DE1042232B - Process for making light colored resins from steam cracked petroleum benzine - Google Patents

Description

The present invention relates to the manufacture of resins from steam cracked petroleum streams and in particular a process for improving the color of these resins.

It is known that resins can be made by Friedel-Crafts polymerization of steam-cracked petroleum streams. The resins produced in this way are usually dark yellow to red in color. It has also already been proposed to use fractions boiling below 85 ° C. as starting materials for this polymerization in order to remove the heavier diolefins and the most difficult to convert C ₇ olefins before the polymerization. These compounds add greatly to the color of the resins, and if they are removed from the batch beforehand, the products will be considerably lighter. However, proceeding from such a charging means that a considerable part of the feed that would normally be used for resin formation is lost, since the starting materials are obtainable by refining boiling up to about 15O ^1-175 ° C.

It has now been found that starting materials with a much wider boiling range can be used and Can produce lighter resins if you take raw materials that are as dry as possible and the concentration on the catalyst during the polymerization keeps it low.

It is usually very difficult to keep hydrocarbon feed streams completely dry in a refinery. In many cases, they are stored above water, and even when they are not, they easily absorb moisture from the atmosphere. For most uses, the presence of a small amount of water in these hydrocarbon streams does not interfere; therefore no effort is made to avoid their contact with water. However, it has been found that a reduction in the water content to 130 parts to 1 million parts of hydrocarbons or less, combined with a reduction in the catalyst concentration to below 0.5%, calculated on the charge, has a very beneficial effect on the color of the resins formed affects.
. Thus, the present invention is important as a valuable process for making light colored unsaturated resins from the highly unsaturated steam cracking petroleum fractions. However, the cyclic diolefins, such as cyclopentadiene and methylcyclopentadiene, are preferably removed beforehand from the steam-cracked starting fraction _{which predominantly boils below the C 9 fraction.} At least 50% of the entire isoprene-containing fraction present, which boils from the start of boiling up to 38 ° C., is also separated off. The cyclic diolefins, a process for the production of light-colored resins from steam-cracked petroleum spirits

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V. St. A.)

Representative: Dr. W. Beil and A. Hoeppener, lawyers, Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority: V. St. v. America April 17, 1956

including cyclopentadiene and methylcyclopentadiene, is removed preferably by dimerization and distillation. The isoprene fraction is either driven out completely, or the isoprene content is regulated

3 °. therein by fractional distillation and / or appropriate mixing of the streams. The resulting stream represents a fraction boiling below the boiling point of the C ₈ or Cg hydrocarbons

and is then below 70 ° C in the presence of an aluminum halide catalyst in solid form, as Polymerized in sludge or in solution. Conversion degrees of 25 to 50% are achieved.

These resins are light colored and have high softening points. They are particularly suitable as paper coatings, for printing ink mixtures, as components of rubber mixtures and, mixed with resins with a high softening point, for the production of floor slabs and tiles. According to the invention, petroleum fractions such as luminous oil, gas oil and petroleum are cracked in the presence of steam at from 550 to 800.degree. C. and streams of unsaturated petroleum fractions are obtained. The fractions which pass predominantly below the boiling range of the C ₉ fractions, but which also contain fractions up to C ₁₄ , are separated and heated to about 105 to 120 ° C. in order to dimerize the cyclopentadiene contained therein in a known manner. Then one removes a C ₈ - to C ₉ - and a lighter fraction as top product and

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separates the dimeric concentrates as a bottom product. The overhead stream practically free of cyclopendienes one fractionates and removes at least half of the isoprene-containing and below 38 ° C boiling fraction, if possible even all isoprene. The feeds so obtained predominantly boil between 38 and 150 to 175 ° C, but can also contain components that boil at 20 ° C. Analyzes of typical feeds of this type are as follows:

Composition,
Weight percent Boiling range
38 to 150 ° C | 20 to 170 ° C 68 to 30
8 to 20
5 to 1
19 to 49 Olefins
Diolefins
Paraffins
and naphthenes ...
Aromatics 51 to 62
10 to 15
3 to 4
25 to 30

According to the present invention, these starting mixtures are treated with clay or other drying agents, to their water content at least up to 130 parts per 1 million parts of the hydrocarbons to diminish. The charge thus dried is then brought to -40 to with vigorous stirring + 70 ° C, preferably at 30 to 50 ° C, with less than 0.5%, preferably with 0.2 to 0.4%, of an aluminum halide catalyst in touch.

The resulting resin is washed with water and / or alkali to remove the catalyst, and then drives off the unpolymerized ingredients. The raw resin thus obtained is then driven out the other volatile components in a vacuum or with steam to remove the liquid polymers, and wins as a residue a solid resin product with a softening point of 85 ° C or about that.

The following examples are intended to illustrate the invention, but not to limit it.

example

A number of comparative experiments were carried out ao, for which the starting material was approximately 45 Up to 150 ° C boiling mixture was used, from which practically all of the isoprene and the cyclodienes had been removed. The catalyst concentration and the water content the loading were modified and there was the effect of this action on the color of the products. The following data were found:

attempt concentration
of the Al Cls catalyst,
"/ ο, related
on the loading H2O in the
Loading, parts
to 1 million parts KWS Properties
Softening point
⁰ C η of the resins
colour
(Gardner) 1 1.18 268 93.8 8.5 2 1.25 257 93.5 8.5 3 1.23 310 97.0 8.5 4th 1.08 336 97.0 8.5 5 1.15 300 94.0 8th 6th 1.20 283 92.5 8.5 7th 1.20 303 92.0 8.5 8th 1.03 268 94.0 9 9 0.80 289 94.3 9 10 0.63 289 99.0 9 11 0.73 16 88.0 7th 12th 0.58 10 96.5 7.5 13th 0.38 52 95.0 6th 14th 1.00 48 92.0 7th 15th 0.44 126 96.5 6.5 16 0.40 22nd 99.0 6.0 17th 0.40 22nd 100.5 6.0

These data show that the catalyst concentration alone has no influence on the color of the resin (see Experiments 9 and 10), while the reduction in the water content of the charge results in a slightly lower color value with the catalyst concentration remaining the same (see Experiment 8 compared to Experiment 14 and Experiment 15 versus Experiment 16). If, however, the catalyst concentration is reduced below 0.5 and the water content below 130 parts to 1 million parts, the resulting resins are only very slightly colored (see experiment 8 versus experiments 11, 12, 13, 15 and 16). 6 _p

Claims (3)

Patent claims: 1. Method of making light-colored Resins made from steam-cracked petroleum spirit, characterized in that a steam-cracked Petroleum fraction with a boiling range of 38 to 175 ° C, which is practically entirely different from the cyclic Diolefins and as far as possible has been freed from isoprene, and no more than 130 parts Water to 1 million parts contains hydrocarbons, in the presence of at least 0.2, but less than 0.5% of aluminum halide catalysts at temperatures between -40 and + 70 ° C polymerized. 2. The method according to claim 1, characterized in that there is a steam cracked, from 38 to Hydrocarbon petroleum fraction boiling at 175 ° C isolated, heated so high that practically all cyclodienes are dimerized from the resulting Product is an overhead product of the dimerized cyclodienes remaining as bottom product separates, the head product fractionated to 5 6 from practically all constituents boiling up to 38 ° C 3. The method according to claim 2, characterized parts, including isoprene, to be separated, a drawing that the top product is fractionated, Product boiling between 38 and 150 ° C, resulting in at least 50% of the product boiling up to 38 ° C. winnt and this in the presence of an aluminum the shares, including the isoprene, Separate halide catalyst at about - 40 to + 7O ⁰ C 5, a between 20 and 170 ° C boiling polymerized. Product wins and it polymerizes. © «09 660/345 10. 55