbon number olefins can be obtained as distillate fractions of such oils. The fractions or oils are suitable as lubricants (e.g. for train gears) and can be converted by hydrogenation or other well known reactions into paraffins or polar compounds with a geminal structure which are valuable as lubricants or components of blended lubricants.

New polyolefin oils from monomers of the formula

CH2 = Ä -2-

109886/1992

where R denotes a CBU group or -CgH, group and R .. denotes an alkyl group having 1-10 carbon atoms "close to exceptionally high viscosity indices and high traction coefficients. These polyolefin oils" consist essentially of non-isomerized, genuine oligomers, such as genuine ones Polyisobutylene oligomers (e.g. CjgEL ₂ , C ₂₀ H ^ ₀ , ^C 24 ^H 48 ** " ^C 48 ^H 96 ^ *" ° ^{he new} oils are suitable as oils for the electrical sector, as chemical intermediates or as transfer materials (ie, as The hydrogenated oils are new and are "particularly valuable as power transmission materials," especially when they are hydrogenated to a bromine number less than 10, preferably less than 5. The unique properties of these new oils , regardless of whether they are olefins and / or paraffins, can be detected by a combination of gas chromatography and nuclear magnetic resonance spectroscopy (HER) n. A characteristic feature of these olefins and the paraffins produced therefrom by hydrogenation are "clustered" and sterically hindered geminal methyl groups and isolated methylene groups. The individual individuals in the range G ^ g to C ^ g can be separated from the total oil by gas chromatography. Such a new polyolefin oil with a viscosity index according to JiSTM of more than 85 consists essentially of monoolefins with carbon numbers C "24» Cgg » ^C 32» ^ 36 ^and ^ ^ 40 * ^ ^es * ^{cn have} repeating isobutylene structures.

In general, improved transmission fluids and components for transmission fluids when a polar group is incorporated into a hydrocarbon with a geminal structure.

-3-109886 / 1992

leads (for example in polyisobutylenes with geminal Structure). Preferably the compound does not contain any aromatic or olefinic unsaturation. The polar molecule thus obtained seems to adhere more strongly to metal surfaces (compared to the parent hydrocarbon) and thus leads to higher power transmission or traction. That these power transmission fluids exhibit high traction is unexpected because of the literature (J. Rounds, Chem. & Eng. Volume 5 »No. 4 October 1960 and the citations given therein) teaches that hydrocarbons which have polar groups at one end which reduce the static and dynamic friction of mineral oils.

Compounds used as power transmission fluids or as ingredients power transmission fluids or other lubricants are suitable can be represented by the following structural formula:

R I

--JCH ₂ C - | - (0Η ₂ ) _η , -1

3 ^E 2

therein η denotes an integer from 1-30, n ¹ O or 1, and R, R- and R ₂ represent one of the following groups or a combination of such groups: methyl, ethyl, propyl, isopropyl, butyl -, isobutyl, tert-butyl, isopentyl, neopentyl, cyclohexyl, methylcyclohexyl, indanyl, hydrindanyl, cyelohexylindanyl, cyclohexylhydrindanyl groups; and Y stands for one of the following functional groups: keto groups, carboxyl groups, salts of acids, ether, alcohol, ester, acyl halide, acyl hydrazide, mercapto, epoxy, thioester, thiolester, thioether, phosphate Groups (including mixed esters or _Λ

109886/1992

Coester), phosphite groups (including mixed ester groups), Sulphate, sulphite, sulphonate groups, halogen atoms, oxime, imino. Amido, amino, or maleic anhydride adduct groups. There can be more than one functional group in a "given molecule" ("For example imino and amino groups). In addition, the indany! compounds and / or their cyclohexyl units with lower alkyl radicals substituted with 1 "to 6 carbon atoms be, for example with a methyl group. Tin complexes described below are also polar compounds in Meaning of the invention.

In the polar compounds described, the various named functional groups represented by the following structural formulas:

Ketone group 0
H Carboxyl group 0.
Il -C-OH Alcohol group -OH

and OH t

^E 4

Ester group 0 R _x 0

Il I 2 II

-O-C-R, and -C-O-C-Rf

^R 4 acyl halide group 0

Il

-C-X thioether group ~ S-R,

109886/1992

Epoxy group A. Phosphate (or mixed - ^0R 4 -C CR.
IIT ^- phosphate) group I.
-0-P = O
I.
OR, - ■ ^R 5 ^R 6 R ₄ OR ₅ Thioester group S.
It and C-O-P = O -C-OR ₃ R ₃ OR ₇ Thiolester group 0
Il
-CSR ~ Phosphite (incl. OR ₄ Mixed ester) group -0-P

Other suitable

phosphorus-containing groups

belong to ■ OR. OR.

ι ^{1 day} ι t

-0-P = O -0-P

f I

^E 5 ^E 5

Ry, and R.

| Τ IT ¹

- P = O -P

R ₅ R ₅

Sulfates 0

It

-0-S-OR.
ti 4

⁰ -6-

109886/1992

and R, O

I Il J

R ₄ O

Halides. CX ₉ ■ X / CX,

-CX ₉ -C-CX, -C = C

CX ₉ CH, CH,

ι J ti £ t J ι -> ι J

-C-CX ₉ -C CH, -C-CX = C-CX ₉ -C-CH,

f \ ΓΙ j

^CH 3 CCCH, ^CH 3 ^CH 3

CH,, -C-CX ₂ -C = CX-C-CH ₃ or similar,

CH ₃ CH ₅

where X is a chlorine atom, bromine atom or iodine atom and a or several water atoms of the corresponding hydrocarbon are replaced by halogen.

Amino groups include O .R.

¹¹ /

-C-H-

^X 5 '° / 4

-C-HH-W

and 0 R "

-C-SH- (OB ₂ ) _n «-H

wherein ri is an integer from 1 to 12;

belongs to amino groups * 4

-N

^X R ₅ -7-

109886/1992

and any group formed by reduction of the amide (for example with hydrogen in the presence of Raney-Niekel in a solvent, such as ethanol) can be obtained.

In the structures given, R 1 and R 6 can represent an alkyl group having 1 to 7 carbon atoms or a cyclic or alkyl-substituted cyclic hydrocarbon radical which can be saturated, olefinic or aromatic (and is preferably saturated). These radicals include the groups already described as R, R ^ and R ₂ ; however, the radicals which can be used for R ~ and R ₈ are not restricted to these. R ,, R- and R ~ are hydrogen atoms or any radicals or groups which are specified for R ~ and Rg. Rg is a methyl group or a hydrogen atom. If the radicals R ^, R ,, R-, Rg and R are on the same molecule, they can represent the same or different radicals.

A preferred class of polar compounds included under those described The structural formula is derived from the "real" polyisobutylene oligoiaeren or the other yinylidene polymers described in more detail below by chemical reactions, as described in the examples below, or obtained by conventional organic reactions necessary to produce polar derivatives of olefins are used. In the pail of the polyisobutylene oligomers, these polar compounds can be represented by the following formula

CH,

CH ₂

CH,

-8- 109886/1992

in which η, η ¹ and Y have the meaning already mentioned.

These polar compounds are particularly valuable as power transmission materials when they are added in a predominant proportion (for example 50 to 90 Vdlum- $) or in the effective minimum amounts (for example $ 1, preferably $ 3> and typically at least $ 6) to base oils, such as paraffinic lubricating oils (preferably solvent refined and / or dewaxed lubricating oils), naphthenic lubricating oils (preferably naphthenic acid-free), polyolefinic oils. Fluids and synthetic naphthenic lubricating oils (for example, according to US Pat. No. 3,287 _} 259). All of the base oils mentioned can be partially or fully hydrogenated to improve their chemical and / or thermal stability and to have a longer duration with hollow traction under operating conditions to ensure. Particularly valuable lubricants include a hydrogenated base oil which contains less than 5% by weight of gel aromatics and less than 10% by weight of olefins and which also has a polar compound with a geminal structure from 0.520 <fo upwards, which preferably corresponds to the formula given above.

One embodiment of the invention is represented by mixtures of lubricants which contain chemical compounds which can be formed by the action of various chemical reagents on the polyolefins or polyolefin oils. Similar reactions can be carried out with other geminally substituted olefins to give the polar compounds of the invention. These compounds are valuable as lubricant additives, especially lubricants for traction transmissions, _ _q _

109886/1992

Friction gears and differentials with limited slip.

A typical toric traction transmission is described by Hewko et al., "Tractive Capacity and Efficiency of Rolling Contacts", Proceedings of the Symposium on Rolling Contact Phenomena , Elsevier-Verlag Amsterdam, 1962, pp. 159-161.

The flow of the lubricant through the drive device can be by spray lubrication or by spray lubrication or splash lubrication. In a further embodiment, the lubricant is in the form of a mist or aero-oil applied. When lubricating with atomized lubricant, the lubricant can be used to improve re-separation and / or an effective amount of a polymeric additive (e.g. 0.01 to 2 wt of the polymer), which is an acrylic acid, methacrylic acid, olefin (for example isobutylene,) or styrene polymer (for example a polymer of c *. -Me thy! Styrene) with one of the Viscosity determined mean molecular weight in the range of 10,000 to 2,000,000 (preferably 100,000 to 500,000) can. Such additives or additives are described in known literature references. Among the specified polymers Additives are polyolefins and polyolefins with polar groups (for example poly (methyl methacrylate)).

One embodiment of the invention provides a tensile force or Adhesive gear is that contains at least two mutually rotatable parts in one for transmitting a torque suitable mutual assignment exist. On the over-

109886/1992

On the surfaces of these parts, a transfer agent is provided which contains at least 1% by weight , preferably at least 5% by weight, of an oxygen-containing chemical derivative of a branched olefin hydrocarbon having 12 to 120 carbon atoms, preferably 20 to 80 carbon atoms. This olefinic coal material has the following formula:

CH *

I J

CIL

CH,

CH,

• GH

■ C _

in which η is an integer from 0 to 29, in particular 2 to 10 and Z stands for one of the following groups:

(A) CH,

HI ⁵ -C = C

CH,

(B)

-CH

CH,

CH,

(C)

-CH =

CH,

C - mi - • OxIp

CH,

-CH

Il

G -CHp -— "C (CH-2) -ζ

(E)

CIL

= CH

-i) (CH-j;) -

-.11-

109886/1932

Such a connection is formed, for example, when this Olefin is split into two fragments at the double bond, so that each of these fragments at the original junction contains a carboxyl group. Other compounds can be further implemented by either of these fragments by further degradation (e.g. decarboxylation), further oxidation or by both methods.

One method of making these compounds is ozonolysis. Depending on the type of olefin, various new compounds and devices can be produced. If, for example, Z is a group (A), these compounds can be prepared by at least one of the following reactions are formed:

CH

CH

H
!
CO

O =

CH, i 5 C

CH, ⁵

II -0 = 0 + 0 =

CH, C.

CH,

I '

-C

+ CO or

-C— OH

CH ₃

-C - OH I CH ₃

if 7, is a group (B), these compounds can * deB olefins

109886/1992

be formed by the following reaction:

CH ₂ '0 -CH ₂ C CH ₅ > -CH ₂ C CH ₅ + CH ₂ O

when Z represents a group (C), these compounds can by at least one of the reactions

I ⁵ HI

-CH = C-CH ₂ -C (CH ^) ₅ ^ -CHO + HC-C-CH ₅

, 0 = C CH ^ 0 ->

—C OH

are formed.

If Z stands for a group (D), such compounds can be formed by the following reaction:

-CH ₉ -C-CH ₉ -C-- (CH,), - ^ - CHp C CH ₉ C (CH ^ U + CHoO

if Z stands for a group (E), this compound is obtained by at least one of the following reactions:

CH ,, CH, C

1 i I

- C ~ GH - C (CH ^ U -: - »-CH ₀ - C =" 0 + CH

. 3 5 2 - - j,

0 = C — Ö (CH ₅ )

₅ ) ₅ OH

A class of the preferred oxygen-containing compounds of the Invention contains at least 11 carbon atoms (especially at least 15 carbon atoms) and has the following structural formula on ·

-13- 109886/1992

CH,

ι -

- ο

CH,

- 13 -_

CH,

CH ₉ - C
² I.

ί -

C! -

CH,

-Z ¹

in which η is an integer from 0 to 29 inclusive and Z ^{1 is} one of the following groups ":

H
-C = O

-C - OH

O -C - OH

Il

-CH ₂ - C - CH,

-CH,

Il

C -CH,

Typically, mixtures can be obtained that range from 85 "to 99 percent by weight of one of these oxygen-containing compounds with a polyisobutylene structure or a mixture of these oxygen-containing compounds Connections included.

Epoxides can be prepared from any of the olefins described by reacting the oilefin ^S with 30 to 95% (for example 90%) hydrogen peroxide. This reaction is preferably carried out in the presence of a ΜοΟ, catalyst.

The substituted polybutene components according to the invention are usually liquids and have good solubility in mineral oils. These derivatives can therefore be particularly suitable as lubricant additives or as additives to other oils or petroleum products (such as rubber process oils, hydraulic fluids, fuels, cooling oils, textile machine lubricants, cooling media for nuclear reactors, paints, etc.).

109886/1992

Choice of the molecular weight (or the viscosity) of the polyolefin used as feed can be based on the derivatives a desired viscosity or molecular weight can be set.

An.important requirement for a power transmission fluid or a power transmission fluid for use in a power transmission system of an automobile is that it not only has good reaction properties, but also a good lubricant for the differential gear and differential ball and a good lubricant for the rollers and bearings Treads is. Although such a transmission fluid could also be used as the hydraulic fluid in the toric device when using a hydraulic fluid of low traction (ie, high viscosity index (VI)), it is preferred that the hydraulic fluid contain an indicator, such as a easily visible dye, so that leakage of the hydraulic fluid into the main part of the drive device can be detected when this main part is checked for the presence of transmission fluid, for example with the aid of a dip stick _c

To prevent evaporation losses of the liquid or the fluid and to ensure protection against the ingress of contaminants into the transmission fluid, the power transmission system should completely closed and well sealed. When using volatile transfer liquids the seals and the system resist the bridge kS ^ ziöia, the is generated by the vapor content of the liquid or the fluid at the operating temperatures «-15-

109886/1992

The "accompanying drawing shows a typical vapor phase chromatogram in the range C ^ Ms G ^ ₂ J of a new polyisobutene oil according to the invention. The resolution Ms achieved almost to the base line (the dashed line is the base line) indicates that only a very low content of gec: The gas chromatogram of the same oil after hydrogenation corresponds to that of the figure with respect to the resolution Ms practically to the baseline.

Each peak in the drawing is formed by a single type of hydrocarbon (for example C ₂ q), for which a maximum of "clustered" and sterically hindered geminal methyl groups and iso-

en /
lated methyl groups are characteristic.

The gas chromatograms of commercial polybutene oils show that these oils do not consist essentially of true oligomers of isobutene, but rather contain considerable proportions of practically all types of hydrocarbons of the corresponding carbon number which can be present within the range of the carbon numbers of the oil. For example, with a commercially available polybutene oil, sharp GC peaks within the C- r bis

^c i6> ^c i7> ^ iQ »^ 20» ^ 23> could be identified. This oil was also far from baseline dissolution (i.e., it produced a "smeared" chromatogram), indicating the presence of numerous isomeric forms of the other possible species of the corresponding carbon number (e.g., C ₁₈ , C ₂₂ , C ₂₆ ). _%

-16- 109886/1992

The novel polyisobutylene oils and hydrogenated polyisobutylene oils according to the invention have a higher viscosity index (usually at least 10 $ higher) than oils of the same viscosity "at 99 ^° C., which were prepared from polyisobutylene by known methods. Although the invention includes oils which essentially consist of isobutene oligomers in the carbon number range C _1? ^ is C, α, the preferred polyisobutene oils described have a viscosity index in the range from 90 to 150 (typically at least 95) and consist essentially of true polyisobutene oligomers with carbon numbers in the range from 20 to 40. The term "viscosity index" as used herein (when not specified as "ASTM") means the viscosity index of the viscosity-temperature function (VTP-VI) j as determined by the method of WA Wright according to ASTM Bulletin No. 215, 84 ( 1956) This value is similar to that obtained according to ASTM D 2270, which is referred to as ASTM-VI .

The solvent and the catalyst must be suitable ^ se -selected to be oligomers of the olefinic feedstock to form which have the lowest possible content of disproportionation? - and isoinerization products, which are present in oils of the known processes. The solvent acts as a polar solvent, which is used during the reaction carbonium ions formed as an intermediate product are solvated and complexes the catalyst to form a catalytically active species which remains in the solution phase, üfitromethane and nitroethane also dissolve considerable amounts of the monomers, but a small proportion of the oils. It will

-17-

109886/1992

believed that the latter property is in part responsible for the narrow molecular weight distribution obtained using these "preferred solvents" in the product, resulting in a favorable product distribution. It has been found that suitable solvents which meet these requirements are nitromethane , Nitroethane, nitropropane, nitro "benzene, benzene, lower alkylbenzenes and mixtures thereof. Suitable lower alkyl benzenes include toluene, the xylenes and ethylbenzene. Nitro compounds are preferred (a particularly preferred solvent being nitroethane). Polyisobutylene oils with a KV _gg = 1.50 to 20 and VTF-VI = 95 to 115 can be produced in good yield.

The preferred method of making these fluids uses essentially anhydrous stannous chloride as the catalyst and nitromethane (or nitroethane) are used as solvents. However, a small amount of water can act as a reaction promoter.

The catalyst used in the preferred process (to make oils having an average molecular weight up to about 1000) is stannous chloride. The stronger Lewis acid catalysts, such as aluminum chloride, aluminum bromide, titanium tetrachloride and antimony pentachloride, do not cause any noticeable polymerization of the monomers in nitromethane. Boron trifluoride in nitromethane causes the formation of an oil as a product of isobutene that has a viscosity index of about 75. Stannous chloride does not catalyze the polymerization of these monomers in a satisfactory manner in solvents such as ether, water, dioxane, acetic acid, acetone, acetonitrile, acetic anhydride, _- | g_

109886/1992

Diethylene glycol monoethyl ether, chloroform, methyl acetate, diine thoxyethane, N-methylpyrrolidone and hexamethylphosphoric acid amide.

This system operates at low pressure around room temperature implemented and gives a high ratio of product formed to catalyst consumed, is highly selective for isobutylene and permits the use of feeds of widely varying compositions. It can be easily adjusted to produce the desired products and is well suited for a continuous process with circulation.

The product formed is recovered by simple phase separation. The product distribution is so narrow that simple Vacuum fractionation is required if no heavy by-products are formed. Those occurring as by-products Dimers, srimers and tetramers are used industrially and can also be easily cracked to isobutylene, which is recycled.

The most important reaction variables are temperature and feed rate in relation to the amount present of the catalyst (which determines the reaction rate).

* (Τομρβη)

109886/1992

In general, the temperature may range from -30 to + 100 ° C vary, with a preferred range -3O is ⁰ C to + 50 ° G and the area most preferred 0 ° to 35 ° C. Electrical oils are generally obtained at lower temperatures than the components of transmission fluids. The volume of the oil produced is generally at least equal to the volume of the solvent in a given experiment; however, the ratio of the volume of the oil produced to the volume of the solvent present can easily exceed an amount of 10: 1 The procedure is carried out by continuously withdrawing the reaction medium and separating the product from the catalyst and the solvent, the ratio of solvent to product is generally maintained at 2: 1 to 1: 2. The catalyst can be used in an amount of 0.1 to 40 percent by volume of the solvent present, preferably from 1 to 20 percent by volume of the solvent present, can be used.

The concentration of the free monomer in the reaction medium is relatively low and can with a gaseous feed controlled by the pressure maintained at a certain temperature. In the case of liquid olefinic feeds, this takes place this regulation through the addition rate. In this way the molecular weight of the product is adjusted. In general a pressure of about 0.07 to 19.33 at absolute, in particular from 0.7 to 7 at absolute, has proven to be the most suitable proven.

- 20 -

109886/1992

The feed can be 5 to 100 percent vinylidene monomer (For example, isobutylene), while the remainder of any inert hydrocarbons consists. The presence of hydrocarbons that do not contain vinylidene groups does not interfere », as those defined here Vinylidene monomers are selectively polymerized by the catalyst system. For example, the Effectiveness of isobutene removal from mixtures of isobutene and other butenes and / or butanes from the special process, but is relatively insensitive to small amounts of impurities such as air, water, organosulfur or organonitrogen compounds.

The distillation necessary to obtain various oil compositions is carried out, can lead to different

results that depend on the vacuum, the device, the rate of distillation and the composition of the distilled Depending on the reaction product. Under certain conditions a considerable amount (more than 15 ^) of trimers can be remain when the oil is topped up to 80 C (from higher-boiling fractions is exempted), while under other conditions a small fraction (less than 10 - 6) des Trimers or tetramers remain. It is more typical when 1/3 of the tetramer remains in the oil and 2/3 of the tetramer remains and. almost all of the trimer will be removed. In addition, the distillation is limited by the "thermal stability of the oil. At temperatures (the

- 21 109886/1992

Head fraction) of 175 to 225 ° G can crack the oil become so pronounced that the pressure begins to rise "(usually "the pressure is less than 1.0 mm Hg). The values obtained by gas chromatography (GC) work good information about the relative proportions of dimers, Trimerem, etc. to about G ^ o

The oils produced by the process can be a number range of molecular weight from 224 to about 2000, The preferred product contains predominantly products ranging from the tetramer to the decamer. The tetramer exists in the present case predominantly made up of a main component and a subordinate component. Using of isobutene, the hydrogenated tetramer present as the main component has the following structure:

CH, -

CH,

CH,

CH,

CH,

CH

3.

CH,

H
C-CH ₉ -C-CH,

Il CH,

CH,

and the subordinate component has the following structure:

CH,

CH

CH,

CH,

CH,

CH,

CH,

CH,

The latter structure type predominates above the letrameric one (that is, with the pentaery or higher homologues). the repeating unit for components that represent pentamers and higher oligomers is indicated in the formulas by the brackets appear. The higher olefins such as 2-methylbutene-1 form the corresponding regular structures when they oligomerize under the process conditions described will.

fc For the production of new, non-isomerized oligomer oils Vinylidene monomers suitable for the process described have the following formula:

CH ₉ = C

in which R is -CH, or -Cp ^H 5 ^{xmA R far is an} alkyl group having 1 to 10 carbon atoms.

In the unsaturated form obtained directly, these oligomers are suitable as electrical oils. If the oils are to be used as transfer fluids, they can be hydrogenated using conventional hydrogenation catalysts such as Raney nickel, platinum, palladium or rhodium to improve their resistance to oxidation. The olefinic oils, however, are relatively stable and do not require any further treatment to make them useful as transfer fluids. B ¹ Ur most uses, such as

- 23 10 9 8 8 6/1932

Transfer fluid, the higher molecular weight products can remain in the material of the tetramer "through decamer"; however, the dimers and trimers should together are separated therefrom with dea monomers. This is done in a simple manner by distillation.

The oils produced by the process of the invention are particularly advantageous when used as transmission fluids or transfer fluids (especially in mixtures with saturated cyclic compounds) because they have a high traction coefficient and excellent viscosity-temperature properties exhibit.

The requirements placed on a transmission fluid are described in American patents 2,549,377, 3,440,894 and 3,411,369. Compounds According to the Invention can be incorporated as additives in these known transmission fluids. Exemplary transmission devices, for which the transmission fluids according to the invention can be used are described in the American patents 1 867 553, 2 871 7U, 3 006 206 and 3 184 990.

These oils also find use in seals and as reactants, electrical oils, and the like.

109886/1992

example 1

A 1 1 three-necked round bottom flask was equipped with a mechanical stirrer ,, a gas inlet tube (which also serves for the periodic 'removal of the product), and a reflux condenser containing a _v immersing into the liquid layer thermometer. The reflux condenser was closed with a gas outlet pipe which led through a Queek silver barrier into the atmosphere. 200 ml of nitromethane and 5 ml (11.15 g) of nitromethane were added to the flask and the passage of isobutylene began. The reaction mixture was kept at 3-1 ° G with the aid of an ice bath. The isobutylene feed rate was 7.2 g / min., Resulting in a product formation of 8.5 ml / min. (Density about 0.85). At intervals of 20 minutes, the supply of isobutylene was interrupted and the stirrer was switched off and the layers were allowed to separate. The oil layer above (170 ml) was removed and the bottom layer of nitromethane, to which 5 ml (3% of the product volume) fresh nitromethane had been added to compensate for the loss of solubility, was returned to the reactor. The compartment was four passes lasting 20 minutes each the reaction interrupted. The catalyst in the nitromethane layer was destroyed in a simple manner with water with the slight formation of HCT vapors. There were no difficulties in destroying the catalyst due to an exothermic reaction. The combined oil layers (665 ml including 20 ml nitromethane) were washed with water, with 5% sodium hydroxide solution and again twice with

- 25 109886/1392

Water washed. To make handling easier, a Solvents such as pentane or heptane can be added.

Although the oil of this example contains all of the new polyisobutylene oligomers of the series Cg to Cp ₀ .... Cg ⁺ , fractional vacuum distillation can be used to obtain a fraction that is relatively pure in a given oligomer (e.g. C- ig) «

In the reaction carried out in this example, small amounts of water can be present in the catalyst and / or the starting material act as a promoter for the reaction. If extremely pure materials are used in the process, so a small amount of water can be added to initiate or accelerate the reaction. Also a lower one Alcohol (such as methanol) or a lower acid (such as acetic acid) can be used as a promoter. In general, the Reaction rate (compared to an anhydrous system) can be accelerated by adding 0.1 to 1.5 moles of HpO per mole of SnCl. can be added.

Polyolefins formed as products, such as the one in this example, may contain residual tin and chlorine (e.g. 250-5000 parts Cl per million parts). As is discussed in more detail below, these elements, in particular tin, are present as organometallic compounds that give the product HD properties (properties

- 26 109886/1992

a high pressure lubricant). If desired however, the chlorine (which is present in an amount of 2000 parts per million parts, for example) can be obtained by heating the Product can be removed from the product with calcium oxide (lime) and subsequent filtration. Also mildly catalytic Hydrogen treatment (for example, a hydrogen pressure of 14 kg / cm, 200 ° C, Harshaw NI-O104P catalyst) can be used in order to reduce the content of tin and chlorine to very low values (reducing the chlorine content, for example from 2000 to 6 parts per 1 million parts).

The procedure described in this "example" can also used to convert butadiene into trans-1,4- and 1,2-polybutadienes to convert. This is surprising because the cationic catalyst systems known to date convert butadiene into cyclic Polymers is transferred.

1-decene can also be polymerized with the catalyst system of this example if it is used instead of SnCl-AlCl. In particular, high yields of an oil with low viscosity are obtained. Oxygen-containing derivatives of these poly-1-decenes can be prepared in a similar manner by ozonolysis can be obtained as in the procedure of the next example .

Example 2
Polyisobutylene oil from Example 1 (260 ml, 221.4 g) and 800 ml

109886/1992

ORIGINAL INSPECTED

anhydrous methanol was added to a 2 L three-necked round bottom flask given, which was provided with a gas inlet tube, a mechanical stirrer and a reflux condenser. The flask was kept at about 0 ° G with the aid of an ice bath while an oxygen-ozone Strpm (5.2 mmol 0, per minute) during a Duration of. 150 minutes passed. After this time, the product was subjected to "hydrolytic work-up". For this purpose 300 ml of distilled water were added and the mixture was refluxed for 90 minutes. The oil layer was diluted with 500 ml of pentane and. one after the other with about 250 ml of water (twice) 5 / o ferrous sulphate solution, 5% sodium carbonate solution, water, 5% Sodium carbonate solution and water (twice) extracted.

The combined sodium carbonate and water extracts were acidified with concentrated hydrochloric acid and with Ether extracted. After drying, the ether was removed, yielding 8 g (3.6 #) of an acidic fraction.

The main pentane layer was dried over calcium chloride and the pentane removed on a steam bath. There were 194 g (87.6 percent by weight) of a neutral fraction were obtained. Analysis of this material by infrared spectroscopy showed that it had predominantly carbonyl (aldehyde or ketone) functionalities and lesser proportions of hydroxyl functionality would have. The analysis by Gas-Plüssig-

- 28 109886/1992

phase chromatography showed that the composition of the product substantially consisted of a repeating structural pattern of three main components in a given molecular weight range "· i ^{It st} possible that other components are not separated by the use of 183 cm-silicone oil columns and 183 cm-Polyäthylenglykolkolonnen In addition, low levels of constituents were found. There was only a very small amount of unreacted oil. This product obtained is sometimes hereinafter referred to as "PIB-Eeton" or "PIB-Ketone, with hydrolytic work-up " designated.

Example 3

The neutral product (PIB-ketone) from Example 2 was tested for its traction using a Roxana four-ball tester from Roxana Machine Works St. Louis Mo. It showed a higher traction or power transmission than the original polyisobutylene (a torque of about 85 g compared to an original value of about 72 g) and _> a higher traction than commercial polybutenes (torque about 66 g "). This indicates that the Product is suitable as a power transmission fluid or as a component of a power transmission fluid,

Example 4

The PIB ketone from Example 2 was distilled under vacuum and separated into several fractions. One of those factions

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in the range from 80 ° C to 110 ⁰ C at a pressure of 0.8 mm Hg was collected. This fraction contained relatively few components. The individual components were isolated by gas chromatography and characterized and identified with the aid of the data obtained by infrared spectroscopy, mass spectroscopy and nuclear magnetic resonance spectroscopy. The predominant component was

CH, CH, CH, 0 ι 3 ι 3 ι 3

CH ₅ CH ₅ CH ₅

O \ jU.A w ΟιΙλ O Uli / -

4,4,6,6,8,8-hexamethyl-2-nonanone. The two in lesser ones Proportions of the components present were identified as

CH ₅ CH ₅ CH ₅ CH ₅ CH, C-CH * C C1L-C-CiL-C OH

J. rj> \ J \ J i.Xf \ \ J vlin

CH, CH, CH, CH,

0 i 0 7th

1,1,3,3,5,5,7,7-octamethyl-i-octanol and

CH, CH, 0 CH,

I ³ 1 ³ II

riiT η riTT r \ prr rx ptl Π rip

T 2 ι 2 I.

.CH ₅ CH ₅ CH ₅

2,2,6,6,8,8-hexamethyl-4-nonanone identified.

The structural formulas of higher boiling fractions correspond these specified structures, but after the first tert-butyl group a corresponding number of additional units of the formula

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ι *

-CH ₉ -C- * I CH ₅

are inserted (for example, "up to a total carbon number of at least about 49 for ketones and at least about 50 for alcohols).

The "PIB ketone" is therefore a mixture that consists predominantly of ketones (at least about 75 mol $>).

fc example 5 ■

The neutral product obtained in Example 2 (50 g) was in Dissolved 200 ml of diethyl ether and reacted for 4 hours under reflux with an excess of lithium aluminum hydride (8.0 g). The excess Li-Al hydride was decomposed by reacting with ethyl acetate, with carefully 200 ml of 15 $ Hydrochloric acid was added. The ethereal layer was extracted twice with 250 ml of water, dried over calcium chloride and the ether removed on a steam bath. The oily product (48 g, 96 weight percent) was characterized as alcohol by the infrared spectrum. There wasn't any remaining carbonyl absorption. The gas chromatogram this compound showed a repetition of two main peaks, caused by components with the same molecular weight, which are passed through this column (183 cm, silicone rubber) were no longer separated.

The alcohols that have a large non-polar fraction and one

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containing very strongly polar alcohol groups are sometimes referred to as ^W PIB alcohol "" hereinafter. They are valuable solvents and are "particularly suitable as components of power transmission fluids and as components of solvents for polymers such as polystyrene and polymethyl methacrylate. They can also be used as intermediates for the preparation of the corresponding acetic acid esters.

Example 6

The alcohols from Example 5 (20 g) were mixed with an excess (30 ml) of esbetic anhydride and left for one hour heated in a steam bath. Excess water (100 ml) was added to decompose the excess acetic anhydride. The mixture was heated for an additional hour. Then were 100 ml of ether added and the ether layer separated. The ether layer was made twice with portions of about 100 ml of water extracted and then dried over calcium chloride. After removing the ether, an infrared spectrum of the remaining Added 20 g (100 percent by weight) of the oil. The infrared spectrum indicated the presence of carbonyl groups (esters) and the practical absence of hydroxyl groups (alcohol). This ester was both on its own and in mixtures (for example with hydrogenated polyolefin oils or hydrogenated paraffinic or naphthenic lubricating oils or with synthetic ones Haphthenes or adamantanes) as a power transmission fluid suitable. The ester is also a valuable component of a gear lubricating oil, especially a lubricating oil

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for a limited slip differential. Typical blended fluid or lubricating oils (these oils köitnen be partially or fully hydrogenated) to 95 ° i of such ester, and 99 to 5 l ° a 'paraffinic, or naphtheneschen Polyolefinöls or a mixture of such oils contain about 1.

Example 7

In a 21 flask, a solution was prepared by mixing 100 g of HydroxyI-amine hydrochloride, 600 ml of water, 400 ml of a 10 $ strength sodium hydroxide solution and 400 ml of ethanol Ketone (40 ml, 34 g) was added. The resulting mixture was heated and stirred at 80 ° G for 30 minutes. The entire mixture was diluted with 1000 ml of water and extracted with 500 ml of ethyl ether. The ether layer was extracted twice with 500 ml portions of water. The ether layer was dried over calcium chloride and the ether w on a steam bath removed. The oil obtained (28 g, 82.4 percent by weight) was examined by infrared spectroscopy. It was found that it contained oxime groups and had essentially no unreacted carbonyl functionality. This oxime is found in paraffinic and naphthenic mineral. oils are soluble and suitable as a component of a power transmission fluid or as a viscosity stabilizer for an oil-extended, unvulcanized rubber formulation.

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- ■ 33 -

A 3 liter round bottom flask was fitted with a gas inlet tube, a mechanical stirrer and a reflux condenser. the The device was charged with 1500 ml of acetic acid and 500 ml of a polyisobutylene oil prepared according to Example 1. By this mixture became a stream of oxygen-ozone for 240 minutes (5 1 per minute; 5.3 mmol of ozone per minute) passed. the The temperature was kept in the range from 25 to 50 ° C. with the aid of a water bath. The reaction mixture initially passed of two phases, but became towards the end of the reaction period. homogeneous.

The crude mixture was then subjected to an "oxidative work-up" subject. For this purpose it was heated to 90 to 100 ° G and over a period of 50 minutes 500 ml a 30% strength hydrogen peroxide solution was carefully added. The mixture was then refluxed at about 110 ° C. for 6 hours. 1000 ml of ether and 150 ml of water were added, the mixture was stirred and then the layers separated. The ethers

layer was twice with water and twice with a $ 0.2 igen ferrous sulfate solution (500 ml each). After that it was the ether layer with 500 ml of a 10 $ sodium carbonate solution and washed twice with 1000 ml of water each time. As the sodium salt the acid is more soluble in water than in sodium carbonate solution for the most part causes the separation. The remaining ether layer was dried over calcium chloride and the ether

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removed on a steam bath to give the neutral ketone fraction. Gas chromatography and infrared spectroscopy indicated that the product was similar to the product of Example 2, but had a more complex composition and showed evidence of strong isomerizations. This neutral fraction was obtained in an amount of 252 g (55.0% by weight) and is hereinafter sometimes referred to as "PIB-ketone, oxidative work-up". The sodium carbonate extract and the two water extracts obtained thereafter were combined, acidified by the careful addition of excess hydrochloric acid and extracted with diethyl ether (500 ml). The ether layer was dried over calcium chloride and the ether removed on a steam bath. The resulting liquid acid fraction was in an amount of 134 g (32.3% by weight) and is sometimes referred to hereinafter as "PIB-8 acid ⁿ . The infrared spectrum showed the absorption bands characteristic of carboxyl functions.

10 io PIB ketone paraffinic hydrogenated in a solvent-refined oil resulting in a torque transmission of 67 g compared to a value of 58 g, which is obtained with the hydrogenated oil without additives. The "PIB ketone, oxidative work-up" leads to similar results.

Each of the polar compounds described acts as an additive to improve power transmission or traction in

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any mineral oil, which may be paraffinic or naphthenic, including hydrocracked oils or in any compatible synthetic fluid (silicones, ester oils, polyolefins, fluorinated fluids). The polar compounds can be used as high pressure additives and / or antiwear additives. The polar end of the molecule is obviously strongly attracted to the metal surface and it comes to this _e ¥ ise by the protective effect of the "framework" with geminal structure a lesser .Verschleiß the surface about.

Example 9

The sodium salt of the acidic fraction can be used in a simple manner can be obtained if the first water extraction, which follows the extraction with 10 $ sodium carbonate solution, according to Example 8 is carried out. When these two extracts are mixed together a phase was eliminated. This phase can be diluted with diethyl ether and separated. By Drying over calcium chloride and removing the ether on a steam bath gives a viscous liquid product which exhibits the infrared spectrum of a sodium salt of a carboxylic acid.

This product is suitable for use as a detergent, as a surfactant and as a solubilizing agent (solubilizing agent Middle). At least $ 20 diethyl ether can be dissolved in water which contains a few percent of this salt will.

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The sodium salt can also be obtained directly from the acid and a suitable one Base can be produced under almost anhydrous conditions. Salts of others can also be used in a corresponding manner Metals,! For example lithium, calcium, magnesium, Barium, zinc and cobalt. These salts are

valuable means for compounding lubricating greases, hydraulic oils. Lubricating oils and the like. These salts (e.g. Na ⁺ ) can be used to increase the viscosity and / or reduce the acidity of lubricants, in particular lubricants for traction or adhesion gears *. '-.

Example 10

The acidic fraction prepared according to Example 8 (25 ml, 22.6 g) _for 200 ml of methanol and 30 ml of 96% sulfuric acid were placed in a 500 ml round bottom flask and refluxed for 6 hours. 200 ml of water and 200 ml of diethyl ether were added and the layers were separated. The ether layer was extracted in P in the order given with water, 10% sodium carbonate solution and water, 200 ml being used for each extraction. The ether layer was dried over calcium chloride and the ether removed on a steam bath. The neutral ester obtained as the product was present in an amount of 18 g (80 percent by weight). This product is sometimes referred to hereinafter as "PIB ester". Gas chromatography indicated that the product consisted of three major components with a repeating structural scheme at each general molecular weight value. The repeating units were

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characterized by that consisting of four carbon atoms

unit

CH,

—GHp-O

CH ₃

Analysis by infrared spectroscopy showed that for ester functionality and the lack of acid functionality expected absorption.

The ester was useful as a power transmission fluid and as a component for mixed power transmission fluids or fluids. A particularly valuable base stock comprises from 1 to 99 i ° of the ester and 99 to 1 "/> of at least one paraffin or naphthenes with a SAEs viscosity at 38 ° C in the range of 25 to 25 000th

Example 11

1 g of an acid prepared according to Example 8 was 1 ml Thionyl chloride mixed and carefully heated on a steam bath until the evolution of gas ceases. Then v / urde heated and the thionyl chloride under a stream of nitrogen evaporates. The solution, which was kept at 80 to 90 ° C. for 5 minutes, was closed with a water jet vacuum created. The product obtained was an oil with a pungent odor, the infrared spectrum of which is characteristic of acyl halides Showed absorption.

Example 12 That as the product of the example. 11 obtained acyl halide

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was poured into 25 ml of methanol. There were 50 ml v / ater and 50 ml of diethyl ether were added and the layers were separated. The ether layer was once with 50 ml of 5 $ sodium carbonate solution and extracted twice with 100 ml of water each time. The ether layer was dried over calcium chloride and the Ether removed on a steam bath. Bas scored oily ~. product was determined by gas chromatography and infrared spectroscopy analyzed, which showed that it was with the PIB-iister des Example 10 was identical.

Example 15

50 g of a of Example 8 produced an acid and excess (20 g) at 85 $ hydrazine hydrate (the remaining 15 i ° are water) were mixed in a 250 ml Erlenmeyer flask while stirring with a magnetic stirrer. The mixture warmed up immediately. The temperature was then increased to 125 ° C. by external heating and excess hydrazine was evaporated under a well-drawn hood. The temperature was held at 125 ° C for two hours and then increased to 185-210 ° C where it was held for an additional two hours. An infrared spectrum of the very viscous material indicated that it was essentially converted to the acyl hydrazide. This product was dissolved in diethyl ether (400 ml) and extracted twice with 500 ml of water each time. Serious emulsification problems were encountered with many of these extractions. These emulsions were broken with a concentrated sodium chloride solution, but occasional phase separation was still possible

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a period of one to two days required. The ether layer was dried over calcium chloride and the ether removed on a steam bath.

The product obtained was very viscous and light orange Coloring. An infrared spectrum was recorded again, which showed somewhat sharper absorption bands. Absorbances at around 3.1 were particularly characteristic of this product Microns and 6.1 microns typical of ayl hydrazides. This hydrazide differed from others in that it was was liquid rather than solid and it was soluble in pentane, white oil (white mineral oil) and other hydrocarbons, but insoluble in water. This behavior is opposite to that of oleic hydrazide, which is solid and insoluble in oil. Are adipic acid dihydrazide, acetyl hydrazide and benzoyl hydrazide also pests that are soluble in water, but in hydrocarbons are insoluble. The hydrazide obtained in this example is special because of these solubility properties valuable as a power transmission medium or as a viscosity stabilizer in oil-extended non-compounded synthetic rubbers. It is also suitable as an emulsifier and as an antiozonant in rubber.

Example 14

10g of the acid prepared in Example 8 were in 50 ml Dissolved methanol, which contained an addition of 1 mol of water. During one hour, 3 g of sodium borohydride were in small

109886/1992.

Proportions added. Then 100 ml of ether and 100 ml of water were added and the layers were separated from one another. The ether layer was washed twice more with 100 ml of water and this ether layer was then discarded. The combined water layers were carefully acidified with concentrated hydrochloric acid and 100 ml of ether were added The layers were separated. The ether layer was diluted with 100 ml of water, dried over calcium chloride and the ether removed. The acid obtained was converted into the corresponding ester by the methods described in Examples 11 and 12. Gas chromatography showed that the middle The amount of one of the three main ingredients described in Example 8. Since it is well known ₃ that sodium borohydride does not reduce carboxylic acids under these conditions, but does reduce esters, ketones and aldehydes, it must be assumed that the middle and greatest proportions are present Component the original represents the same acid component and that the other peaks different carbonyl.! -; represent constituents which v / e.-ien of the strong Icsliohmachena mentioned effect> ilee Katriupsalses of the carboxylic acid were not separated *

⁴ O f; des gaai ^ S Example 2 1-3 ^^ 3 "derive neutral ie ^ rii ^T -mräe ^r > longitudinal? .. '; zn 85? i« = ige "^ asterr ·. · ¹ Esci ^ säiir *: (■ *>■■; ml) iie ^ eTieiij which ^{contained 9} r chvorric acid and on ei - · ■ '■: ■.! ■ nnipio'

ι Ha

was heated to about 90 0. This mixture was allowed to stand for 2 hours with occasional shaking. then 200 ml of water and 200 ml of ether were added. The ether layer ' was extracted with water, 10% hydrochloric acid, 10% sodium hydroxide solution and twice with water. It was then passed through a chromatography column (91.4 xm χ 2.5 cm) with aluminum oxide for the chromatography was filled. The ether used to elute was removed, a dissolved salt of chromium (III) remained as the product. Analysis by gas chromatography showed that the obtained product is an essentially purified form of the specified ketone

CH
I.

CIL

C f CH * C.

CH ₃ J

-C CIL

χ. ^X = ¹ - ¹⁰

depicted.

The paramagnetic complex with europium (III), / Tris (dipivaloiue thana to) -europium (III ) J-2 , 2,6,6-th fcrame thylheptanedionate, hereinafter referred to as Eu (DPM) ₃ , can be used as an NMR-ShLftreagent are used and therefore represents a means of identifying oxygen compounds, v / ie that according to Example 4 and Beif: j [iiel 15. Eu (DFM) ₃ can be used to induce selective pro-umrenonance shifts, the chemical shift Differential

zvAi between geminal methyl groups and between isolated methylene groups, as in afcark branched alcohols

and ketones are present.
Shifts

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BATH ORIGINAL

Example 16

The reaction product according to Example 1 contains substantial proportions of tin and chlorine. Probably are tin and chlorine bound in a highly soluble and compatible form to one or more of the isobutylene oligomers. In any case, this can

Recovered polyisobutylene oil also contain tin and chlorine. This new tin and / or. Polyisobutylenes containing chlorine »! Has improved anti-wear properties (e.g. a Abrasion scratches "wear-scar" in the four-ball tester in the size order from 0.4 to 0.6 mm compared to around 0.75 mm a solvent-refined paraffinic lubricating oil mi b comparable viscosity). Chemical derivatives of these compounds (such as the derivatives obtained in Examples 2-6 and 10) can also have improved anti-wear properties that are wholly or partially caused by the presence of tin and chlorine. on the other hand can benefit from the improved anti-wear properties be wholly or partly an inherent property of this derivative.

An anti-wear additive (which can be used, for example, for adding to conventional naphthenic distillate oils, hydro-refined oils, hydrocracked oils, white oils, solvent-oil refined oils paraffinic oils or mixtures of two or more of these oils can be used Reaction products (or oils containing tin and chlorine) can be obtained by methods such as, for example, extraction with a solvent (preferably acetone) for

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the assumed organotin-chlorine complex. Too "preferred Solvent components include acetone, ethanol, methanol, methyl ethyl ketone, Dimethylformanide, furfural, nitromethane, nitroethane and the like, that is, solvents which do not dissolve the oil but the more polar complex. By diene additives "or additives is in concerts, "where a level of 100 parts tin per 1 million parts of the oil and typically a range of 50 parts tin per 1 million parts oil to 10 percent by weight Tin is achieved, an easily detectable protection against achieved.

Eii; r embodiment of the invention therefore relates to mi, '-: lubricating oil additives, which the tin-containing products dt. * * Polymerization of isobutylene using an ethylene chloride catalyst between -80 ° C and 100 ° C at ei μ ν' ·: \ Represent pressure from 0 to 17.6 at. These additions k ■ "?! ' en 0005-50 weight percent tin contained. I: ■ · 3 products can e.g. also as additives or additives .reibstoffen (for example, diesel oil, gasoline and Düsenti material) are added, in order to prevent wear..

L j) three-necked round bottom flask with 1 1 capacity, the one with ί :: mechanical stirrer and one; The thermometer was charged with 200 μl of nitroethane and 5 ml (11.2 g) of stannic acid. ^N he temperature was maintained with the help of one of the t'.i 30 C ^ e, while; for an hour

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BATH ORIGINAL

Isobutylene was initiated. After this time the stirring was stopped and the top oil layer (530 ml) was separated from the nitroethane layer below (160 ml). After washing and drying over calcium chloride, the Distilled oil layer. A fraction boiling up to 82 ° C at 2 mm Hg (which was discarded), one of Fraction boiling at 82 ° G at 2 mm Hg to 175 ° C at 1 mm Hg with a value KVqqOq = 18.14 cSt.

The device described, in which only the flask had a capacity of 500 ml, was charged with 200 ml of nitromethane and 20 ml (44.6 g) of stannous chloride. The temperature was held at 15 ° 0 for 21 minutes and isobutylene was fed in at the rate indicated above. The upper layer was washed with water and dried over calcium chloride. Then it was distilled and the fraction boiling up to 80 ° C. at 1 mm Hg was removed. The oil remaining as residue (KVqqO _ß = 46.74 cSt) was kept for the wear test.

The same device was used in another experiment using 200 ml of nitromethane, 200 ml of pentane, 20 ml (44.6 g) of stannous chloride and 150 microliters of water as the feed. The temperature was held at -10 ^D C for one hour while isobutylene was fed at the same rate. The mixture was stirred for an additional 30 minutes. The oil obtained as the product was washed

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and dried over calcium chloride. The pentane was removed under a water jet vacuum and the product was distilled to a boiling point of 80 ° G at 1 mm Hg. The small amount of the distillate was discarded. The yield of bottom fraction (KVqqOq about 420 cS) was about 500 ml. It contained 4.5 $> tin and 2.5 ° /> chlorine after filtration through diatomaceous earth at 80 to 100 ° C. This oil (100 ml) was mixed three times with each . 25 ml of acetone extracted. The extracts were combined and the acetone was removed by heating to 90 ° C under a stream of nitrogen. The extracted oil (about -90 ml) and the extract (10 ml) had similar viscosities. The initial oil contained 4.6% tin, the extracted oil contained 1 $ tin and the extract contained 33 $ tin. Like the other tin-containing products listed, this oil and extract can be added to lubricants to provide anti-wear properties.

Example 17

A polyisobutylene oil (33 g, about 1 mole) made according to Example 1 was dissolved in 150 ml of carbon tetrachloride dissolved and bromine was added dropwise to the stirring solution. White fumes could be heard over the reaction vessel to be observed. These vapors reacted strongly acidic on damp indicator paper. Those caused by hydrogen bromide Vapors indicate that a substitution reaction occurred in addition to the expected addition reaction. The addition of bromine

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continued until the color of the unreacted bromine persisted when heated for several minutes. The total amount of the bromine added was about 40 g or so 2 1/2 times the theoretical amount required for the addition reaction. The CCl.-layer was washed twice with water, extracted once with sodium bisulfite solution (to remove the excess bromine) and twice more with water. Of the Carbon tetrachloride was removed by heating on a steam bath. This left a light brown oil, which is shown below sometimes referred to as "PIB bromide". The infrared spectrum this oil showed -CH, -C-C- and -CBr-functionality. The oil was a starting material for active halogen and was found to be useful as an anti-welding agent Agent (anti-welding agent, anti-weld component) in cutting oils. The yield was 60 g of that obtained as the product Oil. The chloride can also be produced by a corresponding reaction of the olefin with chlorine and is a Valuable high pressure additive, especially for the lubrication of traction or adhesion gears. PIB bromide (or "Individual brominated polybutenes" can be mixed with diamines or other polyamines (for example at reflux in dimethylformamide as a solvent) to form an imine amine. These are compounds of the following structure particularly good components for power transmission fluids:

(CH,) ^ CH ^ C-

^{5 5 ά} . \
CH

CH,! ³

H ■ Ν-

NH ₂

109896/1992

In this formula, η is preferably 2 to 10 ("Deispiexs-

wise 2) and n ¹ 1 to 20 (e.g. 3).

A preferred polar power transmission medium is 5,5,7,7,9-

Hexamethyl-4-azadecylamine.

Example 18

330 grams of polyisobutylene oil (about 1 mole) prepared according to Example 1 was mixed with 100 grams (about 1 mole) of maleic anhydride mixed and in a flask equipped with a reflux condenser with stirring to a temperature of 225 ° C ■ heated, which was reached within a period of about 1.5 hours. The reaction could be confirmed by infrared spectroscopy to be tracked. Within a certain time, the absorption due to double bonds in the oil disappeared. At the same time, the absorptions attributable to maleic anhydride disappeared and new bands appeared. These Bands still showed anhydride functionality. After 6 hours the reaction was stopped and the reaction mixture allowed to cool and stand overnight. That During this time, the mixture separated out some solid matter. 500 ml of pentane were added and the mixture was cooled in ice, to cause another precipitation. The solids were filtered off from the mixture on a porous glass filter and washed with a small amount of cold pentane. After drying, the resulting white solid weighed 23 g and exhibited an infrared spectrum through which it could be found was identified as unreacted maleic anhydride. The pentane was removed on a steam bath, with a very

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viscous, sticky oil was obtained. The yield was 400 g. The infrared spectrum of the reacted with the formation of derivatives Oils showed some remaining maleic anhydride with a large proportion of another anhydride, probably Polyisobutylene succinic anhydride. This viscous oil was suitable as a detergent, as an anti-wear agent and as an intermediate for producing a hydrazide.

Example 19

11.8 g (about 0.2 mol) of 85% hydrazine hydrate were added to the product from Example 24 (42 g, about 0.1 mol) with stirring. The temperature of the mixture rose to about 80 ° C. during the addition. The resulting mixture was stirred for one hour and then heated to 150 ° C. while nitrogen was bubbled through the mixture for 2 hours. This removed the excess hydrazine and converted the portion present as salt into hydrazine. The resulting mixture was dissolved in ether and extracted with water to remove hydrazine and its salts. The ether was removed, leaving a very viscous, sticky, yellow-brown oil (33 g, 70 % of theory). The infrared spectrum of this material was similar to the infrared spectrum of other acyl hydrazides. The connection is a valuable part of a "power transmission fluid".

Example 20 Polyisobutylene oil prepared according to Example 1 was fractionally distilled at atmospheric pressure to give a product

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- AO _

^f r j -

containing at least 80 percent by weight of the Gg-isobutylene oligomer ("tetraisobutylene"). This predominant Cj, fraction had a boiling range of up to 245 O and more than 90 percent by volume distilled over at 240 O. Gas chromatographic analysis showed that these dominant C., - fraction v / ess than 10 weight percent C ₁₂ ~ oligomer and less than 10 weight percent of the Con ~ ^unt ^ higher oligomers contained.

Example 21

In a 5 l kettle equipped with a vibromixer, 2260 ml Cold aged lard oil (winter strained lard oil) mixed with 400 ml of tetraisobutylene (prepared according to Example 20). The mixture was heated to 121 ° C and the vibromixer operated at maximum speed. Then 239 g Sulfur was added and the temperature of the mixture was increased to 190.5 ° C. and held at this value for 2 hours. Thereafter the mixture was cooled to 93.3 ° C and air at a moderate rate (below a value at the splash and Mixing took place) passed through the mixture for one hour with the help of a glass tube. The obtained sulfurized Oil was analyzed and found to contain 8.23% sulfur. A 10 gram portion of the sulfurized oil was added dissolved in 100 g of a commercially available solvent-refined paraffinic lubricating oil which has a viscosity of 99 ° G of 40.45 SUS, an ASTM viscosity index of 104 and, according to ASTM D 2007, contained 12 ^ aromatics. the Oil solution remained clear and it formed after testing

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at 2.2 C overnight and for a week at room temperature no deposition.

Example-22

Cold-aged SpepkÖl (2550 ml) was mixed with 450 ml of 80% pure triisobutylene in a 5 l kettle equipped with a vibromixer mixed, which has been prepared by a distillation according to Example 20, but at a lower temperature was. The mixture was heated to 121 ° C and the vibrating

'' mixer operated at maximum speed. These conditions were maintained while 266 grams of sulfur was added over a 30 minute period. The temperature was increased to 190.5 ° C. and left at this value for 2 hours. The mixture was then cooled to 93.3 ° C for one hour and air was passed through the mixture using a glass tube at a moderate rate, below the rate at which splashing occurred. The resulting sulfurized oil was analyzed and found to be 8.6 % sulfur based

ψ on the total mass, contained. A 10 gram portion of the sulfated oil was dissolved in 100 grams of the solvent refined paraffinic oil described in Example 27. After testing at 2.2 ° C. overnight and at room temperature for a week, the oil solution remained clear without any separation.

Example 23

A suitable lubricant for a controlled slip differential that is also a valuable resource for the

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is the lubrication of a friction gear ratio / (traction

drive transmission) comprises a mixture of the following ingredients (all hydrogenations were carried out to a saturation of at least 98%):

Volum ° / o component gg, g _c

(cSt) (cSt)

7.0 Hydrogenated Gosden SH06 11.04 polybutene

28.0 Hydrogenated Cosden SH15 33.5 Polybutene

31.6 Hydrogenated poly-oc-methyl 23.0 2463 Styrene

21.0 Hydrogenated poly-oC-methyl 4.65 39.6 Styrene

7.4 Anglamol 93 (HD additive)

3.0 Amoco 9000 (dispersant)

1.0 Ultraphos 11 (static modifier)
(Low Static Modifier)

1.0 Synthetic sulfurized oil from Example 21 or 22

The additive Ultraphos 11 is a surface-active organic phosphoric acid ester of a linear aliphatic ethoxylated alcohol. The hydrogenated poly (alpha-methylstyrene) lies predominantly in the hydrindane form. A valuable transmission fluid can also be formed when some or all of the hydrindane groups are through

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the corresponding indane groups have been replaced. The forms of a dicyclohexylalkane polymer exist as minor components of the hydrogenated poly (alpha-methylstyrene). Suitable transfer fluids may be prepared up to 100 of such io "dumbbell""(dumbbell) polymers using.

Other hydrocarbons found in these transmission fluids may be present (in addition to the oils already mentioned, such as hydrogenated paraffinic or naphthenic lubricating oils) -can by reacting (for example by alkylation) of isobutylene or polyisobutylene with naphthenic hydrocarbons (such as adamantanes, hydrindanes or cyclohexene). This isobutylene reaction products with Adamantanes are described in Example 24.

Example 24

A solution containing 25 volume fo Äthylaluminiumsestjuichlorld was added to a mixture of 50 ml dimethyladamantane and 1 ml of tert-butyl chloride. Gaseous isobutylene (45 g) was bubbled in while the mixture was maintained at 0-5 ° C. The reaction was interrupted with 5 ml of water, the reaction mixture was extracted with water and distilled in vacuo. The distillation flask was maintained at 280 ⁰ C to cfacken all present high boiling products. The top fraction passed over at about 170 ° C. About half of the oil was cracked in this way while

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the remainder distilled over without awning. About 30 ml of oil was obtained. This oil had a value KV _nn o _n 4.40 cSt and VTF-VI of 26. A similar experiment hei -30 ° C gave
about -20 ml (almost the total amount .wurde cracked) with a value KVqqOq of 4.22 cS and VTP-VI of 62. Analysis by infrared spectroscopy indicated that the oil obtained as the product contained the adamantane group. This oil is suitable as a transmission fluid or as a component of a transmission fluid. One of the predominant components of this transfer film has the following structure:

CH,

CH;

C-

CH,

in which η is an integer from 1 to about 20 and R ^{1 is} the group

CH,

or one of the in the description of the invention Olefin hydrocarbons represents enumerated olefinic end groups.

The adamantane compounds that have these olefinic end groups contain, can be converted into polar compounds,

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which have one of the aforementioned functional groups. This reaction can be carried out by the methods described in the examples Reactions take place.

Example 25

As a component of a basic approach to a transmission fluid 3-0yclohexyl-1-, 1,3-trimethylindane can be used. These Compound has the following structural formula (I)

(D

W This compound was prepared in a t-l Sehüttelautoklaven made of steel, the fixed-dC-methylstyrene, 100 g of dimeric indane (3-phenyl-1,1,3-trimethylindan), and 2 g of a catalyst of 5 $> rhodium on Coal (Englehart Industries)

was
charged / The autoclave was filled with hydrogen under one

Pressure of 119.5 atu charged and heated to 100 ° C Der The pressure fell to 21.1 atmospheres after 1.5 hours. The autoclave was cooled and the contents mixed with Peatan. The pentane solution would be through a silica gel column (61 cm χ 5.1 cm)

109886/1992

passed and eluted with more pentane. The first "two fractions (total 9 g)" consisted of the fully hydrogenated hydrindane derivative. The next 5 fractions contained 80 g of the above-identified compound I. About 10 g of the unreacted starting material was recovered by further elution. The structure of the compound I was elucidated by a combination of infrared spectroscopy, NMR spectroscopy and mass spectrometry. The purity obtained by GC analysis was about 80 56. The oil had a KVggO «of 3.24 cSt, KV ₃₈ O ₀ of 25.17 cSt and VTP-VI of -139. The 3-cyelohexyl-1-, 1,3-trylmethylindane was subjected to a tensile test using a "Roxana" four-ball tester. The torque value obtained for this sample was 68 grams. The corresponding value of the completely hydrogenated material (hydrindane derivative) was 70 g. The non-hydrogenated sample showed a torque value of 59 g. The accuracy of a single measurement in this test is - 1 to 2 g.

Example 26

ι * ι iiiHi ι π ■ »■ ii ι ι,

1,1,3-Trimethyl-3- (2,2-dimethylpropyl) hexahyd ^ indane can be used as a component of a hydrocarbon base that is used to compound a lubricant for a traction or friction transmission. This compound was easily obtained by hydrogenating the corresponding indane. The compound is particularly noteworthy because it has a very low viscosity compared to the corresponding compound in the series of <* - methylstyrene dimers

109886/1992

(KYqo about half) and because their viscosity index is wide . higher than that of the parent compound. The fully saturated and aromatic forms are roughly the same ' Eraft transmission (traction) properties.

1,1,3-Trimethyl-3- (2,2-dimethylpropyl) indan (80 ml), which had been prepared in the manner described in Example 25, was placed in a 300 ml shaking autoclave containing 2 g ο fo Rhodium on charcoal was charged. The autoclave was charged with hydrogen under a pressure of 105.5 atm and heated to 200 ° C. The autoclave was cooled for 6 hours, the oil removed and filtered. The crude product had a KV _gg o _c of 1.86 cSt, KV ₅₈ O _Q of 5.91 cSt and VTP-VI of 108. Since it appeared that there was a small amount of volatile material (which was probably formed by cracking during the hydrogenation) ) the sample was fractionally distilled and the fraction boiling up to 60 ° C. at 0.2 mm Hg was removed (topped up to 60 ° C. at 0.2 mm Hg). Only about 2 to 5 ml of the distillate was collected. The viscosity properties corresponded to the following values: KV _QQ o _n of 1.91 cSt,

₈ O _c of 6.46 cSt and VTP-VI 85. The sample contained at least 60 fo of the cis-trans isomers of structural formula II.

CH ₅ C-CH,

CH, -

⁵ (II)

109886/1992

The joint was subjected to tensile testing using the Roxana four ball apparatus that was modified to perform torque measurements. This sample showed torque "of 65 g. The corresponding torque of unhydrogenated e £ -methylstyrene dimer is 59 g. The accuracy the test is about - 1-2 g.

Example 27

400 ml of nitromethane and 300 ml of distilled isobutylene trimer were placed in a 1 liter flask and heated to 85.degree. 6 ml of SnCl- were added. Then 75 ml of C <-methylstyrene were added dropwise over 35 minutes. The temperature rose rapidly to 95 ° C and was held at this value. After the addition was complete, the mixture was stirred for a further minutes at 95 ° C. and then cooled to room temperature. The above oil layer was separated and washed twice with water, and the water layers were discarded. The oil layer was _{dried over OaCl 2} and distilled and the 80 ml of the product boiling from 60 to 100 ° C. at 0.5 mm Hg were retained. The major component (about 60 volum fo) was identified as a compound of structure III by a combination of infrared spectroscopy, NMR spectroscopy and mass spectroscopy. It had a value of 1.65 cSt, KV, _Q o "of 5.69 cSt and VTF-VI of -2.

JO V ^

1.0 9886/1992

(III)

The same compound could be made using diiso-

trutylene are produced.

This compound, 1,1,3-trimethyl-3- (2,2-dimethylpropyl) indane, can be used as a component of a hydrocarbon base for a transmission fluid used (e.g. for the base

according to Example 23).

The connection was made in the manner described below. It turned out to be fairly pure isobutylene trimers used, but the main product was obviously from Isobutylene dimer derived. The following is likely

Balance before:

A η π, η tr ~ -

' ^C 8 ^H 16 ^{+ C} 4 ^H 9

CH, CH

is

) ₃ C-CH ₂ -C = CH (CH ₃ ) ₃ C-CH = C

^H 3

Stannous chloride in nitromethane causes under certain conditions

109886/1992

but does not rapidly polymerize "certain olefins of isobutylene oligomers (also other olefins, including polar olefins such as methyl methacrylate, will not polymerized). Olefins that can be polymerized in this way are styrene, cC-methylstyrene, isoprene, butadiene, Isobutylene, 2-methylbutene-1. If the oC methyl styrene cation can be produced in the presence of a large excess of the other olefin, it should be the predominant reaction an addition reaction may occur. If this reaction is carried out under conditions which are known for the formation of the indanedimer, Carried out with cC-Methy! styrene, then substituted Obtain indane. The compound of this example shows a remarkably low viscosity and a high viscosity index compared to the corresponding derivatives of the cC-methylstyrene dimer.

The joint was subjected to a tensile test using the Roxana four ball apparatus. About this sample torque obtained was 63 g.

Table 3 shows torque values obtained in the Roxana four-ball device for some of the polar compounds described here.

Table 4 shows the structural formulas of some cyclic polar compounds which are used as constituents of Lubricants for a traction or friction transmission are suitable. These components are particularly valuable when used in an amount of about 0.5 to 10

109886/1992

Percentage by weight in a Sehmiermitter base which contains at least one fully or partially hydrogenated oil of styrene polymers (or polymers of substituted styrene, such as cC-methylstyrene), polyolefins, naphthenic or paraffinic lubricating oils -. These polar Verbindüngen may also be used 'in lubricants which also comprise 0.1 to 95 i ° of the polar compounds with geminal previously described structure. Sebacic acid esters, such as dioctyl sebacate or dibutyl sebacate, can be used as polar components (in a proportion in the range from 0.5 to 10 percent by weight) of lubricants, such as the lubricants specified above for a traction or friction transmission. For example, up to about 7 volume percent of such an ester can result in a substantial increase in the traction coefficient of the mixture of hydrocarbon base oils given in Example 23 or in the total mass of lubricant given in Example 23. The ozone treatment described in Example 2 can also be used to improve the initial and post-aging (with copper according to ASTM D 1934-B) performance factors of hydrorefined mineral oils 2U used for electrical purposes, particularly hydrorefined naphthenic oils with a SUS viscosity in the range from 40 to 20,000 SUS at 38 ° C. For example, a naphthenic distillate with a viscosity of 2000 SUS (at 38 ° C), which at 329 ° 0 and 70.3 atmospheres 100 % H ₂ , a liquid hourly space velocity LHSV of 0.3 had been hydroraffinated in the presence of sulfided ₉ Mo oxides on Al ₃ Oj, with

109886/199 2

0.5 weight percent ozone brought into contact. It was a dark-colored oil obtained, which after treatment with 96? b-HpSO., washing, neutralizing and treating with adsorbent (to remove the dark colored products) made a good cable oil.

Methods for the analysis of the branched olefinic and paraffinic Oils described here (as in Example 1) are described in J. Pol. Sci., Part A-1, Volume 9, Pages 717 to 745 (March 1971).

Example 28

200 ml of nitromethane and 5 ml of SnCl. are in a three-necked round bottom flask with 500 ml capacity, the with a gas inlet tube, mechanical stirrer, reflux condenser, a external bath and a thermometer was provided, while isobutene was passed into the mixture, which was kept at 36 ° C will. The isobutene is fed to the flask at such a rate that after the air has been displaced from the Piston at the outlet no gas flows out. After 26 minutes, the flow of isobutene is interrupted and the contents of the Transfer the flask to a separatory funnel. The conversion of isobutene is quantitative. After standing for 5 minutes the nitromethane layer (202ml) is used for phase separation drained from the bottom part of the funnel. The oil layer (235 ml) is washed twice with saturated aqueous sodium chloride solution, once with 5 $ aqueous sodium chloride solution and two more times with saturated aqueous sodium chloride solution washed. The oil layer is then over

109886/1992

dried anhydrous calcium chloride and transferred to a vacuum distillation apparatus. It is distilled, the entire portion boiling below 80 ° C. at 0.5 mm Hg being removed. The remaining oil fraction (100 ml) has the following properties: KV ₀₀ O _n ■ = 4.25 cSt ~ KV, _D o _n = 22.42 cSt, VTF-VI = 98; ASTM-VI = 104. (The value KV means the kinematic viscosity, determined according to ASTM D 445). The distillate (100 ml) contained about 49% of trimers and tetramers of 49 ° f. (As determined by gas chromatography). Any dimer present would remain in the trap (10 ml). The loss due to batch drying is about 30 ml.

Example 29

Example 28 was repeated, with the modification that the oil was distilled and the portion boiling from 80 to 200 ° C. was collected as the oil fraction. This fraction had the following properties: KV ₀₀ O ₀ = 3.23 cSt, KV ₅₃ O ₀ = 14.09 cSt, VTF-VI = 105, ASTM-VI = 104. This shows that the "high viscosity index of the product does not cover a wide mixing range due to the molecular weight of the product.

Example 30

The polymerization is carried out in the manner described in Example 28, except that the reaction temperature at 25 ° C is maintained .. This can be obtained ml of the product in 26 minutes 235th The distillation gives 33 ml

109886/1992

a low-boiling distillate (40 % trimer, 57 i ° tetramer) and 188 ml of a remaining oil. This oil is passed through a 30.5 cm column filled with activated aluminum oxide. The oil obtained is completely clear and has the following properties: KVqqOq = 13.56 cSt, ₈ O ₀ = 145.2 cSt, VTF-YI = 96, ASTM-VI = 96.

All of the polyolefin oils according to the invention can according to known methods are partially or fully hydrogenated (for example using one made of palladium catalyst consisting of activated carbon, at 'a hydrogen pressure of 175.8 at and a temperature of 274 ° C),' to improve their stability. The polyolefin oils or hydrogenated oils can be fractionated in vacuo at 40 to 250.degree be distilled. Distillate fractions that span the full boiling range can be used as feedstocks can be used from which individual hydrocarbons (olefins or paraffins) can be obtained.

The branched one present as the main component

Hydrocarbons in the distillate fractions can be separated and separated into fractions using chromatography of fairly high purity. This separation can be achieved by programmed linear temperature and isothermal gas chromatography take place. In most cases, chromatographic fractions can contain a single molecular type each Include carbon number, using silicone rubber columns under isothermal conditions at a

109886/1992

Temperature in the range τοπ 210 to 280 ° C can be obtained. In certain cases these columns were used to create fractions obtained from hydrocarbons with several different Passed carbon numbers. These concentrates can then be chromatographed again in analytical columns, whereby pure chromatographic fractions of one type of molecule with a single carbon number are obtained.

Example 31

A polyisobutylene)! was made by careful vacuum cracking. made of commercially available polyisobutylene (number average molecular weight 23,000) in a round bottom flask equipped with a stirrer at about 375 ° C and 1 mm Hg. The product obtained was continuously distilled over, with essentially no reflux or no fractionation taking place. The products obtained as distillate and in traps were combined and again distilled at 100 ° C. at 0.3 mm Hg. The more volatile distillate fractions were discarded. The remaining less volatile, thermally cracked W isobutylene bottom fraction which 'is about 35 to, 40th fo of the total charge can be used as the olefin oil for preparing polar compounds, for example according to the reactions of Examples 2, 5-19, 21 and 22. Fractions which are obtained from these bottom fractions by gentle distillation can also be used to prepare these polar compounds.

109886/199 2

Example 32

The "thermally cracked" polyisobutylene oil from Example 29 was hydrogenated in a 1 liter hydrogenation reactor made of stainless steel "at a hydrogen pressure of 175.8 at at 274 ° C. for 6 hours". The catalyst "consisted of 0.5 ~ / ° palladium on coconut charcoal with a grain size corresponding to a sieve with 4 to 8 meshes per 2.54 cm (mesh size 2.38 to 4.76 mm).

A gas chromatogram of the hydrogenated, thermally cracked Polyisobutylene contains a series of peaks that are homologous Represent a series of two different basic classes of branched hydrocarbons. A class is symmetrical, has an odd number of carbon atoms and has two terminal isopropyl groups. The second group is unbalanced, consists of an even number of carbon atoms and contains an isopropyl group and a tert as end groups, Butyl group. The gradual increase in the carbon number in each series has an additional G>, isobutylene unit causes in the hydrocarbon chain. There weren't any appreciable proportions of the odd-numbered species found in these non-volatile fractions, the two terminal ones have tert-butyl groups. In area C .... to C. ~ were the concentrations of the Cj ^ and C «-species are far lower in the In terms of the concentration of the higher carbon compounds, which is likely to result in the loss of one Part of these hydrocarbons in the volatile fractions is due. The purity and the. Molecular weight data for each type of hydrocarbon recovered

109886/1992

Tons Gj «j- to C ^ ₀ are listed in Table 1. The purity of these fractions varied from 96.7 to 99 ⁺ i ° and the calculated molecular weight for each type of a certain carbon number was in good agreement with the experimental molecular weight value obtained by vapor pressure osmometry.

The identity of these branched hydrocarbons, determined by NMR spectroscopy, is given according to the structural assignments given in J. Pol. Sci., Part A-1, Volume 9, pages 717-745 (March 1971). The position of the observed resonance lines in CCl. and assignments for the methylene and methyl protons of these series of hydrocarbons are summarized in this reference. It has been found that methyl and methylene protons of the same type that the same level of steric hindrance and the same ^"1 heaped! Arrangement" have substantially for each individual species of the hydrocarbon the same chemical shifts in CCl. show regardless of their carbon number. A differentiation and assignment of a number of the maximally “accumulated” methylene and maximally “accumulated” geminal dimethyl groups in these compounds was possible from 100 MHz spectra obtained using CgDg as solvent. The position of the observed proton resonance lines for these groups in CgDg and their arrangement in the C..Q- to C, ,, - hydrocarbons are summarized in the above literature reference.

109886/1992

Table 2 shows the refractive indices of the C ₁₁ - "to (^, .- hydrocarbons determined at 25 ° C."). These values are listed in comparison with the "calculated values obtained for these compounds by the method of Greenshields and The difference in the refractive indices δ Rl (calculated value minus experimental value) has been found to increase with an increase in the carbon number. This table also includes the density values obtained from the calculated molar volumes (25 ° C.) of the hydrocarbons and two experimental density values which were determined for the C 1 and C 1 hydrocarbons, positive deviations between the calculated and observed density values were found for the C 1 and CU g hydrocarbons.

Essentially pure individual olefins can be obtained from the non-hydrogenated Polyisobutylene oils obtained and characterized in a corresponding manner.

Characteristic of the new branched, paraffinic and olefinic "hydrocarbons" are "clustered" and steric hindered methyl and methylene groups. This accumulation effect is lower with the hydrocarbons Carbon number a little less pronounced, but becomes with the enlargement of the carbon chain is noticeably larger. That Introducing methylene groups between two internal geminal methyl groups or between one internal one

109886/1992

geminal methyl group and a tert-butyl group (INCC-position to each group) gives a strong "bending of the hydrocarbon chain. This bending results in a much stronger" clutter "and steric hindrance of the different _protons% turn the free rotation of the individual methylene The resulting changes in anisotropy cause a chemical shift in the proton resonance signals in the direction of lower fc field strengths (downfield chemical shift).

The lower limit of this resonance shift down in branched Paraffins (CCl.-solutions) is 66 Hz (1.10 ' Parts per 1 million parts) for internal geminal methyl groups and 85 Hz (1.42 parts per million parts) for isolated methylene groups. This applies to the polymer polyisobutylene, in which the isobutylene repeating unit leads to a maximum "clustering" of both the geminal methyl and also leads to the isolated methylene groups. The branched, hydrocarbons with lower carbon numbers, C-j-t » C..p and CLc, have no maximally "accumulated" geminal methyl groups.

The presence is characteristic of the C - ,, - hydrocarbon of both clustered and maximally clustered geminal methyl groups. This compound is the first type of molecule in this series of compounds shows the maximum "accumulation" of a geminal methyl group. Shows a geminal methyl group

.10 9 8 8 6/1992

then maximum "accumulation" when they (1) in oC position two isolated methylene groups and (2) is in ß, ß-position to two quaternary carbon atoms. This "accumulation" is comparable to the maximum "accumulation" of the geminal Methyl groups in polyisobutylene of higher molecular weight (e.g. from 200,000+). The resonance signal or the resonance line of the maximally "accumulated" geminal methyl group, as well as the resonance line of the maximal "clustered" geminal methyl groups of polyisobutylene is shifted in the direction of lower field strengths and appears at 65 to 66 Hz (1.08 to 1.10 parts per 1 million Parts). The two isolated methylene groups in this molecule (as terminal isolated methylene groups in the Compounds with a longer carbon chain) are adjacent to a maximally "clustered" geminal methyl group and are therefore more sterically hindered and "clustered" than the isolated methylene groups of the C-j? "and C ^^ - compound. This increased concentration of methyl groups causes the methylene resonance to shift by 5 Hz down to 80 Hz (1.33 parts per million parts), with only a single line of resonance for both isolated terminal methylene groups is observed. These methylene groups are defined as "clustered" methylene groups and are found in all hydrocarbons with higher carbon numbers (C- ^ g and above) .

The Cjg hydrocarbon is the only other compound in this row, which has a single maximally "heaped"

109886/1992

has geminal methyl group. This type of molecule, which is symmetrical about the maximally "clustered" geminal methyl group, has two isolated methylene groups which have exactly the same molecular bypass. These groups are therefore magnetically equivalent. The CMR spectrum of the CjQ compound both in CCl. as well as in CgDg as solvent shows a single proton resonance line for these "clustered" methylene groups. All of the odd carbon compounds in this series are characterized by this molecular symmetry and have terminal isolated "clustered" methylene groups that are identical. The unsymmetrical Cp _Q hydrocarbon is the first type of hydrocarbon in this hydrocarbon series that has a maximum "accumulated" methylene group. An isolated methylene group shows maximum "clustering" when it is adjacent to or between two maximum "clustered" geminal methyl groups, as in polyisobutylene.

The subsequent new hydrocarbons with higher carbon _{numbers (Cp * to C. Q} ) have an increasing number of maximally "accumulated" geminal methyl and maximally accumulated methylene groups. They consist of two basic types, (1) a type of hydrocarbon with an odd number of carbon, which has two terminal isopropyl groups and is arranged symmetrically around a maximally accumulated geminal methyl group or a maximally accumulated methylene group, and (2) a type of hydrocarbon with an even carbon number, which has a terminal isopropyl group. and tert-butyl group

10 9 886/1992

and does not contain a center of symmetry. The C ₃₃ and Cp hydrocarbons are shown below. A denotes a maximally “accumulated” geminal methyl group and B a maximally “accumulated” methylene group.

CH ₃ -CE,

CH, CH,

I ³ I \

(1) HC-CH ₀ -C-CH ₀ -ABA-CH ₀ C-CH ₀ -CH

J ² I ² , ² I ² t

CH ₃ CH ₃ J CH ₃ CH ₃

and

CH, CH, CH

I ³ I ³ I.

I I

(2) CH 1 -C -CH ₅ -ABABA-CH ₀ -C-CH _{0 -CH}

The integrated intensities of the observed resonance for each species of a given carbon number stood in accordance with the theoretical number of maximally clustered ethylene groups and maximally clustered geminals Methyl groups predicted for each of the structures given. The number of maximum accumulated methylene groups is always one less than the number of maximum accumulated geminal methyl groups. more details the characterization of compounds containing side chains can be found in the publication in J. Pol. May be. can be removed.

109886/1992

- 72 - Molecular weight 2133584 Error, % Table 1 io "calculated Factions +3.0 purity +3.9 j 156.3 measured more relative +0.7 Coals and molecular weight of the obtained 170.3 . -2.8 substance number 212 ". 4 161. +0.9 11 Purity,; 226.4 177 -2.7 12th 268.5 214 -0.8 15th 99+ 282.5 219 +1.4 : 16 97.5 324.6 271 -1.0 *
19th '99 + 338.6 275 +0.6 20th 99+ 380.7 . 322 -2.5 23 '99+ 394.7 344- -1. $ 24 99.0 436.8 377 -0.6 , 27. 96.7 450.8 397 .28 96.9 492.9 ' 426 -0.9 31 99+ 507.0 444 +1.2 32 99+ 549.0. 490 - 35 . 98.8 563.1 513 36 .98.7 544 39 97.3 570 -40- '. 99+ ■ 99+ - ". · —ST9 +. _

a Determined by capillary gas chromatography. "b Determined by vapor pressure osmometry.

109886/1992

■ - 73 - 2 1.4165 ERI
. (ber.-acc.) 2133584 Tabel Physical Properties 1.4257 -0.0022 Refractive index RI 1.4380 -0.0003 calculated
Density (25)
g / cm * 3
"calculated measured
(25 ⁰ C) (25 ⁰ C) 1.4441 0.7375 Coals
material
number 1. ¹ H ¹ IS 1.4530 +0.0019 0.7561 11 1.4? 54 1.4564 +0.0003 . O.7816. 12th 1.4380 1.4615 · ■ +0.0028 0.7942 15th 1.4648 +0.0021 O.8O92 16 1.4533 1.4679 + O.OO36 .0.8185 19th • l ". 4592 1.4704 + O.OO34 0.8282 20th 1.4636 1.4725 +0.0049 0.8355 23 1.4684 1.4750 +0.0047 0.8419 24 i.4713 1.4768 +0.0055 0.8479 -27 1.4753 1.4780 + O.OO5O O.8525 28 Ί..4772 I.4798 +0.0069 O.8575 31 1.4805 • 1.4815 + O.OO58 O.86O7 ^c 32 1.4818 +0.0066; 0.8651 ^d 35 - 1.4849 O.8674 36 1.4856 O.8712 39 1.4881 40

a After Greenshields and Rossini

b From the "calculated fourth of the molar volume at 25" C.

c Measured value = 0.8584 g / cm

d Measured value = O.863I g / cm

109886/1992

Table 3 Testing in the Roxana four-ball tester

Name of the sample

Test duration

Tensile strength (torque in g)

KV ₃₈ O VTP-Vl

Scratch

CO ISJ

1. PIB (starting material)

_ ^ 2. PIB ketone (batch 1)

Q (oxidative processing)

2 3. ΡΪΒ-ketone (approach 1)

_σ> (oxidative work-up)

4. PIB ketone (batch 1)

(Oxidative processing)

5. PIB ketone (batch 2)

(Oxidative processing)

6. PIB ketone (batch 2)

(Oxidative work-up) 1/2 min

min

min
min

mm
min

1/2 min

min
1-1 / 2 min

min

1/2 min

min
1-1 / 2 min

min

1/2 min

min
1-1 / 2 min

min

73.3

72.8 73.9

83.2 82.5 84.0

84.4 83.0

85.8

83.8 82.5 85.2 85.9 86.9

75.9 73.9 77.8 82.8 85.5

74.0 71.4 76.5 80.5 82.3

4.49_ 24.14

3.97 21.14

please refer

please refer

middle

middle

middle

middle

middle

middle

Name of the sample

7 * PIB ketone (batch 2)

(Oxidative processing)

8. PIB ketone (hydrolysed _o tables workup)

to

9. PIB ketone (hydrolytic processing)

CD

. PIB ketone (hydrolytic work-up), mixture

11. PIB ketone (hydrolytic processing), Metal catalyst

12. PIB ketone (hydrolytic work-up), high temperature

Experimental min 3 (, Fortse Tabel duration min Tensile value min (Torque min ment in g) 1/2 77.5 1 min 71.5. 1-1 / 2 min 83.5 2 85.5 min 89.2 1/2 min 72.6 1 min 71.9 min 73.4 1/2 * 71.3 1 min 70.9 1-1 / 2 min 71.7 2 min 72.3 min 73.5 1/2 74.6 1 min 74.5 1-1 / 2 min 74.7 2 min 75.2 min 75.4 1/2 74.2 1 min 74.2 1-1 / 2 min 74.1 2 min 74.9 min 75.4 1/2 71.9 1 71.5 1-1 / 2 72.2 2 73.0 74.3

VTF ₇ VI scratch

middle

middle

small amount

very low

very low

small amount

co co cn co

Table 3 (continued)

Name of the sample

Test duration

Tensile strength (torque in g)

^K7 38 ^o V-TP-VI scratch

CO CD IO

13 .. L-10 ketone (hydrolytic
Work-up) (Indopol
Polybutene)

14. L-10 ketone

15. L-10-Ee ton

16. PIB-acetone / acid) 75
(25 Io PIB)

17. PIB acid

18. PIB alcohol (75
(25 % PIB)

19. PIB-Sster

1/2 min 1 min

1/2 min

1 min 1-1 / 2 min

2 min 2-1 / 2 min

1/2 min

1 min 1-1 / 2 min

2 min

1/2 min 1 min

1/2 min

1 min

- 1/2 min 1 min

1/2 min 1 min

63.0 63.0 62.9

70.8 67.6 73.9 77.9 78.5 79.9

72.1 68.7 75,
76

.5 .3

77.5

75.5 74.8 76.2

74.0 73.9 74.2

70.8 69.9 71.8

81.
80.

57.8

67

see sample 14

17.51

377.9

25th

middle - * CO CO cn strong OD . £ - <■

strong

82.2

middle

small amount

very
small amount

except-

properly,

small amount

Table 3 (continued)

Name of the sample

Test duration

Tensile strength (torque in g)

KV _OQ o

KT- _Q o YTF-YI scratch

20. PIB ester + 10 % KO 880 *.

21. PIB-Br

22. 40/60 PIB ketone / polybutene

CD OO OO

23. Sample 22+

KO

24. 10/90 PIB-ketone / H.P.O. ** H.P.O. ** Polybutene PAIiVCH ***

1/2 min

1 min

1/2 min
1 min

1/2 min

1 min

1/2 min
1 min

1/2 min

1 min

1/2 min

1 min

1/2 min

1 min

1/2 min

1 min
1-1 / 2 min

2 min

71.7 71.9 71.6

69.1 69.1 69.1

77.2 76.5 78.0

68.5 68.6 68.4

66.6 65.5 67.7

57.9 57.7 58.2

67.5 67.7 67.2

75.4

74.7 76.2 75.9 76.2

3.99 3.34 6.83

20.51

16.36

96

82

97.87 -72

very NJ small amount CO very CO strong cn
CO

small amount

strong

strong

middle

middle

-J I

* K0880 is a typical commercial additive system, that for use in conventional transmission fluids for "Ford" -type automotive automatic transmissions is determined. The system includes HD additives, antioxidants, antifreeze agents, dispersants, Corrosion protection agents (anticopper corrosion) and antifoam agents.

** Hydrogenated paraffinic oil.

*** PAMVCH = a hydrogenated dimerization product of cC-methylstyrene, which is predominantly in the hydrindane form. All percentages in Table 3 are percentages by volume.

109886/19 92

Table 4 Polar transmission media

(a)

(b)

C-O-CHo

H ₃ C CH ₃

Cc) H-

H ₃ CC

CH3 -O-C-CH3

. CH ₃

• r

H ₃ CC

CH ₃

(e)

0-C-CHr

(f)

10 9 8 86719 9 2

Claims (29)

Claims Branched olefinic or paraffinic hydrocarbon with 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39 or 4-0 carbon atoms, the ^ at least one Pair contains maximally accumulated geminal methyl groups, and a polar compound derived therefrom, thereby marked that the hydrocarbon has the formula Y 4 is CH ₂ - 0 _to in which η is an integer of 3 Ms 9 and Y a group. CH,. . I ³ CH, - C - ■ ⁵ I. CH ₃ represents when the hydrocarbon has an even carbon number; and
Z one of the groups • H H, -CH ₂ -C-CH ₂ -C (CH ₃ ) ₅ ,
CH ₃ H ? -C = C -CH ₂ -C CH 109886/1992 CH- ί CH, CH, -CH = C-CH ₂ -C (CH ₃ ) ₃ , -CH ₂ -C-CH ₂ -C (CH ₃ ) ₃ and -CH ₂ -C = CH-C (CH ₃ ; "means; and in the
Y a group CH ₃ HC- I CH, and Z stands for a hydrogen atom when the hydrocarbon is a paraffin with an odd carbon number,
and that the polar compound derived therefrom has the formula 'CH CH, CH, CH, CH ₂ - 3 y in which η is an integer from 1 to 30, n ¹ 0 or 1 and Y is a polar group of a ketone, a carboxyl group, carboxylic acid salt, ether, alcohol, ester, acyl halide, acyl hydrazide, mercapto, epoxy -, thioester, thiolester, thioether, phosphate, phosphate mixed ester, phosphite, phosphite mixed ester, sulfate, sulfite, sulfonate, oxime, amide, imine, amine or maleic anhydride adduct group or a halogen atom means. 2. Polar compound according to claim 1, characterized in that that η in the formula is a whole 109886/1992 Means number from 3 to 20. 3. Branched hydrocarbon according to claim 1, characterized in that it is at least contains a maximally accumulated methylene group. 4. Branched paraffinic hydrocarbon according to claim 1, characterized by the formula CH i CH CH CH ₃
C - CH ₃ -CH ^CH 3 in which η is a number from 2 to 8. 5. Branched paraffinic hydrocarbon according to claim 1, characterized in that it has a even carbon number and a cumulative tertiary butyl group having. 6. Branched paraffinic hydrocarbon according to claim 1, characterized in that it an odd carbon number and a terminal isolated one has accumulated methylene group and that its molecule is symmetrical about a central carbon atom is arranged, daa carries a maximally accumulated geminal methyl group. 109886/19 9 2 7. Branched paraffinic hydrocarbon according to claim 3, characterized in that it has an even carbon number of at least 20. 8. Branched paraffinic hydrocarbon according to claim 1, characterized in that it Has 16 or 20 carbon atoms and unequal 'Contains terminal isolated methylene groups. 9. Branched paraffinic hydrocarbon according to claim 1, characterized in that he an odd number of at least 23 carbon atoms has, contains two terminal isopropyl groups and symmetrical about either a central carbon atom with a maximally accumulated geminal methyl group or a maximally accumulated methylene group is arranged. 10. Branched paraffinic hydrocarbon according to claim 1, characterized in that it has a has an even carbon number of at least 24 than terminal groups are an isopropyl group and a tert-butyl group and does not contain a center of symmetry. 11. Polar compound according to claim 1, marked net by a structure of the formula 109886/1992 Γ ⁵ c - CH, - CH CH
I. 3 η C -
ι I.
CH 3. -Z in Z ^f a group 0
Il
-C-CH ₂ -C (CHj (a) or Ό -OH, OH Jf 1 -C-OH, -C-CH ₅ , (c) (d) (e) -0-CR ₅ ,
(f) -C-WH- (CH ₂ ) _n "-N or N (G) and n ^{1 is} O or 1, η is an integer from O up to and including 17, R is a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl, neopentyl, Cyclohexyl, methylcyclohexyl, indanyl, hydrindanyl, cyclohexylindanyl or cyclohexylhydrindanyl group, R, and Rq C | "-Alkyl groups or saturated, olefinically unsaturated or aromatic cyclic or alkyl-substituted cyclic hydrocarbon radicals and R. and R, - 109886/1992 Mean hydrogen atoms or groups IU and in which 'the radicals R, R ,, R-, R _r and Rg within the same molecule can be the same or different radicals. 12. Polar compound according to claim 11, characterized in that η is an integer from 1 to 15 when Z ^{1 is} the group (a), that η is an integer from 2 to 16 when Z ^{1 is} the Group (b), (e), (f), (g) or (h) and η is an integer from 3 to 17 when Z 'is a group (c), (d) or (i) . 13. Use of a polar compound according to claim 1 as part of a lubricant mixture that also contains a hydrocarbon base, 14. Use according to claim 13, characterized in that that an effective amount of a polar compound according to claim 11 is used as a constituent of the lubricant composition will. 15. Use of a polar compound as a component of a lubricant mixture, characterized in that that one is a polar compound of the formula 109 886/1992 CH. CiL CH, - (CH ₂ ) _n , -Y uses, in which n, n 'and Y have the meaning already mentioned have and R, R .. and Rp methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclohexyl, methyleyclohexyl, indanyl, Hydrindanyl, cyclohexylindanyl or cyclohexylhydrindanyl groups mean. 16. Use according to claim 13 to 15, characterized in that that the polar compound is added to the lubricant mixture in an amount of at least 1 percent by weight is added. 17 «Lubricant mixture, characterized by the content of at least one compound of the formula CH, (J CH 3 1 in. the Π "is an integer from 3 to 29 inclusive and Z '" is one of the groups H
(a) -C = O (b) -C - OH 109886/1992 (c) -C - OH CII, (d) -CH ₂ - 0 Il C - CH 0
I /
(e) -CH ₀ - C - CH ₀ - C (CH,). "mean. 18. Lubricant mixture according to claim 17, characterized in that it is at least $ 10 2,2,6,6,8,8-hexamethyl-4-nonanone, 4,4,6,6,8,8-hexamethyl-2-nonanone . or 1,2,3,3,5,5,7,7-octamethyl-i-octanol or contains a mixture of at least 2 of these compounds. 19. Use of a hydrocarbon according to claim 1 his 10 in the form of an oil, characterized in that this oil has at least four different compounds Has structure which (A) is a branched olefinic hydrocarbon having 16, 20, 24, 28, 32, 40, 44 or 48 carbon atoms and / or (B) a branched paraffinic hydrocarbon with 16, 20, 24, 28, Represent 32, 40, 44 or 48 carbon atoms and have the formula CH, CH CH, CH, CH, CH, 109886/1992 have, in which η is an integer from 3 "up to and including 11 means and Z -CH ₀ - C - CH ₀ - C (CH,) ,, ^{2/2 3 3} . * CH ₃ or means when the hydrocarbon is a paraffin and. . Z for one of the groups CH, ι ' (B) -6 = C - CH ₂ - C CH ₃ CH, - CH = C - CH ₀ - C (CH,), CH ₀ - CH - C - CH ₂ - C (CH ₃ ) ₃ CH ₃ '
-CH- C = CH-C (CH ₃ ) ₃ when the hydrocarbon is an olefin. 20. Use according to claim 19, characterized in that that the oil is less than 10 109886/1992 Weight percent of other olefinic or paraffinic Contains hydrocarbons. 21. Use according to claim 19, characterized in that the content of other hydrocarbons in the oil is such that a gas chromatogram of the oil in the range Cj.g to C, ₂ shows almost baseline resolution and no base range formed by other hydrocarbons Contains peaks. 22. Use according to claim 19 to 21, characterized characterized in that the oil has a bromine number less than 10. 23. Use according to claim 19 to 22, characterized in that the oil obtained has a value of KVq ₉ in the range from 1.5 to 20 and VTP-VI in the range from 95 to 115. 24. Use according to claim 22, characterized in that the bromine number is less than 5 is. 25. Use of a polar compound of the formula 109886/1992 \ j ' ■ CH, 2 y (CH ₂ ) _n , -Y in which η is an integer from 1 to 30, n 'O or 1 and R, R ^ and R ₂ methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl , Neopentyl, cyclohexyl, methylcyclohexyl, indanyl, hydrindanyl, cyclo- fc hexylindanyl or cyclohexylhydrindanyl groups and Y a functional group of a ketone, a carboxyl, carboxylic acid salt, ether, alcohol, ester, acyl halide, acyl hydrazide, mercapto, epoxy, thioester, thiolester, Mean thioether, phosphate, phosphate mixed ester, phosphite, phosphite mixed ester, sulfate, sulfite, sulfonate, oxime, amide, imine, amine or maleic anhydride adduct group or a halogen atom,
as a transmission medium in a friction or tensile force ^ gearbox that has at least two mutually rotatable Parts in a suitable for transmitting a torque has mutual position. 26. Use according to claim 25, characterized in that that the polar compound according to claim 2 is used. 27. Use according to claim 25 or 26, characterized in that the polar compound 109886/1992 used together with a hydrocarbon base that is 15 "to 100 percent by volume of at least one paraffinic oil, naphthenic oil, olefinic Homopolymer oil, olefinic copolymer oil, or one at least
such / partially hydrogenated 01s. 28. Use according to claim 25 "to 27, characterized characterized in that a polar compound according to claim 11 is used. 29. Use according to claim 26 to 28, characterized in that the polar compound is used in the form of a mixture with a hydrocarbon base, the gas chromatogram of which _{shows approximately baseline resolution in the range Cj, -to C 1} -Q and is free of a substantial base range and peaks generated by other oxidized hydrocarbons. 109886/1992 L e r s e i t e