DE3328716A1 - ALKENYL AMBER ACID ANHYDRIDE PREPARATION, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

Alkenyl succinic anhydride preparation, process for its preparation and its use

"The invention relates to an improved liquid alkenyl succinic anhydride mixture with excellent paper sizing properties and a method for their Manufacturing. The invention also relates to an improved method for gluing paper or cardboard products. According to a further feature of the invention there is provided an improved method of rendering water repellent Cellulosic goods made available.

It is known that long straight chain alkenyl succinic anhydrides can be used as effective paper sizing agents (see, for example, U.S. Patents 3 102 064, 3 821 069, 3 968 005 and 4040 900 (Re. 29 960) These alkenyl succinic anhydrides have also been called Treatment agents for fabrics or goods are used (see US Pat. No. 2,903,382). The appropriate molecular weight range of the alkenyl group on these sizing agents has been established variously described as having from 8 to 35 carbon atoms.

It is also known that the known sizing agents are best in a highly dispersed form, for example. wisely in the form of an aqueous emulsion. Alkenylsuccinic anhydrides, which are made from straight-chain Alpha olefins are produced at ambient temperatures Solids and therefore not effective in making these formulations. With regard to this Commercially available alkenyl succinic anhydride paper sizing agents become a fact from isomerized straight-chain α-olefins (i.e. straight-chain internal Olefins) or made from branched-chain olefins (see, for example, the frequent reference to

"Isooctadeceny! Succinic anhydride" in U.S. Patent 3 102 064).

It has been stated that the alkenyl group molecular weight of the more preferred or effective alkenyl succinic anhydride sizing agents corresponds to a carbon number in the range of 13 to 22 carbon atoms. Mixtures with different carbon numbers have also been described (see. For example, the reference to C. ₅ _ _2Q -Alkeny! Anhydride in US Patent No. 4,040,900).

The present invention relates to a two-component alkenyl succinic anhydride preparation with excellent paper sizing properties from the following components:

(A) the reaction product of maleic anhydride and straight chain α-olefins in the C ₁ -C ₁ "range having an average molecular weight of about 182 to 238 and

(B) the reaction product of maleic anhydride and straight-chain internal olefins or branched-chain olefins in the C ₁ , -C ^ range with an average molecular weight of about 2 to 24

308,. .

wherein the component (B) has a molecular weight higher than that by at least 10 units of component (A).

Preferably, the above-mentioned mixture contains about 5 to 40 'i of the component (A), especially from about 10 to 35% of component (A).

The invention also relates to a method for: Gluing paper done in the manner

that within the moist paper pulp an alkenyl succinic anhydride preparation, as described above.

The invention also relates to a method for treating a cellulosic tissue or tissue Goods to make them water-repellent by impregnating the goods with the new invention Alkenyl succinic anhydride preparations.

The invention also relates to a preferred process for producing the alkenylsuccinic anhydride preparation according to the invention from maleic anhydride and a mixture of straight-chain α-olefins

in the C._-C "^ area, which consists of j

(A) introducing the α-olefins into a distillation zone, in which at least part of the lowest-boiling α-oil is evaporated and drawn off overhead will,

(B) the remaining bottoms fraction from the distillation zone to reduce the α-olefin content to less than 15% of the total olefin content of the soil fraction to belittle

(C) the overhead obtained in step (A) α-olefin fraction with the isomerized olefin bottoms fraction the stage. (B) to unite and

(D) the combined olefins from step (C) with maleic anhydride react to recover the alkenyl succinic anhydride product.

Another embodiment of the method according to the invention consists in the non-isomerized α-01efin overhead fraction, which has been recovered from step (A), and the isomerized olefin bottoms fraction of

-10-

Step (13) to react each independently with maleic anhydride, and the alkenylsuccinic anhydride products obtained then to combine to obtain the alkenylsuccinic anhydride according to the invention.

The α-olefin content in stage (B) is preferably to less than 10 years and in particular less than 5% the total olefin content of the soil fraction is reduced.

¹ ^ Among other things, the invention is based on the surprising finding that alkenylsuccinic anhydrides based on certain straight-chain ct-olefins, which were previously not considered suitable, can be combined in specific mixtures with other alkenylsuccinic anhydrides, with an excellent paper sizing product being obtained.

Another advantage of the present invention resides in the fact that when straight chain α-01efine as feedstock for manufacture

used by liquid alkenyl succinic anhydrides ■ ''. olefin processing to a lesser extent is required before the formation of the alkenyl succinic anhydride.

The preparation according to the invention can be produced in this way that the alkenylsuccinic anhydride components described are simply combined or optionally the leading olefins are combined and then the desired alkenysuccinic anhydride is produced will. For example, a broad range of straight-chain α-01efine mixtures that are produced by Wax cracking, produced by Fischer-Tropsch synthesis or by ethylene oligomerization, is distilled to obtain light and heavy fractions

th. The heavy fraction is then isomerized to move the double bond into internal positions, and will be with the light fraction before making the alkenylsuccinic anhydride preparation according to the invention combined.

The olefin feed for component (A) of the present invention The preparation should consist predominantly of a straight-chain 1-olefin. Smaller amounts of Chain branching or internal olefins such as are found in conventional "α-olefins" can also be used are present.

The olefin feed for each of components (A) or (B) may consist of a single carbon number, a mixture of contiguous carbon numbers or from a combination of carbon numbers within exist in this area.

The olefin feed for component (B) can be straight chain or branched. Branched chain olefins can be obtained from various sources, for example by oligomerization of lower olefins in the C ₃ -C ₁₁ range. If the chain is straight, the olefin should be essentially free of α-olefin. These straight-chain olefins can be obtained from η-paraffins by known processes, for example by dehydrogenation and chlorination / de-. hydrochlorination. Alternatively, the straight chain olefins can be prepared by isomerizing α-olefins using acidic or basic catalysts in accordance with the preferred processes of the present invention.

To carry out the method according to the invention as the olefin feed for component (B) a straight

chain internal olefin used, which is obtained by isomerization of straight-chain α-olefins in the C. -C ₉₂ range. This isomerization can be carried out using acidic or basic catalysts. The isomerization should be sufficient to leave no more than about 15% alpha-olefins, and preferably less than 10%, and more preferably less than 5% alpha-olefins. These olefins can be increased by the addition of branched chain olefins or internal straight chain olefins obtained from other sources as described above. In general, the olefin feed for component (B) should be essentially free of straight chain α-olefins.

The new sizing agents have all the features and advantages of the known sizing agents. Furthermore The new sizing agents according to the present invention give a paper sized therewith a special one good resistance to acidic liquids such as acidic printing inks, citric acid, micic acid etc., in comparison to a paper which has been sized with known sizing agents. Additionally In addition to the properties mentioned above, these sizing agents can also be used in combination with alum and with other pigments, fillers and other ingredients that can be added to paper are used will. The sizing agents according to the invention can also be used in conjunction with other sizing agents to achieve additive sizing effects. Another advantage is that they don't The strength of the paper deteriorates and, when used with certain additives, the strength of the increase finished arches. Only mild drying or curing is required to get the full value of the sizing agent to develop.

The sizing of paper using these sizing agents is subject to various modifications will. What is essential is the fact that in all of these processes an even distribution of the sizing agent is achieved takes place within the fiber slurry in the form of small droplets that are in intimate contact get with the fiber surface. An even distribution can be achieved by adding the sizing agent to the pulp with vigorous stirring or by adding a previously prepared fully dispersed emulsion. Chemical dispersants can can also be added to the fiber slurry.

Another important factor in the effective use of the sizing agents of the present invention is their use in conjunction with a material which is either cationic in nature or otherwise capable of ionizing in such a manner or to dissociate so that one or more cations or other positively charged components are obtained. These cationic agents, as they are mentioned below, have proven to be valuable means of promotion the retention of the sizing agents as well as being valuable in that they are in close proximity to the latter bring to the pulp fibers. Of the materials used as cationic agents in the sizing process can be used, be alum, aluminum chloride, long-chain fatty amines, sodium aluminate, substituted polyacrylamide, chromium (III) sulfate, animal glue, cationic thermosetting resins and polyamide polymers are mentioned. Of particular interest for use as cationic agents are various cationic starch derivatives, such as primary, secondary, tertiary or quaternary amine starch derivatives as well as other cationic ones Nitrogen-substituted starch derivatives, also cationic

see sulfonium and phosphonium starch derivatives. Such Derivatives can be made from all types of starch including corn starch, tapioca starch, potato starch, Waxy maize starch, wheat starch and rice starch. In addition, they can be granular in their original form Form or can be converted into pregelatinized cold water soluble products.

All of the aforementioned cationic agents can be added to the starting material, i.e. H. the pulp slurry, either before or after the addition of the sizing agent or added together with this. For maximum distribution, it is preferable that the cationic agents either subsequent to the addition of the sizing agent or directly in combination with it is added. The actual addition of either the cationic agent or the sizing agent to the material can be used at any point during the papermaking process before the final conversion of the moist pulp into a dry web or one dry arch. For example, these sizing agents can be added to the pulp while the latter is in a headbox, in a Dutchman, in a water digestion vessel or in a cloth chest is located.

In order to achieve good sizing, it is useful that the sizing agents in a uniform manner within the fiber slurry are distributed in the smallest possible particle size. One method of accomplishing this The aim is to use either mechanical means of the emulsifying agent prior to its addition to the starting material Devices such as high-speed stirrers, mechanical homogenizers etc. or by adding a suitable emulsifying agent. If possible, it is

-IS-

moderate to use the cationic agent as an emulsifier. This method is particularly successful when cationic starch derivatives are used. Of the usable non-cationic emulsifiers which are used as emulsifiers for the sizing agents can be hydrocolloids, like conventional starches, non-cationic starch derivatives, dextrins, carboxymethyl cellulose, gum arabic, gelatine and polyvinyl alcohol and various surfactants

¹ ^ imagines. Examples of such surface-active agents are polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitol laurate and polyoxyethylene sorbitol oleate laurate. If such non-cationic emulsifiers are used, then it is

* 5 often expedient to use a cationic agent separately Pulp slurry after adding the emulsified To add sizing agent to the latter. In preparing these emulsions using an emulsifying agent the latter is usually first in. Water is dispersed and the sizing agent is then added introduced with vigorous stirring. Optionally, the emulsification methods described in US Pat. No. 4,040,900 be applied.

Further improvements in the water resistance of the paper made using these new sizing agents obtained can be obtained by making the obtained webs, sheets or molded products hardened. This hardening involves heating the paper to temperatures between 80 and 150 C during 1 to 60 minutes before. However, it should again be pointed out that post-curing is not essential to to carry out the invention successfully.

The sizing agents according to the invention can of course

successfully used for the sizing of paper that of all types of both cellulosic fibers and combinations of cellulosic Fibers obtained with non-cellulosic fibers has been. The cellulosic fibers that can be used include bleached and unbleached sulfate fibers (Kraft fibers), bleached and non-bleached suIfit fibers, bleached and non-bleached soda fibers, neutral sulphite fibers, ha Ib- chemical and semi-chemically ground wood fibers, ground wood fibers and combinations of these Fibers. These terms refer to pulp fibers that are manufactured using a variety of processes used in the pulp and paper industry. Synthetic fibers can also be used of the viscose rayon type and regenerated cellulose fibers are used,

All types of pigments and fillers can be used in the papers to be sized with the sizing agents according to the invention can be added. Such materials are, for example, clay. Talc, titanium dioxide, calcium carbonate, Calcium sulfate and diatomaceous earth. Other additives such as alum as well as other sizing agents can also be used in conjunction with these sizing agents.

With regard to the proportions, it should be noted that the sizing agents can be used in amounts between approximately 0.05 and approximately 3.0% of the dry weight of the pulp in the finished web or in the finished sheet. While amounts in excess of 3 % can be used, the benefits of improved sizing properties are usually not economically justified in this case. The exact amount of sizing agent depends on the range mentioned.

means that is used, mainly on the type of pulp used, the specific working conditions as well as the end use of the paper. For example, requires a 5

Paper that has good water resistance or ink retention possesses the use of a higher concentration of the sizing agent than a Paper that does not meet these requirements. The same factors also apply to people

■ ^ ge of cationic agent used in conjunction with these Sizing agents can be used. In practice there will be no problem with these materials to be used in any concentration that corresponds to the respective working conditions. Under ordinary circumstances

Stands ¹ ^ is a range of 0.5 to 2.0 parts by weight of the cationic agent per 1.0 part by weight of sizing agent generally sufficient. It should be noted that the cationic agent is present in an amount of at least 0.025 1 of the dry weight of the pulp in the paper.

The alkenyl succinic anhydride preparations according to the invention according to the present invention can also be used to manufacture cellulosic goods To impart water repellency. The above-described water-repellent preparations can - applied to cloths in aqueous emulsions, which are similar to those used to glue paper. The emulsion can be applied to the goods can be sprayed on, the product can also be dipped into the emulsion to ensure that the derivative is evenly distributed in the To distribute goods. The impregnated product is then removed from the solution and air-dried. To After drying in the air, the cloth is then heated, preferably to a temperature of more than 100 C,

^L to cause the impregnated agent to harden within the cloth. It has been found that a temperature of. about 125 C for a period of 15 to 20 minutes. At lower temperatures, longer periods of time are required to effect the curing process. The curing time should be as short as possible and generally less than 1 hour. At higher temperatures, the thermosetting can be carried out in shorter periods of time. The upper limit of the temperature at which the curing process can be carried out is limited to the temperatures at which the goods turn brown or discolored. Using the preparation according to the invention, it is preferable to impregnate the goods with approximately 0.7 to 2.5% by weight of the alkenyl succinic anhydride, based on the goods.

The following examples illustrate the invention without restricting it.

Examples . ■

example 1
25th

This example describes the preparation of a standard straight chain alkenyl succinic anhydride which is suitable for gluing purposes.

The feed olefin is derived from petroleum wax cracking and originally contains approximately 88% straight chain α-olefin. It consists of a mixture of homologues from C _1c -C. _ir ,, containing unc ^ about 18 % C ₁ , -,

19 % C ₁ , -, 18 \ C ₁₇ , 13 SC _{1P /} 15% C ₀ and 12% C_ _n . Ib I / ■ Io iy ZU

This mixture is made using an acidic catalyst

lysators isomerized until the α-olefin content is reduced to 7%. The double bond has moved into the 2 position as well as into other internal positions

emotional.
5

The mixture of straight-chain internal olefins as described above is in an amount of 329 g (1.35 mol) with 98 g (1.0 mol) of maleic anhydride in an autoclave for 3 1/4 23 0 ⁰ C heated. "More than 95% of maleic acid anhydride -.- react with the olefin, an alkenyl succinic anhydride product is recovered. This crude product is stripped of unreacted maleic anhydride and olefin min by heating to 260 ⁰ C at 25 mmHg with nitrogen for a period of 40.

'.

The remaining alkenyl succinic anhydride is a straw-colored liquid with a pour point of about 5 C which remains fluid but forms some solid when left overnight at room temperature.

This product is very similar to a normal im Commercially available straight chain alkenyl succinic anhydride. It delivers good paper sizing results a variety of tests as described in U.S. Patent 4,040,900.

Example 2

An alkenyl succinic anhydride is prepared as described in Example 1, except that the carbon number range of the olefin feed is 25 % from C ₁ J, 30% from C. g, _{29-5 from C 17} and 15%

C ₁₀ exists. The α-olefin content. that after the Isomeri-Io

sation remains is 7 V ,. The derived alkenylbornstinic anhydride is a clear liquid that does not generate solids when left to stand overnight at 5 ° C.

-20- Example 3

An alkenysuccinic anhydride is prepared from the same straight chain α-olefins as described in Example 1, with the exception that the olefin isomerization step is omitted. The alkenyl succinic anhydride product is a solid which is unsuitable for sizing using normal aqueous emulsion techniques.
10

Example 4

The cc-olefin inbeschickung, which has been used in Example 1, wherein a lower boiling fraction is obtained, the 88 I, consisting of C ^ and 9% of C ₁ is distilled, wherein the average molecular weight is determined at 212 . An alkenyl succinic anhydride is prepared from this olefin using the steps of Example 1 except that the isomerization step is omitted. This alkenysuccinic anhydride is a solid which is unsuitable for glueing.

Example 5

A preparation according to the invention is produced by using the alkenylsuccinic anhydride from Example 4 as component A and a Q. "-alkenyl-"

Ί o ~ I ο

_succinic anhydride as component B. The C, _{r Λθ -α-}

Ί ο— Ι ο

Olefin fraction is present in the bottom fraction obtained in the distillation of the C, .- fraction of Example 4

will. This C ₁ ,. "Fraction contains approximately 3 4 % C ₁ , Ib-10 Ib

34 Z C ₁₇ and 27 Z C _1R with an average mol-

weight of 237. The C ₁ , - ",, - parliamentary group is

Ib-Io

The α-olefin content is set to 7 Z isomerized and an alkenylsuccinic anhydride is prepared as in Example 1. The finished alkenylsuccinic anhydride mixture contains 22.5% of component A and 77.5% of component B. This preparation is a clear liquid at room temperature. It remains fluid, but forms some solids when left overnight at 5 ° C.

Example 6

There is another preparation according to the invention after prepared in the manner described in Example 5, with

• * - ° with the exception that the C, _r ., O-olefin that is used to produce

1 b— I ο

of the alkenylsuccinic anhydride of component B has been used, isomerized more completely before the reaction with maleic anhydride. In this case, only 2% α-01efin remain after the isomerization and not 7%. This C _{H r} . "- olefin is made with maleic

1 ο — ι ο

acid anhydride reacted and the alkenyl succinic anhydride obtained is with the alkenyl succinic anhydride from Example 4 in a ratio of 22.5 / 77.5 mixed as in Example 5. This preparation is a liquid at room temperature and does not form solids when left to stand overnight at 5 C.

Example 7
30th

Paper sizing tests and sizing efficiency studies are carried out using the methods described in U.S. Patent 4,040,900. For each alkynysuccinic anhydride tested eight results are obtained. The alkenyl amber

Acid anhydride is added to the paper in two different amounts added, in an amount of 0.2 and 0.4%, based on the dry fiber weight. A cationic starch additive is used twice at the time in each case the addition of alkenylsuccinic anhydride is used. Tests are carried out at these two times, when they are carried out, 0.5% alum is also added. The sized papers are made using both the Hercules Sizing Tests (80% reflectivity endpoint) and the potassium permanganate test described in U.S. Patent 4,040,900 examined.

For each of the alkyl succinic anhydrides, the times are for Reaching the end point of the average values determined, the results summarized in the table being obtained.

Tabel

Alkeny / succinic anhydride Time in s to end point

Example No. carbon area (average of 8 tests)

1 15-20 104

2 15-18 110

5 15-18 121

6 15-18 165

The results of the table show that the invention Alkenyl succinic anhydrides according to the present invention, namely Examples 5 and 6, a better one Compared to the known alkenylsuccinic anhydride preparations, they cause a sizing effect of Examples 1 and

Example 8

A formulation similar to that of Examples 5 and 6 is made by mixing 20% of the alkenylsuccinic anhydride of Example 4 with 80 % of the alkenylsuccinic anhydride based on a mixture of branched olefins in the C. to C _2Q range

and has been produced by the oligomerization of propylene. This preparation is at room temperature a liquid and does not form solids when left to stand overnight at 5 C.

Claims (25)

Patent Attorneys European Paten! 'Attorney's * Dr. Müller-Bor * and Partner POB 260247 D-8000 Munich 2Θ Dr. W. Müller-Bore f Dr. Paul Deufel Dipl.-Chera., Dipl.-Wirtsdi.-Ing. Dr. Alfred Schön Dipl.-Chem. Werner Hertel Dipl.-Phys. Dietrich Lewald Dipl.-Ing. Dr.-Ing. Dieter Otto Dipl.-Ing. ; / sm CHEVRON RESEARCH COMPANY 525 Market Street, San Francisco, CA 94105 / USA Alkenylsuccinic anhydride preparation, processes for their production and their use Claims Alkenyl succinic anhydride preparation, marked by (A) the reaction product of maleic anhydride and straight-chain α-olefins in the C. -C. "range, and IJ Tu the reaction product of maleic anhydride and straight-chain internal olefins or branched (B) chain olefins in the C -C ₂₂ range, where the Component (B) has a molecular weight at least 10 units higher than that of component (A). 2. Preparation according to claim 1, characterized in that it comprises about 5 to about 40% of the component (A) contains. 3. Preparation according to claim 2, characterized in that it comprises about 10 to about 35% of the component (A) contains. 4. Preparation according to claim 1, characterized in that that the average molecular weight of the olefin feed for component (A) is about 182 to 238 and the weight average molecular weight of the olefin feed for component (B) is about 224-308. 5. A method for gluing paper, characterized in that that intimately in the wet pulp prior to the final conversion of the pulp to a dry web an alkenyl succinic anhydride sizing agent is dispensed from (A) the reaction product of maleic anhydride and straight chain α-olefins in the C. -. C ₁ -, - range and (B) the reaction product of maleic anhydride and straight or branched chain internal olefins Olefins in the C. -C 4 range, where the component (B) has a molecular weight which is at least 10 units higher than that of component (A). 6. The method according to claim 5, characterized in that the sizing agent used is about 5 to about Contains 40% of component (A). 7. The method according to claim 6, characterized in that the sizing agent used contains from about 10 to about 35% of component (A). 8. The method of claim 5 characterized in that the average molecular weight of the olefin feed for component (A) about 182 to 238 and the average molecular weight of the olefin feed for component (B) is about 224-308. 9. The method according to claim 5, characterized in that the sizing agent used in the form of an aqueous Emulsion is present. 10. Process for the treatment of cellulosic goods, to make these water-repellent, characterized in that the goods are made with an alkenyl succinic anhydride preparation treated that out (A) the reaction product of maleic anhydride and straight chain α-olefins in the C ₁₃ -C »range and (B) the reaction product of maleic anhydride and straight-chain internal olefins or branched-chain olefins in the C ₁ .- (! "" Range, wherein the component has a molecular weight which is at least 10 units higher than that of the Component (A), and the impregnated fabric is thermoset at temperatures lower than that Temperatures at which the cellulose-containing goods discolour. 11. The method according to claim 10, characterized in that the preparation is about 5 to about 40% of the component (A) contains. 12. The method according to claim 11, characterized in that the preparation is about 10 to about 35% of the component (A) contains. -4- 13. The method according to claim 10, characterized in that that is the average molecular weight of the olefin feed for component (A) about 182 to 238 and the average molecular weight of the olefin feed for component (B) approximately 224 to 308. 14. A process for the preparation of alkeny / succinic anhydride from maleic anhydride and a mixture of straight-chain α-olefins in the C ₁ -, C ^ range, characterized in that Ά) introduced the α-olefins into a distillation zone in which at least part of the lowest boiling α-olefin evaporates and overhead is deducted, (B) the remaining bottoms fraction from the distillation zone to reduce the α-olefin content to less than 15% of the total olefin content the soil fraction is isomerized, (C) the α-olefin fraction withdrawn at the top from stage (A) with the isomerized olefin bottoms fraction of stage (B) is combined again and (D) the combined olefins from stage (C) with Maleic anhydride for the recovery of the alkenyl succinic anhydride product implemented. 15. The method according to claim 14, characterized in that that the α-olefin content in stage (B) to less than 10% of the total olefin content of the bottom fraction is reduced. 16. The method according to claim 15 ,. characterized, that the ct-olefin content in stage (B) to less than 5% of the total olefin content of the soil fraction is reduced. -ΞΙ 17. The method according to claim 14, characterized in that that the amount of olefin withdrawn overhead in step (A) is about 5 to 40% of the total used olefins. 18. The method according to claim 17, characterized in that the amount of olefin which is withdrawn overhead in step (A) makes up about 10 to 35% of the total olefins used.
'' 19. The method according to claim 14, characterized in that that the average molecular weight of the olefins withdrawn overhead in step (A) is approximately 182 to 238 and the average molecular weight of the bottom fraction olefins in the step (B) approximately 224 to 308. 20. A process for the preparation of alkenysuccinic anhydride from maleic anhydride and a mixture ^of straight-chain α-olefins in the C ₁ -C - "range, characterized in that (A) Introducing the α-olefins into a distillation zone are, in which at least part of the lowest boiling α-olefin evaporated and overhead is deducted, (B) the remaining bottom fraction from the distillation zone to reduce the α-olefin content to less than 15% of the total olefin content of the . Bottom fraction is reduced, - (C) independently the non-isomerized α-olefin overhead fraction, recovered in step (A) and the isomerized olefin bottoms fraction of stage (B) are reacted with maleic anhydride and gg (D) the reaction products of step (C) for recovery of the alkenyl succinic anhydride product are combined will. -6- 21. The method according to claim 20, characterized in that the α-olefin content in step (B) to less than 10% of the total olefin soil fraction content will. 22. The method according to claim 21, characterized in that that the α-olefin content in step (B) to less than 5% of the total olefin soil fraction content is reduced. 23. The method according to claim 20, characterized in that the amount of olefin in the step (A) about Head withdrawn is approximately 5 to 40 percent of the total olefin used. 24. The method according to claim 23, characterized in that that the amount of olefin withdrawn overhead in step (A) is about 10 to 35% of the total used olefins. 25. The method according to claim 20, characterized in that the average molecular weight of the in overhead olefin withdrawn from step (A) is about • 182 to 238 and the average molecular weight of the olefin in the bottoms fraction in step (B) is about 224-308.