DE2724491A1 - PROCESS FOR PRODUCING LINEAR DIMERS OF ALPHA-ALKYLSTYRENE - Google Patents

Description

PATENT LAWYERS 8 MUNICH 86. POST BOX 8602 45 272 A 49 1

Attorney's file 28 092 3 -jp; ß | -5

Monsanto Company

St. Louis, Missouri / USA

Process for the preparation of linear dimers of alpha-alkylstyrene

The invention relates to a process for the preparation of linear dimers of alpha-alkylstyrenes. In particular The invention relates to a process for the preparation of linear dimers of alpha-alkylstyrenes from a purified, monomeric starting material. The invention relates to reaction moderating compounds which catalyze the clay Dimerization of Purified Alpha-Alkylstyrene to the effect that the amount of linear dimer produced based on the cyclic Dimer is increased.

Polymers of alpha-alkylstyrenes are compounds that

V / wi.

43-21-43O5A GW 7 ₀ 9 8 5 0/1 0 0 1

• ((Wl 4fl S2 72 S Munich W, MaucriurthriMraUe 45 banks: Bayerische Vereinebank Munich 4SJ100

«S7043 telegrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 3 (90002624

913310 TELEX: 0524SW BERG d Postscheck Munich 65343-80S

* 272U91

find use for a wide variety of purposes. Perhaps the most widely used polymers of alpha-alkylstyrenes are their diners. As is well known, the Alpha-alkylstyrenes as hydraulic fluids, heat transfer fluids, lubricants and oils Plasticizer use.

Recently, however, it has been discovered that the dimers of alpha-alkyl styrenes, in particular those of alpha-methyl styrene, can be used as starting materials which excellent traction fluids can be produced. Traction fluids are fluids with high traction coefficients used as fluid media in traction gears or devices can. Although traction fluid technology is in a relatively early stage of development, a fundamental discussion can be found in the U.S. U.S. Patent 3,411,369 can be found. The patent contains a Discussion of the function of traction fluids in traction devices, as well as the concept of the traction coefficient.

The dimers of alpha-alkylstyrene, especially those of Alpha-methylstyrene can be hydrogenated directly into Transferred fluids with a high traction coefficient will. The hydrogenation of these dimers in order to improve their traction coefficient can be carried out with known hydration

70985071001

272U91

tion techniques can be achieved. If they are essentially are fully hydrated (e.g. less than 2% unsaturation) these compounds make excellent traction fluids.

The dimers of alpha-alkylstyrene can assume a wide variety of isomeric forms. For example take the Alpha-methylstyrene dimers are known to have the following Forms to:

(1) CH.

C-CH-

t *

CH,

t J

C-CH,

ι "5

2,4-diphenyl-4-methyl-1 penten (a linear dimer)

2,4-Dipheny1-4-methy1-2-pentene (a linear Dimers)

1,1,3-trimethyl-3-phenylindane (a cyclic Dimers)

50/1001

* 272U91

While it is generally known that the cyclic Dimer (3) is a solid at room temperature and the linear dimers (1) and (2) are liquids at room temperature, further differences between the linear and cyclic forms have not been the subject of previous studies.

However, there is an essential difference between the cyclic and linear dimers in terms of the possibility of using the resulting traction fluids. Accordingly, it has recently been found that although the hydrogenated linear and cyclic dimers are similar Traction coefficients (e.g. 0.0094 for the hydrogenated linear dimer of alpha-methylstyrene and 0.090 for a hydrogenated cyclic dimer of alpha-methylstyrene) have that the hydrogenated linear dimers have more suitable viscosity properties than the hydrogenated cyclic ones Dimers. For example, the viscosity of a hydrogenated linear dimer of alpha-methylstyrene is about 30,000 centlstokes at -20 ° F (-29 ° C), while the viscosity of a hydrogenated cyclic dimer of alpha-methylstyrenes at the same temperature is about 2OO,000 centistokes amounts to. This difference is very important because, in most contemplated traction device applications, the viscosity of the traction fluid should be below 50,000 centlstokes.

70985071001

The discovery of the possibility of using the Diraere des Alpha-alkylstyrene as a feedstock for traction fluids has significantly increased the need for an economical process for their manufacture. A process which produces predominantly linear dimers with a minimum of cyclic dimers is particularly desirable.

The process known today for the production of dimers Alpha-alkylstyrene monomers break down into three main categories:

(1) Non-catalytic process, (2) Acid-catalyzed Processes and (3) clay catalyzed processes.

From the U.S. Patent 2,595,581 is a for the non-catalytic method, exemplary process for the preparation of the dimeric alpha-alkylstyrene known. According to this process, the dimers of alpha methyl styrene by heating the alpha-methylstyrene monomers associated with at least 10% by weight of inert material are diluted, to about 350 ° C. and under sufficient pressure to keep the monomer liquid. The product obtained is a Mixture of dimers and trimers, with an excess weight of prostitutes.

Exemplary procedures for the acid catalyzed processes are described in U.S. Pat. Patents 2,429,719 and

709850/1001

2,646,450.

From the U.S. A process is known in US Pat. No. 2,429,719 in which an alpha-alkyl styrene monomer with 30 to 60 % sulfuric acid is brought into intimate contact at temperatures from 170 ° F (76.7 ° C) to 200 ° F (93.3 ° C). the Reaction takes a few hours (2-8) to complete and requires 0.5 to 5 volumes of acid per volume of monomer. After the completion of the reaction, the product becomes separated from the acid, neutralized and / or washed with water. While using this procedure predominantly one linear dimeric product with a minimum concentration of cyclic dimers can be made by it the presence of sulfuric acid is somewhat difficult. Special acid-proof equipment is required plus the need to keep the end product completely acid-free.

From the patent specification 2,646,450 a process is known in which an alpha-alkylstyrene monomer intimately with a Catalyst is brought into contact, which consists of 8O to 90% by weight of phosphoryl halides and 2 to 20% by weight of a strong Mineral acid. Typical phosphoryl halides used are phosphoryl chloride and phosphoryl bromide; typical strong mineral acids used are hydrochloric acid, hydrobromic acid and sulfuric acid. The reaction is

709850/1001

272U91

finishes comfortably in about 0.5 to 6 hours. After the Reaction, the catalyst is removed or neutralized by the reaction mixture with water or an aqueous, alkaline solution. is washed. Because of the acidic nature of the catalyst used in this process many of the same complications and the equipment needed in the acid catalyzed process used.

Clarification on clay-catalyzed processes is given by U.S. Patents 2,433,372; 2 450 027 and 3 161 692.

US Pat. No. 2,433,372 describes a process in which alpha-methylparastyrene monomer is heated to at least 150 ° C. and then brought into contact with 2 to 10% by weight of an activated clay catalyst such as Fuller's earth. A violent exothermic reaction results and the temperature must be controlled by cooling. The temperature is maintained between 200 and 250 ° C until the refractive index (n _ß ) 1.5600 is reached, at which point the reaction is complete. The hot reaction mixture is then filtered to remove the catalyst and the residue is allowed to cool and crystallize. Since this patent describes the product as a solid dimer in contrast to a liquid dimer, this product consists largely, if not entirely, of cyclic

70985071001

272U91

Dimers.

The U.S. U.S. Patent 2,450,027 describes a process similar to that previously mentioned, except for In this process the reaction temperature is below 200 ° C is held, raw starting material (as shown by the examples) is used and the end product is a liquid (i.e. mostly linear dimer).

The U.S. Patent specification 3,161,692 describes a method with the l, l, 3-trimethyl-3-phenylindane (a cyclic dimer) is made by taking alpha methyl styrene monomer with an acid activated montmorillonite-type clay. For this procedure a relative Pure monomeric starting material (i.e. 90-99%) is preferred, although more unpurified starting materials are also used can be.

The clay catalyzed processes for the production of dimer alpha-alkylstyrene (including the dimers of substituted alpha-alkylstyrene) have many beneficial properties. These processes do not require any special equipment as neither high pressure nor strong acids are used. The separation of the product is easy because, after the reaction has ended, the product and the catalyst are separated from one another by filtration.

70985071001

It has been found, however, that when using relatively pure starting materials in the known Clay-catalyzed processes of U.S. Patent specification 3 161 692 a product with a high proportion of cyclic! Dining arises. Those clay-catalyzed processes that are used to Preparation of a predominantly linear, dimeric product as used in U.S. Patent 2,450,027 are based on raw raw materials. Although products with a high content of cyclic! Dimers through a clay-catalyzed process with crude or relative Pure, monomeric starting materials, can be prepared in the well-known clay-catalyzed processes only crude, monomeric starting materials are used to produce predominantly linear dimers.

Since raw starting materials have a lower concentration of real monomers than relatively pure or purified starting materials, their use results in a lower overall capacity than that which is possible would be if starting materials with high real monomer content were used. That is, a clay catalyzed Process for making products from predominantly linear dimers that are "pure" or "purified" monomeric starting material used, an essential would have greater capacity than the known methods.

70985071001

There is therefore a need for a new process for the preparation of linear dimers of the alpha-alkylstyrenes. Such a new process should have the simplicity of the known clay-catalyzed processes, but the simplicity Have the ability to produce a linear, dimeric product with low concentration from purified monomeric starting materials on cyclic dimer.

Surprisingly and unexpectedly, a new process was found for the production of linear dimers of alpha-alkylstyrenes found. This new process maintains the simplicity of the known processes, uses purified monomers Starting materials and produces products with low concentration of cyclic dimers.

The invention relates to a new clay-catalyzed process for the production of dimers of alpha-alkylstyrenes. It also relates to a new clay catalyzed process for the production of linear, dimeric alpha-alkylstyrenes. Further The invention relates to a new clay-catalyzed process for the production of linear, dimeric alpha-alkyltyrenes from purified alpha-alkylstyrene starting materials.

These and other objects are achieved by a process which comprises contacting an alpha-alkyl-isocyanate monomeric starting material with a clay catalyst in the presence

709850/1001

a reaction moderating compound. That Starting material in this process according to the invention can be raw or purified, although the inventive advantages over known methods are also great appear clearly when a purified or pure starting material is used.

The invention is based on the surprising discovery that the presence of certain compounds in the reaction mixture during the clay-catalyzed dimerization of a purified alpha-alkylstyrene monomer feedstock affects the reaction to increase the ratio of the linear dimer produced. The compounds that achieve this effect, hereinafter referred to as "reaction moderating compounds", are usually aldehydes, ketones, alcohols or hydroxyesters.

These reaction moderating compounds usually have 1 to 10 carbon atoms and are usually effective at a concentration of 0.1 to 10% by weight of the reaction moderating compound, based on the weight of the monomeric starting material.

The invention relates to a process for making predominantly linear dimeric alpha-alkylstyrene products from purified monomeric alpha-alkylstyrene starting materials

70985071001

'"OWGINAL IN6FECTE0

by contacting the monomers with a clay catalyst at a temperature of about 50 ° C to 150 ° C in Presence of 0.1 to 10% by weight of a reaction moderating agent Compound based on the weight of the starting monomeric material. A preferred temperature range for This process is carried out from 70 ° C to 130 ° C, and a more preferred temperature range from 90 ° C to 110 ° C.

In a preferred embodiment of the invention, the reaction moderating compounds from the Group selected from aldehydes, ketones, hydroxyesters and alcohols. Such reaction moderating compounds are preferred having 1 to 10 carbon atoms; more preferably those having 2 to 8 carbon atoms, and most preferably are those with 3 to 6 carbon atoms.

In a particularly preferred embodiment of the invention Alpha-alkylstyrene is alpha-methylstyrene.

The clay catalysts used in the process of the invention are known. For example, those from the USPatentschriften 2,433,372; 2,450,027 and 3 161 692. Preferred are montmorillonite, bentonite and attapulgite clays. More preferred are montmorillonite and attapulgite clays. Activated montmorillonite clays are particularly preferred.

7098507100T

Most preferred are sulfur sauce treated montmorillonite clays such as those available from Chemetron Corporation be sold under the trade name KSF / 0.

This invention has a significant technical advantage over the known clay-catalyzed dimerization processes, as it involves the production of predominantly linear, dimeric products from purified monomeric starting materials allows, while the known processes usually from such starting materials products with high Generate concentration of cyclic dimers.

In order to obtain predominantly linear alpha-alkylstyrene dimeric products by the known clay-catalyzed processes, it is usually necessary to use crude starting material. Since raw starting material contains only about 70-80% real alpha-alkylstyrene monomer compared to 95-100% real alpha-alkylstyrene monomer in purified starting material, the process of the present invention yields about 1/3 more dimeric product than known processes with it Amount of raw material. The use of more concentrated starting material in the process of the invention results in a higher "payload" than in the known clay-catalyzed dimerization processes.

As used herein, the term "predominantly"

70985071001

st g

U 4 9

denotes 80% or more. Accordingly, in a dined product that is "predominantly linear" there is or 80% more of the total dimers present than linear dimers before.

As used herein, the term "raw" refers to crude raw material. Thus, for example, a typical "crude" alpha-methylstyrene feedstock will contain only about 70% by weight monomeric alpha methyl styrene as shown below will.

Typically crude alpha methyl styrene Components wt .-%

Acetone O, l%

Benzene 0.2%

Toluene 0.3%

Mesityl oxide 2.5%

Cumene 20.0%

Butylbenzenes 2.0% Alpha-methylstyrene 70.0% Dimethylbenzyl alcohol 0.1% Acetophenone 1.5% Unknown 3.3% The term "purified" as used herein denotes

70985071001

(a) a starting material in a relatively pure state, i.e. not containing any significant amount of components other than the main component, (b) a starting material which was enriched by the partial or complete removal of the secondary components, or (c) either (a) or (b) which has been intentionally diluted. In order to clarify the term "cleaned" as used here, the following examples are given.

(a) Alpha-methylstyrene, which is essentially pure, when generated in a river and containing 95-100% by weight alpha-methylstyrene is encompassed by the term "purified".

(b) Crude alpha-methylstyrene, such as the composition tabulated above, is converted into "purified" alpha-methylstyrene by virtue of the fact that practically all of the minor components it contains except for alpha-methylstyrene removed.

(c) The "purified" alpha methyl styrene as in (a) or (b) defined, is still "purified" despite being intentionally diluted to a lower concentration.

Some raw starting materials contain one or more reaction moderating compounds of the invention.

90985071001

272U91

The use of such raw raw materials in the known processes, however, cannot achieve the salient results of this process according to the invention bring about.

For example, a typical clay catalyzed dimerization process yields about 80 pounds (36.3 kg) of dimer per every 100 pounds of (45.5 kg) actual monomer added. A process in which a raw starting material containing 70% by weight of real monomers is used, therefore only yields about 56% (80% of 70%) of the total input as a dimeric product. However, the method according to the invention, which uses a purified starting material (approx 95% actual monomer) and about 5% by weight of a reaction moderating compound would include about 72% of the total input (starting material plus reaction moderating compound) result as a dimeric end product. Therefore, with the same input, the method according to the invention yields about 1/3 more product than the known methods. The resulting enormous economic benefits are evident.

Already mentioned here, the reaction moderating compounds according to the invention are usually aldehydes, ketones, Hydroxy esters or alcohols. Typical aldehydes known as reaction moderating compounds in the practice of this

J098B071001

Invention can be used, include without limitation butyraldehyde, acetaldehyde, formaldehyde, propionaldehyde, Paraldehyde, paraformaldehyde, isobutyraldehyde, valeraldehyde, 2-methylpentaldehyde, 2-ethylbutyraldehyde, acrolein, Methacrolein, crotonaldehyde, and dimeric acrolein (2-formyl-3,4-dihydro-2H-pyran). Butyraldehyde is preferred, Propionaldehyde, isobutyraldehyde and crotonaldehyde; butyraldehyde is most preferred.

Typical ketones which are used as reaction-reducing agents according to the invention Compounds that can be used include, without limitation, mesityl oxide, cyclohexanone, acetone, pentanone-2, Methyl isoamyl ketone, methyl isobutyl ketone, methyl ethyl ketone, n-amyl methyl ketone, ethyl butyl ketone, diisobutyl ketone, Isobutylheptyl ketone, isophorone, pentan-2,4-one, and diacetone alcohol. Preference is given to mesity oxide, cyclohexanone, Acetone and isophorone; most preferred are mesityl oxide and cyclohexanone.

The hydroxy esters which can be used as reaction moderating compounds according to the invention include, without limitation, ethyl glycolate, 2-hydroxyethyl acetate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl glycolate, butyl lactate, dimethyl maleate, diethyl maleate, ethyl 3-hydroxybutyrate, and methyl 3-hydroxybutyrate a. Ethyl glycolate, methyl glycolate, di-

70985071001

methyl maleate and methyl lactate; is most preferred Methyl glycolate.

Typical alcohols that can be used as reaction-moderating compounds according to the invention include butanol, methanol, ethanol, propanol, Pentanol, 3-methyl-l-butanol, hexanol, 2-methylpentanol, 4-methyl-2-pentanol, 2-ethylbutanol, 2-ethylhexanol, heptanol, octanol, nonanol and their isomers. Preferred are butanol, ethanol and propanol; butanol is most preferred.

The reaction moderating compounds according to the invention can be used either alone or in any combination.

Example 1:

A mixture of 500 g alpha-methyl styrene (99% pure), 25 g mesityl oxide and 5 g clay catalyst (Chemetron KSF / 0) were stirred and heated. An exothermic reaction began at about 70 ° C. and heating was interrupted. Man allowed the temperature to rise to 100 ° C and maintained there by mild cooling. After about 15 minutes, the development of heat and slight heating decreased

70985071001

272U91

the temperature was kept at about 90-100 ° C. At intervals, samples of the reaction mixture were taken using analyzed by gas / liquid chromatography; after For three hours, the composition of the reaction mixture changed only slowly. The catalyst was filtered off. The reaction mixture was distilled and yielded 50 g of first runnings (from mesityl oxide and some unreacted alpha-methyl styrene), and 417 g of dimeric alpha-methyl styrene, with a temperature of 171-175 ° C. at 10 mm pressure. Gas / liquid chromatography analysis showed that 98% of the dimeric product was linear and 2% cyclic. The distillation residue contained higher AMS oligomers (trimers and tetramers).

Example 2;

31 pounds (14.1 kg} alpha methyl styrene (95 + wt% pure) and 1.25 pounds (0.57 kg) of mesityl oxide are poured into a stirrable Reaction vessel introduced. Then 0.31 pounds (0.14 kg) of clay catalyst was added. The reaction mixture is heated. Heating is interrupted between 70 and 80 ° C. The exothermic reaction increases the temperature even further. It was cooled from the outside in order to keep the reaction temperature at 100.degree. After the reaction temperature stabilizes at 100 ° C it becomes 94 pounds

70985071001

(42.6 kg) alpha-methylstyrene was added over a period of 45-60 minutes. The reaction temperature is maintained at about 100 ° C. for 2 to 8 hours , at which time the reaction is complete and the reaction mixture is filtered to remove the catalyst from the reaction mixture. The reaction product is distilled to give 10 pounds (4.5 kg) foreshots, 100 pounds (45.4 kg) of linear, dimeric alpha-methylstyrene, and 16 pounds (7.3 kg) of still bottoms. The dimeric product contains about 95-98% by weight linear dimer and 2-5% by weight cyclic dimer.

Example 3:

A mixture of 200 g alpha-methylstyrene (99% pure), 10 g butanol and 0.5 g tinting catalyst (Chemetron KSF / 0) were heated and stirred as in Example 1. After the distillation, 155 g of dimeric alpha-methylstyrene with a ratio of linear to cyclic dimers of 96 : 4 were obtained.

Example 4: A mixture of 2OO g alpha methyl styrene (99% pure),

2 g butyraldehyde and 0.5 g clay catalyst (Chemetron KSF / 0)

70985071001

25-272U9-!

were heated and stirred as in Example 1. After one hour at 100 ° C, GLC analysis indicated that the reaction mixture consisted of linear and cyclic dimer in a ratio of 90:10.

Example 5;

A mixture of 200 g alpha methyl styrene (95 +% pure), 5 g of methyl glycolate and 1 g of clay catalyst are heated to 90-100 ° C. as in Example 1. After filtering and Distillation gives an 80% yield of dimeric alpha-methylstyrene with a ratio of linear to cyclic dimer of 95: 5.

Example 6;

(No reaction moderating compound was used). A mixture of 200 g alpha methyl styrene (99% pure) and 0.2 g clay catalyst (Chemetron KSF / 0) were heated and touched. An exothermic reaction set in between 40 and 50 ° C. and heating was discontinued. Through a Ice and water cooling bath became the reaction temperature held at about 90 ° C. After one hour the mixture was filtered. GLC analysis indicated that the mixture of II

70985071001

nearem and cyclic alpha methyl styrene dimers in proportion of 6 6:34 consisted.

Although the concept of this invention with respect to the dimerization of alpha-alkylstyrene in general and the Alpha-methylstyrene has been specifically described, the scope of the invention extends widely beyond these major applications. For example, the inventive concept is based on dimerization or polymerization various substituted forms of alpha-alkylstyrene and even applicable to styrene itself.

Accordingly, a further area of application of this invention is a process for the production of a predominantly linear, dimeric product by contacting a purified starting material of a monomer or mixture thereof which through the structure

CCH ₂ ) _n H C = CH ₀

is defined in which m, η and ρ are independently an integer from 0 to 3, with a clay catalyst

70985071001

in the presence of a reaction-moderating compound according to the invention. In a preferred embodiment is η · 1 and ρ + m = 3. In a further preferred embodiment, η = 1, P = I and m = 0. In another preferred embodiment, the compound represented by the structure is alpha-methylparamethylstyrene. In In a most preferred embodiment, the compound represented by the structure is alpha methyl styrene.

Another feature of the invention, which represents a significant economic advantage, is that the reaction moderating compound can be recovered and reused in the method according to the invention can. Accordingly, the net amount of the reaction moderating compound actually used or consumed by the process according to the invention is limited to the amount which is caused by losses.

The advantages according to the invention are further illustrated by the results in Table I, which were obtained in laboratory experiments with the method according to the invention.

f09850M001

DIMERIZATION OF PURIFIED Ot-METHYLSTYROL

CD O »Ol

Response moderator
Compound weight% 5 Amount of
Tonkata
lysators 5 o, 5i React
functional
temp. Reak
ions
Time Cyclical:
linear
Dimers in Yield of residue (g)
linear Di- per 100 g Ii-
mers (mol.%) near dimer 7th K XX 7th N 7th Il 7th N Il test
No. 5 (Wt.%) 5 1, O ^{1 0} C (H) product X H n «Ν / 82.5 N ¹⁷ Ί ^ O Acetophenone 5 0, S ¹ 1 0.2S ¹ 90-135 0.13 26:74 M. N / υ 87 Il £ 10.9 1 Cyclohexanone 5 o, ₅ i 5 0, I ¹ 90 0.9 4.7: 95.3 η M. / »82 N CO
18.8 ~ * 2 Cyclohexanone 5 O, 25 ^X 100 1.1 6.0: 94.0 76.1 79.0 85.0 25.8 16.0 3 Cyclohexanone 5 0.25 ³ V 80 2.3 3.0: 97.0 74.7 77.8 25.6 4th Cyclohexanone 5 0.2S ¹ 80 1.7 2.6: 97.4 77.9 λ, 81 20.4 5 Cyclohexanone 10 0.2S ¹ 80 1.75 3.2: 96.8 _ 7 7th 6th Cyclohexanone - 0.2S ¹ 80 1.7 2.8: 97.2 Il 7th Cyclohexanone 0.2O ¹ 80 3.2 3.1: 96.9 80.2 8th no 0.1 ^X 90 1.3 33.9: 66.1 83.5 9 linear, dimeric forerunner
from the dimerization of.
«-Methylstyrene 10 0.5 ^χ 95 1.0 10.2: 89.8 78.5 10 acetone 100 0.9 5.4: 94.6 80.6 11 Mesity oxide 100 4.0 1.4: 98.6 12th Mesity oxide 90 3.3 1.4: 98.6 13th Cyclohexanone 100 2.1 4.6: 95.4 14th

Oo

O (O QO Vt

15th Cyclohexanone 16 Methyl iso-
amylketone 17th Methyl iso-
amylketone 18th Cyclohexanone 19th Cyclohexanone
Rek. From 18 20th Cyclohexanone
Rek. From 19 21 Cyclohexanone 22nd Butyl acetate 23 Butyl alcohol 24 Butyl alcohol 25th Butyl alcohol 26th Butyl alcohol 27 no 28 water 29 no 30th no 31 no 32 Mesity oxide

O, 1 ^y

Ο, 25

O, 1 ^J 0, l ^]

0.2S

90 90

80 100

100

3.2 3.5: 96.5

74.0 80.8 22.4

1.2 9.7: 90.3 78.5 80.8 21.2

2.0 6.2: 93.8 70.7 74.1 33.5

4.5 1.9: 98.1 78.0 86.4 13.0

4.0 1.5: 98.5

79.1 87.9 10.4

5 0.25 * 100 4.0 1.5: 98.5 80.6 • I 81.7 Il 7th M. 9.9 H 7th M. 5 O, 25 ^X 100 1.9 3.9: 96.1 83.7 Il 12.7 Il 5 Ο, 25 ^Χ 15Ο + ⁸ 7th 1 O, 25 ^X 100 0.5 19.8: 80.2 7th H 81.5 _ 7 Il 5 0.2S ¹ 100 2.7 3.6: 96.4 77.4 7th 13.4 1 0, I ¹ 100 0.6 9.7: 90.3 7th "7 7th 2.5 0, I ¹ 100 2.6 4.9: 95.1 M. O, 25 ² 100 0.5 66:33 0.5 Ο, 25 ^Χ 4210 ⁸ O, 17 ³ 100 0.6 95: 5 ο, ι ⁴ 4155 ⁸ O.5 ⁵ 100 0.7 50:50 2.0 10 ⁵ 100 9.8 4.2: 95.8

ty

33 no 5 O, 25 ⁶ 100 0.7 66:33 _ 7 _ 7 7th _ 7 34 acetone 5 0.25 * 100 0.7 4.8: 96.2 Il H H 35 acetone 5 0.25 ^X 100 0.6 6.3: 93.7 Il H Il 36 »Richlorethylene 1 0.2S ¹ 100 0.9 22:78 Il Il Il 37 Trichlorethylene 5 0, I ¹ 90 0.5 50:50 Il Il H 38 Methyl isobutyl
ketone 5 0, I ¹ 80 1.1 9:91 H H Il 39 Pentanone-2 1 0, I ¹ 80 0.7 5:95 N N H 40 Mesity oxide 1 0.5 * 100 1.1 7:93 79.1 81.4 17.4 "1 Mesity oxide 1 0.4 * 100 1.1 6:94 80.7 82.3 17.5 42 Mesity oxide 1 0.2S ¹ 100 3.1 4:96 79.0 82.1 17.5 43 Mesity oxide 1 Ο, 25 ^Χ 100 2.2 4:96 83.4 (v86 12.8 44 Mesity oxide 1 0.2S ¹ 100 2.2 4:96 84.7 r \, 87 12.2 45 Mesity oxide 0.2S ¹ 100 3.3 2.6: 97.4 _ 7 _ 7

An activated montmorillonite catalyst available under the trade name Chemetron KSF / O is distributed

An activated montmorillonite catalyst available under the trade name Chemetron KSF is distributed

An activated montmorillonite catalyst available under the trade name Chemetron KlO is distributed

40t An activated montmorillonite catalyst available under the trade name Chemetron KlOSF is distributed

^. Florex, an attapulgite clay, available from the Floridin Company <-

^ 6 A

• Λ bentonite

- » ⁷ not distilled

Temperature control not possible ^x not corrected ^xx corrected for unreacted, monomeric (X-methylstyrene ¹ ^

Claims (16)

Patent claims; Process for preparing predominantly linear, alpha-alkylstyrene dimeric products from purified alpha-alkylstyrene monomeric starting materials by contacting the monomers with a clay catalyst a temperature of about 50 ° C. to 150 ° C. in the presence of 0.1 to 10% by weight of a reaction-moderating compound, based on the weight of the monomeric starting material. 2. The method according to claim 1, characterized in that the clay catalyst is montmorillonite or an attapulgite. 3. The method according to claim 1, characterized in that the reaction moderating Compound from the group: aldehydes, ketones, hydroxyesters and alcohols is selected. 4. The method according to claim 3, characterized in that the reaction moderating Compound contains 1 to 10 carbon atoms. 70985071001 _onlel NAL 5. The method according to claim 4, characterized in that the reaction moderation ends Compound contains 3 to 6 carbon atoms. 6. The method according to claim 1, characterized in that the reaction moderating Compound from the group: butyraldehyde, propionaldehyde, isobutyraldehyde, crotonaldehyde, mesityl oxide, cyclohexanone, acetone, isophorone, ethyl glycolate, methyl glycolate, Dimethyl maleate, methyl lactate, butanol, ethanol and propanol is selected. 7. A process for the preparation of a predominantly linear, dimeric product, characterized thereby net that a purified starting material of monomers or a mixture thereof of the formula (CH ₂ ) _n H. (CH ₂ ) _m H. in which n, m and p, independently of one another, are integers from 0 to 3, with a clay catalyst in the presence a reaction moderating connection is contacted. 8. The method according to claim 7, characterized in that - 709850/1001 - ys - characterizes that the moderator of the reaction Compound from the group of aldehydes, ketones, hydroxyesters and alcohols is selected. 9. The method according to claim 8, characterized in that the reaction moderating compound Contains 1 to 10 carbon atoms. 10. The method according to claim 9, characterized in that the reaction moderating compound Contains 3 to 6 carbon atoms. 11. The method according to claim 7, characterized in that the reaction moderating compound from the group: butyraldehyde, propionaldehyde, isobutyraldehyde, Crotonaldehyde, mesityl oxide, cyclohexanone, acetone, isophorone, ethyl glycolate, methyl glycolate, dimethyl meleate, Methyl lactate, butanol, ethanol and propanol is selected. 12. A process for the preparation of a predominantly linear, dimeric alpha-methylstyrene product from a purified, monomeric alpha-methylstyrene starting material, thereby characterized in that the monomers with a clay catalyst at about 50 ° C to 150 ° C 7098507100t in the presence of 0.1 to 10% by weight of a reaction-moderating compound. 13. The method according to claim 12, characterized in that the reaction moderating Compound from the group: aldehydes, ketones, hydroxyesters and alcohols is selected. 14. The method according to claim 13, characterized in that the reaction moderating compound contains 1 to 10 carbon atoms. 15. The method according to claim 14, characterized in that the reaction moderating Compound contains 3 to 6 carbon atoms. 16. The method according to claim 12, characterized in that the reaction moderating Compound from the group: butyraldehyde, propionaldehyde, isobutyraldehyde, crotonaldehyde, mesityl oxide, cyclohexanone, acetone, isophorone, ethyl glycolate, methyl glycolate, Dimethyl maleate, methyl lactate, butanol, ethanol and propanol is selected. 7098507100t